Research Article Synthesis, Characterization, …downloads.hindawi.com/journals/bca/2013/315972.pdfResearch Article Synthesis, Characterization, Antimicrobial, DNA Cleavage, and Antioxidant

Hindawi Publishing CorporationBioinorganic Chemistry and ApplicationsVolume 2013 Article ID 315972 16 pageshttpdxdoiorg1011552013315972

Research ArticleSynthesis Characterization Antimicrobial DNA Cleavageand Antioxidant Studies of Some Metal Complexes Derived fromSchiff Base Containing Indole and Quinoline Moieties

Mahendra Raj Karekal Vivekanand Biradarand Mruthyunjayaswamy Bennikallu Hire Mathada

Department of Studies and Research in Chemistry Gulbarga University Gulbarga-585 106 Karnataka India

Correspondence should be addressed to Mruthyunjayaswamy Bennikallu Hire Mathada bhmmswamy53rediffmailcom

Received 22 April 2013 Accepted 28 July 2013

Academic Editor Claudio Pettinari

Copyright copy 2013 Mahendra Raj Karekal et al This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

A new Schiff base of 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide and 3-formyl-2-hydroxy-1H-quinoline (HL) and its Cu(II)Co(II) Ni(II) Zn(II) Cd(II) and Hg(II) complexes have been synthesized and characterized in the light of microanalytical IR 1HNMR UV-Vis FAB-mass ESR XRD and TGA spectral studies The magnetic susceptibility measurements and low conductivitydata provide evidence for monomeric and neutral nature of the complexes On the basis of spectral studies and analytical datait is evident that the Schiff base acts as tridentate ligand The Cu(II) Co(II) and Ni(II) complexes were octahedral whereasZn(II) Cd(II) and Hg(II) complexes were tetrahedral in nature The redox behavior of the Cu(II) complex was investigated byelectrochemical method using cyclic voltammetry In order to evaluate the effect of metal ions upon chelation both the ligand andits metal complexes were screened for their antibacterial and antifungal activities by minimum inhibitory concentration (MIC)method The DNA cleavage experiment performed using agarose gel electrophoresis method showed the cleavage of DNA by allthe metal complexes The free radical scavenging activity of newly synthesized compounds has been determined at a differentconcentration range by means of their interaction with the stable free radical 11-diphenyl-2-picrylhydrazyl (DPPH)

1 Introduction

Numerous indole-containing natural and synthetic productssuch as reserpine vincristine indolemycin mitomycin pin-dolol dolasetronmesylate indomethacin or sumatriptan arebeing used for the treatment of various illnesses Thereforeindole structure represents a highly relevant heterocyclic sys-tem Many pharmacodynamic compounds containing indolenucleus have been reported to possess a wide variety of bio-logical properties namely anti-inflammatory [1 2] anticon-vulsant [3] cardiovascular [4] antibacterial [5] COX-2inhibitor [6 7] and antiviral activities [8] More specificallyseveral reports describe that indole-2-carbohydrazides andrelated compounds are endowed with antihistaminic [9]antidepressant [10] and MAO inhibitory activities [11] Par-ticularly the compounds having three substituted indole

nucleus are being used as the startingmaterials for the synthe-sis of number of alkaloids agrochemicals pharmaceuticalsand perfumes [12]

Quinoline derivatives have also attracted the attention ofthe chemists because of their presence in many natural prod-ucts possessing significant biological activities [13ndash17] Small-molecule interactions with DNA continue to be intensely andwidely studied for their usefulness as probes of cellular repli-cation and transcriptional regulation and for their potentialas pharmaceuticalsTheCu(II) complexes have been reportedto be active in DNA strand scissors [18] On the other handan increasing interest in antioxidant particularly in thoseintended to prevent the mischievous effects caused by thefree radicals in the human body is an attracting one The freeradicals are also believed to be associatedwith carcinogenesismutagenesis arthritis diabetes inflammation cancer and

2 Bioinorganic Chemistry and Applications

genotoxicity due to the oxidative stress which arises as a resultof imbalance between free radical generations [19 20] Theantioxidant activity of metal complex is found to be inducedby both the identity of the metal and the ligands bound to it[21] The development of new metal-containing antioxidantagents have been reported by several research groups [22]Based on these findings and in continuation of our researchwork on coordination chemistry [23ndash28] we describe thesynthesis of a new Schiff base and its metal complexes with 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide fused to 3-formyl-2-hydroxy-1H-quinoline with the aim of obtainingmore potent pharmacological active compounds

2 Experimental

21 Analysis and Physical Measurements IR Spectra of thesynthesized Schiff base and its metal complexes wererecorded in KBr pellets on a Perkin-Elmer FT-IR instrumentin the range 4000ndash350 cmminus1 1HNMR spectra were recordedin 1198896-DMSOusing a Bruker DRX-400MHz instrument UV-

Visible spectra of the Cu(II) Co(II) and Ni(II) complexeswere recorded on Elico-SL 164 spectrometer in the range200ndash1000 nm in DMF solution (1 times 10minus3M) The FAB massspectra of ligand and its Cu(II) and Zn(II) complexes wererecorded on a JEOL SX 102DA-6000mass spectrometerdatasystem using argonxenon (6 kV 10mA) as the FAB gasThe accelerating voltage was 10 kV and the spectra wererecorded at room temperature using m-nitrobenzyl alcohol(NBA) as the matrix Elemental analysis was obtained fromHERAEUS C H and NndashO rapid analyzer and metal analysiswas carried out by following the standard methods ESRmeasurement was carried out on a BRUKER BioSpin Gmbhspectrometer working at microwave frequency of 9903GHzElectrochemistry of the Cu(II) complex was recorded on a600D seriesmodel electrochemical analyzer inDMFusing n-Bu4NndashClO

4as a supporting electrolyte The experiment was

carried out by using DPPH as reference with field set at 3200gauss Magnetic susceptibility measurements were made atroom temperature on a Gouy balance using Hg[Co(NCS)

4]

as the calibrant

22 Methods All the chemicals used were of reagent gradeand procured from Hi-media and Sigma Aldrich Solventswere dried and distilled before use Melting points of thenewly synthesized compounds were determined by elec-trothermal apparatus using open capillary tubes The metaland chloride contents were determined as per standard pro-cedures [29] The precursors 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide and 3-formyl-2-hydroxy-1H-quinolinewere prepared by the literature methods [16 30]

23 Synthesis of the Schiff Base HL Equimolar mixture of 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide (0001mol)and 3-formyl- 2-hydroxy-1H-quinoline (0001mol) with acatalytic amount of glacial acetic acid (1-2 drops) in ethanol(20mL) was refluxed on a water bath for about 7-8 h Thereaction was monitored by TLC The pale yellow solidseparated was filtered washed with little ethanol dried and

Cl

Cl

NNH

NH

NH

NH

NH

C6H5

C6H5

CONHNH2

OHC

O

O O

EtOHAcOH

CHC

+

4-5hr reflux

Scheme 1 Synthesis of Schiff base ligand HL

recrystallized from dioxane (Scheme 1) Yield 65 mp314∘C Anal Calcd for C

25H17O2N4Cl (Mr = 440) C 6810

H 385 N 1271 Found C 6825 H 391 N 1289 IR(KBr cmminus1) 3311 3229 and 3162 (]NHNH) 1674 and 1661(]C=O) 1608 (]C=N)

1H NMR (DMSO-1198896) 120575 1220 and 1200

(s 2H two CONH) 1160 (s 1H indole NH) 840 (s 1HHC=N) 710ndash820 (m 13H ArH)

24 Preparation of Cu(II) Co(II) Ni(II) Zn(II) Cd(II) andHg(II) Complexes of Schiff Base HL To the hot solutionof 5-chloro-N-(21015840-dihydro-21015840-oxoquinolin-31015840-yl methylene)-3-phenyl-1H-indole-2-carbohydrazide (HL) (0002mol) inethanol (30mL)was added a hot ethanolic solution (15mL) ofrespective metal chlorides (0002mol) The reaction mixturewas refluxed on a steam bath for about 4 h during which nosolid separated out An aqueous alcoholic solution of sodiumacetate (05 g) was added to the reaction mixture to maintaina pH of about 60ndash70 and reflux was continued for about anhour The reaction mixture was poured in the distilled waterThe separated solid complexes were collected by filtrationwashed with sufficient quantity of distilled water then withhot ethanol to apparent dryness and dried in a vacuumover anhydrous calcium chloride in a desiccator The meltingpoints of all the compounds are reported in Table 1

241 Cu(II) Complex of Schiff Base HL

Green Solid Yield 70 mp gt 340∘C Anal Calcd for[Cu(C

50H32O4N8Cl2)]H2O (Mr = 95954) C 6246 H 353

N 1166 Found C 6259 H 332 N 1174 IR (KBr cmminus1)3418 (]H

2O) 3283 and 3221 (]NHNH) 1639 (]C=O) 1548 (]C=N)

1493 1077 and 615 (]Pyridine ring) 514 (]MndashO) 442 (]MndashN) UV-Vis (cmminus1) ]

2 13769ndash17463

242 Co(II) Complex of Schiff Base HL

Light Brown Solid Yield 77 mp gt 340∘C Anal Calcd for[Co(C

50H32O4N8Cl2)]H2O (Mr = 95493) C 6276 H 355


2O) 3271 and 3230 (]NHNH) 1629 (]C=O) 1551 (]C=N)

Bioinorganic Chemistry and Applications 3

Table1Ph

ysicalanalytic

alm

agnetic

susceptib

ilityand

molar

cond

uctanced

atao

fligandHLandits

complexes

Com

poun

dsMolecular

form

ula

MolW

tMP

(∘ C)

(Yield

in)

Elem

entalanalysis

()C

alcd

(Fou

nd)

Magm

oment120583

eff(BM

)Molar

cond

(120583M)

ohmminus1 cm

2molminus1

Colou

rM

CH

NCl

HL

C 25H

17O

2N4C

l44

0314(65)

mdash6810

(6825)

385

(391)

1271(1289)

805

(812

)mdash

mdashYello

wCu

complex

[Cu(C 5

0H32O

4N8C

l 2)]H

2O9595

4gt340(70)

661

(671)

6246(6259)353

(332

)1166(1174)

739(721)

179

31Green

Cocomplex

[Co(C 5

0H32O

4N8C

l 2)]H

2O95493gt340(77)

616

(626)

6276

(6292)355

(382)

1171(1186)

742(762)

501

24Brow

nNicom

plex

[Ni(C

50H

32O

4N8C

l 2)]H

2O95469gt340(79)

614

(619

)6278(6292)355

(369)

1171(1191)

742(759)

290

27Brow

n

Zncomplex

[Zn(C 2

5H16O

2N4C

l)(C

l)]H

2O5574

0gt340(69)

1171(1162)

5372(5399)322

(335)

1002(1019)1271(1289)

mdash49

Light

yello

w

Cdcomplex

[Cd(C 2

5H16O

2N4C

l)(C

l)]H

2O60

441gt340(71)

1856(1865)

4955(497

1)297

(281)

924(935)

1172(119

0)mdash

60Pale

yello

w

Hgcomplex

[Hg(C 2

5H16O

2N4C

l)(C

l)]67459

330(68)

2969(297

5)44

40(4461)236

(242)

828

(836)

1050(1066)

mdash50

Light

Yello

wHL=ligand



1 7447 ]

2 15977 ]

3 19518

243 Ni(II) Complex of Schiff Base HL

Brown Solid Yield 79 mp gt 340∘C Anal Calcd for[Ni(C

50H32O4N8Cl2)]H2O (Mr = 95469) C 6278 H 355


2O) 3305 and 3218 (]NHNH) 1638 (]C=O) 1555 (]C=N)

1478 1063 and 621 (]Pyridine ring) 477 (]MndashO) 450 (]MndashN)(FAB+) MS M∙+ 955 957 959 (10 6 3) mz 937 939941 (25 50 70) 498 500 (50 30) 244 (18) Uv-Vis(cmminus1) ]

1 9680 ]

2 15604 ]

3 25634

244 Zn(II) Complex of Schiff Base HL

Light Yellow Solid Yield 69 mp gt 340∘C Anal Calcdfor [Zn(C

25H16O2N4Cl)(Cl)]H

2O (Mr = 55740) C 5372 H

322 N 1002 Found C 5399 H 335 N 1019 IR (KBrcmminus1) 3420 (]H

2O) 3305 and 3218 (]NHNH) 1634 (]C=O)

1557 (]C=N) 1489 1066 and 615 (]Pyridine ring) 470 (]MndashO) 425(]MndashN) 357 (]MndashCl)

1H NMR (DMSO-1198896) 120575 1312 (s 1H

CONH) 1153 (s 1H indole NH) 845 (s 1H HC=N) 735ndash855 (m 12H ArH) (FAB+) MS M∙+ 557 559 561 (10 1815)mz 539 541 and 543 (48 72 20) 469 (48) 250(60)

245 Cd(II) Complex of Schiff Base HL

Pale Yellow Solid Yield 71 mp gt 340∘C Anal Calcd for[Cd(C

25H16O2N4Cl)(Cl)]H

2O (Mr = 60441) C 4955 H


2O) 3293 and 3221 (]NHNH) 1637 (]C=O)

1550 (]C=N) 1425 1059 and 699 (]Pyridine ring) 469 (]MndashO)419 (]MndashN) 350 (]MndashCl)

1H NMR (DMSO-1198896) 120575 1314 (s 1H

CONH) 1162 (s 1H indole NH) 846 (s 1H HC=N) 720ndash835 (m 12H ArH)

246 Hg(II) Complex of Schiff Base HL

Light Yellow Solid Yield 68 mp 330∘C Anal Calcd for[Hg(C

25H16O2N4Cl)(Cl)] (Mr = 67459) C 4440 H 236

N 828 Found C 4461 H 242 N 836 IR (KBr cmminus1)3295 and 3230 (]NHNH) 1664 (]C=O) 1560 (]C=N) 1420 1060and 640 (]Pyridine ring) 550 (]MndashO) 428 (]MndashN) 352 (]MndashCl)

25 Pharmacology

251 Antimicrobial Assays The biological activities of thesynthesized Schiff base HL and its Cu(II) Co(II) Ni(II)Zn(II) Cd(II) and Hg(II) complexes were studied for theirantibacterial and antifungal activities by the disc and welldiffusion method respectively The in vitro antibacterialactivities of the compounds were tested against two Gram-negative Escherichia coli (MTCC 46) and Salmonella typhi(MTCC 98) and two Gram-positive Bacillus subtilis (MTCC736) and Staphylococcus aureus (MTCC 3160) bacteria

The in vitro antifungal activities were carried out againstCandida albicans (MTCC 227) Cladosporium oxysporum(MTCC 1777) and Aspergillus niger (MTCC 1881) fungi [3132] The stock solutions of the test chemicals (1mgmLminus1)were prepared by dissolving 10mg of the each test compoundin 10mL of distilled DMSO solvent The different concentra-tions of the test compounds (100 75 50 25 and 125 120583gmLminus1)were prepared by diluting the stock solutionwith the requiredamount of freshly distilled DMSO Further the controlledexperimentswere carried out by using freshly distilledDMSOsolvent alone

252 Antibacterial Screening Muller-Hinton agarmedia wasused for the antibacterial studies The pure dehydratedMuller-Hilton agar (38 g) was dissolved in 1000mL distilledwater The pure cultures of the bacterial strains E coli Saureus B subtilis and S typhi were subcultured by inoc-ulating in the nutrient broth and they were incubated at 37∘Cfor about 18 h The agar plates were prepared by using theabove Muller-Hinton agar media and wells were dug withthe help of 6mm sterile metallic cork borer Each plate wasinoculated with 18-h-old bacterial culture (100120583L) using amicropipette and spreaded uniformly using bent glass rod oneach plateThe drug gentamycin is used as standard Differentconcentration of the test compounds were incorporatedinto the wells using micropipette and the plates were keptfor incubation at 37∘C for 24 h Soon after the completionof incubation period the diameter of the inhibition zonegenerated by each test compound against bacterial growthwas measured using antibiogram zone measuring scale

253 Antifungal Screening Potato dextrose agar (PDA)media was used for the antifungal studies The followingingredients were used to prepare the media potatoes (slicedwashed unpeeled) 200 g dextrose 20 g and agar 20 g in1000mL distilled water The pure cultures C albicans Coxysporum and A niger were inoculated on PDA slantsThese slants were incubated at 32∘C for 7 days To these7-day-old slants of fungal strains 10mL of 01 tween-80solution was added and the culture were scraped with sterileinoculating loop to get uniform spore suspension The agarplates were prepared by using the above potato dextrose agarmedia and wells were dug with the help of 6mm sterilemetallic cork borer Each plate was inoculated with 7-day-old spore suspension of each fungal culture (100 120583L) usinga micropipette and spreaded uniformly using bent glass rodon each plate Then each well was incorporated with thetest compound solution of different concentrationsThe drugfluconazole is used as standard All the inoculated plates wereincubated at 32∘C for about 48 h Soon after the completionof incubation period the diameter of the inhibition zonegenerated by each test compound against fungal growth wasmeasured using antibiogram zone measuring scale

254 DNA Cleavage Experiment The extent to which thenewly synthesized ligands and their metal complexes couldfunction as DNA cleavage agents was examined using E coliDNA as a target The electrophoresis method was employed


Table 2 The IR data of ligandHL and its complexes (cmminus1)

Compounds ]NHNH ]C=O ]H2O ]C=N Pyridine ring ]MndashO ]MndashN ]MndashCl

HL 3311 3229 3162 1674 1661 mdash 1608 mdash mdash mdash mdashCu complex 3283 3221 1639 mdash 3418 1548 1493 1077 615 514 442 mdashCo complex 3271 3230 1629 mdash 3423 1551 1489 1061 670 553 435 mdashNi complex 3305 3218 1638 mdash 3430 1555 1478 1063 621 477 450 mdashZn complex 3305 3218 1634 mdash 3420 1557 1489 1066 615 470 425 357Cd complex 3293 3221 1637 mdash 3423 1550 1425 1059 699 469 419 350Hg complex 3295 3230 1664 mdash mdash 1560 1420 1060 640 550 428 352HL= ligand

to study the efficiency of cleavage by the synthesized com-pounds Nutrient broth media was used (Peptone 10 g NaCl10 g and yeast extract 5 gLminus1) for culturing E coli Theelectrophoresis of the test compounds was done according tothe literature method [33]

The freshly preparedE coli culture (15mL) is centrifugedand the pellets obtained which was then dissolved in 05mLof lysis buffer (50mM EDTA 100mM tris pH 80 50mMlysozyme) To this 05mL of saturated phenol was addedand incubated at 55∘C for 10min Soon after the incubationthe solution was centrifuged at 10000 rpm for 10min and tothe supernatant liquid equal volume of chloroform isoamylalcohol (24 1) and 120th volume of 3M sodium acetate(pH 48) were added Again the solution is centrifuged at10000 rpm for 10min and the supernatant layer collected isthen mixed with 3 volumes of chilled absolute alcohol andthe DNA precipitates The precipitated DNA was separatedby centrifugation and the pellet was dried and dissolved inTris buffer (10mM tris pH 80) and stored in cold condition

Agarose (250mg) was dissolved in hot tris-acetate-EDTA (TAE) buffer (25mL) (484 g Tris base pH-80 05MEDTALminus1) and heated to boil for few minutes When thegel attains approximately 55∘C it was then poured into thegas cassette fitted with comb Slowly the gel was allowed tosolidify by cooling to room temperature and then carefullythe comb was removed The solidified gel was placed inthe electrophoresis chamber containing TAE buffer Testcompounds (1mgmLminus1) were prepared in DMSO The testcompounds (25120583g) were added to the isolated DNA of Ecoli and they were incubated for 2 h at 37∘C Soon afterthe incubation period the DNA sample (20 120583L) mixed withbromophenol blue dye in equimolar ratio alongwith standardDNAmarker containing TAE buffer was loaded carefully intothe wells and the constant 50V of electricity was supplied forabout 30min Later the gel was removed and it was stainedwith ethidium bromide solution (10 120583gmLminus1) for 15ndash20minthen the bands were observed and photographed under UV-illuminator

255 Antioxidant Assay (Free Radical Scavenging Activity)The free radical scavenging activity of the test samples wasdetermined with the 22-diphenyl-1-picryl-hydrazyl (DPPH)method [34] Different concentrations of test compounds(10 120583g 50120583g and 100120583g) and standard butylated hydroxyanisole (BHA) were taken in different test tubes and the

volume of each test tube was adjusted to 100120583L by adding dis-tilled DMF To the sample solution in DMF 5mLmethanolicsolution of DPPH (01mM) was added to these tubes Thetubes were allowed to stand for 30min The control experi-ment was carried out as above without the test samples Theabsorbance of test solutions was measured at 517 nm Thereduction of DPPH was calculated relative to the measuredabsorbance of the control Radical scavenging activity wascalculated using the following formula

Radical scavenging activity

=[Control optical density minus Sample optical density

Control optical density]times100

(1)

3 Results and Discussion

All the synthesized metal complexes are coloured solidsamorphous in nature and stable in air Melting points ofthe newly synthesized metal complex were above gt300∘CThe complexes are insoluble in water and common organicsolvents but are soluble in solvents like DMF and DMSOElemental analysis and analytical data of the complexessuggest that the metal to ligand ratio of the complexesis 1 2 stoichiometry of the type [M(L)

2]H2O for Cu(II)

Co(II) and Ni(II) complexes 1 1 stoichiometry of thetype [M(L)(Cl)]H

2O for Zn(II) and Cd(II) complexes and

[M(L)(Cl)] for Hg(II) complex respectively where L standsfor deprotonated ligand The molar conductance values aretoo low to account for any dissociation of the complexes inDMF (24ndash60 ohmminus1 cm2moleminus1) indicating their nonelec-trolytic nature of the complexes in DMF (Table 1) [35]

31 IR Spectral Studies The important IR bands of the Schiffbase HL and its metal complexes are represented in Table 2IR spectrum of Schiff base HL displayed one sharp bandat 3311 and two weak bands at 3229 and 3162 cmminus1 dueto indole NH and two NHNH functions of two amidegroups respectively Two sharp peaks observed at 1674 and1661 cmminus1 are due to two carbonyl groups of two CONHfunctions A band at 1608 cmminus1 is due to C=N of azomethinegroup of the Schiff base Disappearance of band at 1674 cmminus1due to quinolinone carbonyl function with the appearanceof a new band in the region 1290ndash1287 cmminus1 in all the


Table 3 The 1H NMR data of ligandHL and its Zn(II) and Cd(II) complexes

Ligandcomplexes 1H NMR data (120575)HL 1220 and 1200 (s 2H two CONH) 1160 (s 1H indole NH) 840 (s 1H HC=N) 710ndash820 (m 13H ArH)Zn complex 1312 (s 1H CONH) 1153 (s 1H indole NH) 845 (s 1H HC=N) 735ndash855 (m 12H ArH)Cd complex 1314 (s 1H CONH) 1162 (s 1H indole NH) 846 (s 1H HC=N) 720ndash835 (m 12H ArH)HL= ligand

complexes proves the enolization of quinolinone carbonylduring complexation and formation of a new bond betweenenolized oxygen andmetal ion via deprotonationThe shift ofband due to amide carbonyl attached to 2-position of indolefrom 1661 cmminus1 to 1639ndash1629 cmminus1 in case of all the complexesconfirms the coordination of metal ion with oxygen atom ofthis carbonyl function without undergoing enolization [36]The bands appeared at 3305ndash3283 and 3230ndash3218 cmminus1 dueto indole NH and NH of amide function attached to 2-position of indole respectively in case of complexes it provesthe noninvolvement of these NH functions in complexationsince these two peaks have appeared at 3311 and 3229 cmminus1in case of Schiff base HL Absorption frequency of HC=Nfunction which has appeared at 1608 cmminus1 in the Schiff basehas been shifted towards lower frequency by 60ndash48 cmminus1and appeared in the region 1568ndash1548 cmminus1 in all the com-plexes which indicates the coordination of metal ion withazomethine nitrogen atom [37] This is further confirmedby the appearance of new bands in the region 555ndash469 cmminus1and 470ndash419 cmminus1 in all the complexes which are due to]MndashO and ]MndashN stretching vibrations respectively [38] InZn(II) Cd(II) and Hg(II) complexes of ligand HL newbands observed in the region 357ndash350 cmminus1 are due to ]MndashClvibrations

Bands observed in the region 1493ndash1420 1077ndash1059 and699ndash615 cmminus1 in all the complexes are due to pyridine ringvibration of quinoline moiety The broad band observed inall the complexes except Hg(II) complex of ligand HL in theregion 3430ndash3418 cmminus1 is assigned to ]OH vibration of thelattice water molecules [39]

32 1H NMR Spectral Studies The 1H NMR data of SchiffbaseHL and its Zn(II) and Cd(II) complexes are presented inTable 3 The 1H NMR spectrum of Schiff base HL displayedthree broad singlets at 1220 1200 and 1160 ppm which aredue to proton of two amide functions (s 2H CONH) andproton of indole NH(s 1H NH) respectively The signalsdue to proton of azomethine function and thirteen aromaticprotons have appeared at 840 ppm (s 1H HC=N) and 710ndash820 ppm (m 13H ArH) respectively

In the spectra of Zn(II) and Cd(II) complexes displayedtwo peaks at 1312 1153 ppm and 1314 1162 ppm due toproton of an amide function andproton of indoleNH respec-tively The disappearance of the signal at 1200 ppm whichwas there in the spectrum of Schiff base HL confirms theenolization of CONH function of quinolinone moiety and itsinvolvement in complexation with metal ion through oxygenatom of enolized carbonyl function via deprotonation The

signal due to azomethine proton in Zn(II) and Cd(II) com-plexes have been shifted towards lower field strength whencompared to the spectra of ligand they have appeared at 845and 846 ppm respectively The aromatic protons in case ofZn(II) and Cd(II) complex have been resonated in the region735ndash855 and 720ndash835 ppm respectively The shift of theentire proton towards lower field strength when comparedto Schiff base HL proves beyond doubt the formation ofcomplex with metal ion

33 FAB-Mass Spectral Studies The representative Ni(II)and Zn(II) complexes have been subjected for their massspectral studies The FAB-mass spectrum of Ni(II) complexis depicted in Figure 1 shows a molecular ion peak at M∙+955 957 and 959 (2 6 18) which corresponds toits molecular weight confirming the stoichiometry ratioof metal chelates as [M(L)

2]H2O Further fragment ion

observed atmz 937 939 941 (25 50 70) 498 500 (5030) and 244 (20) are due to the sequential expulsion ofH2O C25H16N3O2Cl and C

15H9NOCl species respectively

from the molecular ion This fragmentation pattern is inconsistency with its structure (Scheme 2)

The FAB-mass spectrum of Zn(II) complex (Figure 2)shows a molecular ion peak M∙+ 557 559 and 561 (10 1814) which corresponds to its molecular weight confirmingthe stoichiometry ratio of metal chelates as [M(L)(Cl)]H

2O

Further fragment ion observed at mz 539 541 543 (4872 20) 469 (48) and 250 (58) are due to thesequential expulsion of H

2O 2Cl and C

15H9NO species

respectively from the molecular ion This fragmentationpattern (Scheme 3) is in conformity with the structure

34 Electronic Spectral Studies Electronic spectral data of theCu(II) Co(II) and Ni(II) complexes of the Schiff base HLare given in Table 4 Electronic spectral studies of all thesecomplexes were carried out in DMF at 10minus3M concentrationThe green coloured Cu(II) complex displayed low intensitysingle broad band in the region 13769ndash17463 cmminus1 Thebroadness of the band is assigned due to 2B

1g rarr2Eg

2B1g rarr

2B2g and

2B1g rarr

2Atg transitions which are similarin energy and give rise to only one broad absorption bandand the broadness of the band is due to dynamic Jahn-Tellerdistortion These data suggest that the Cu(II) complex havedistorted octahedral geometry [40]

The electronic spectra of brown coloured Co(II) complexshows two absorption bands observed at 15977 cmminus1 and19518 cmminus1 due to the 4T

1g (F) rarr4A2g (F) (]2) and

4T1g (F) rarr

4T2g(P) (]3) transitions respectively which are


[Mass spectrum]

Data 10FEB02E028

Sample M3L1 Gulbarga univ [4570]

Inlet direct Ion mode FAB+Spectrum type normal ion [MF-linear]RT 098min

BP mz 1540000 Int 10000Output mz range 936202 to 11041543 Cut level 0001051591

100

50

0

100 150 200 250 300 350 400 450 500 550

mz

107

136 154

176 228230

289 307

328 348 392 411 450461

498

503 552 578

Scan number (6 12)

Date Feb 02 2010 1116

Note mdash

(a)

1051591times3100

50

0

600 650 700 750 800 850 900 950 1000 1050 1100

mz

614 648 664741 743 786 861 907

939941

997 1045

(b)

Figure 1 FAB-mass spectrum of Ni(II) complex

Table 4 Electronic spectral bands and ligand field parameters of the Co(II) Ni(II) and Cu(II) complexes in DMF (10minus3 M) solution

Complexes Transitions in cmminus1 Dq (cmminus1) 1198611015840 (cmminus1) 120573 120573 ]

2]1

LFSE (k cal)]1

lowast ]2

]3

Cu(II) complex 13769ndash17463 1530 mdash mdash mdash mdash 2622Co(II) complex 7447 15977 19518 853 877 0843 9680 1480 14622Ni(II) complex 9680 15604 25634 968 812 0780 2192 1470 33188lowastCalculated values

in good agreement with the reported values [41] The lowestband ]

1is not to be observed due to the limited range of

the instrument used but could be calculated using the bandfitting procedure suggested by Underhill and Billing [42]These transitions suggest octahedral geometry for the Co(II)complex

The brown Ni(II) complex under present investiga-tion exhibited two bands in the region 15604 cmminus1 and25634 cmminus1 These bands are assigned to 3A

2g (F) rarr3T1g (F) (]2) and 3A

2g (F) rarr3T1g (P) (]3) transitions

respectively in an octahedral environment The band ]1was

calculated by using a band fitting procedure [42]

The octahedral geometry was further supported by thevalues of ligand field parameters such as the Racah inter-electronic repulsion parameter (B1015840) ligand field splittingenergy (10 Dq) nephelauxetic parameter (120573) and ligand fieldstabilization energy (LFSE) [43] The calculated B1015840 values forthe Co(II) and Ni(II) complexes were lower than the free ionvalues which is due to the orbital overlap and delocalisationof d-orbitals The 120573 values are important in determining thecovalency for the metal-ligand bond and they were foundto be less than unity suggesting a considerable amount ofcovalency for the metal-ligand bonds The 120573 value for theNi(II) complex was less than that of the Co(II) complexindicating the greater covalency of the MndashL bond [44]


100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L

NoteInlet direct Ion mode FAB+Spectrum type normal ion [MF-linear]RT 000min


Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)

Figure 2 FAB-mass spectrum of Zn(II) complex

35 Magnetic Susceptibility Studies Magnetic susceptibilitymeasurements obtained at room temperature for Cu(II)Co(II) and Ni(II) complexes are listed in Table 1 and theywere found to be paramagnetic in nature The observedmagnetic moment for Cu(II) complex is 179 BM Theobserved value is slightly higher than the spin-only value dueto one unpaired electron 173 BM suggesting the octahedralgeometry [45] Thus the present Cu(II) complex is devoidof any spin interaction with distorted octahedral geometryIn octahedral Co(II) complex the ground state is 4T

1g Alarge orbital contribution to the singlet state lowers themagnetic moment values for the various Co(II) complexeswhich are in the range 412ndash470 and 470ndash520 BM for tetra-hedral and octahedral complexes respectively [46] In thepresent investigation the observed magnetic moment valuefor Co(II) complex is 501 BM which indicates octahedralgeometry for the Co(II) complex For Ni(II) complex theobserved magnetic moment value is 290 BM which is wellwithin the expected range for Ni(II) complex with octahedralstereochemistry 283ndash350 BM [47]

36 ESR Spectral Studies of the Cu(II) Complex To obtainthe information about the hyperfine and superhyperfinestructure in order to elucidate the geometry of the complex

and the site of the metal-ligand bonding or environmentaround the metal ion the X-band ESR spectra of Cu(II)complex has been recorded in the polycrystalline state atroom temperature at a frequency of 9387GHz with a field setof 3950G The spin Hamiltonian parameters for the Cu(II)complex is used to derive the ground state In octahedralgeometry the 119892-tensor parameter is with 119892

gt 119892perpgt 20023

the unpaired electron lies in the d1199092-1199102 orbital in ground state

and with 119892perpgt 119892gt 20023 and the unpaired electron

lies in the d119911

2 orbital [48] The observed measurements forCu(II) complex 119892

(2075) gt 119892

perp(2018) gt 20023 indicating

that the complex is axially symmetric and copper site hasa d1199092-1199102 ground state characteristic of octahedral geometry

[49] The 119892value is an important function for indicating

the metal-ligand bond character for ionic 119892gt 23 and for

covalent characters 119892lt 23 respectively [50] In the present

Cu(II) complex the 119892value is less than 23 indicating an

appreciable covalent character for themetal-ligand bondThegeometric parameter (119866) is themeasure of extent of exchangeinteraction and is calculated by using 119892-tensor values by theexpression 119866 = 119892

minus 2119892

perpminus 2 According to Hathaway and

Billing [51] if the 119866 value is greater than 4 the exchangeinteraction between the copper centers is negligible whereasits value is less than 4 and the exchange interaction is noticedThe calculated119866-value for the present Cu(II) complex is 4166


Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O

Scheme 2 Mass fragmentation of Ni(II) complex

indicating that the exchange coupling effects are not operativein the present complex

37Thermal Studies The thermal stabilities of the complexeshave been studied as a function of temperatureThe proposedthermal decomposition pattern with temperature and thepercentage of metal oxide obtained are depicted in Table 5

The Thermo gravimetric curve (TGA) of the represen-tative Cu(II) complex is shown in Figure 3 showing threedecomposition steps The first decomposition occurs at atemperature of 100∘Cwhich is due to the loss of a lattice watermolecule the second decomposition occurs at a temperatureof 335∘C which corresponds to loss of two C

15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙

Scheme 3 Mass fragmentation of Zn(II) complex

species and the third decomposition occurs at a temperatureof 519∘C due to the loss of two C

4H4species Further the

complex underwent decomposition in a gradual mannerrather than with the sharp decomposition up to 750∘Ccorresponds to loss of remaining organic moiety leavingbehind the residue copper oxide

The thermal decomposition pattern of Co(II) Zn(II) andHg(II) complexes shows two decomposition steps each Thefirst decomposition occurs at a temperature of 100 110 and330∘C which corresponds to loss of lattice water moleculewith weight loss of 188 (Cald 159) for Co(II) complexand 309 (Cald 322) for Zn(II) complex and the lossof HCl for Hg(II) complex with weight loss of 531 (Cald533) respectively The second decomposition occurs at


10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)

Derivative weight (mgmin)

minus0166mgmin10087∘C



Figure 3 TG-DTA curve of Cu(II) complex

12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)

Figure 4 Cyclic voltammogram of Cu(II) complex at a scan rate of100mVs

temperatures of 348 340 and 354∘Cwhich correspond to theloss of two C

15H10N3OCl species for Co(II) complex with

weight loss of 6155 (Cald 5947) loss of C15H10N2OCl

species for Zn(II) complex with a weight loss of 4815 (Cald4825) and loss of C

19H13ONCl species for Hg(II) complex

with a weight loss of 4946 (4846) respectively Furtherthese complexes underwent gradual decomposition up to750ndash850∘C corresponds to the loss of remaining organicmoiety leaving behind residue metal oxides of the respectivecomplexes The percentage metal composition in all thecomplexes as done by the elemental analysis agrees well withthe remaining residual metal oxides in thermal studies

38 Powder X-Ray Diffractions Studies Although the synthe-sized metal complexes were soluble in some polar organicsolvents (DMSO and DMF) crystals that are suitable forsingle-crystal studies are not obtained Powder XRD patternof Ni(II) and Zn(II) complexes are being studied in order totest the degree of crystallinity of the complexes Powder X-raydiffraction pattern forNi(II) complex showed 14 reflections inthe range of 5ndash80∘ (2120579) which are arised from diffraction of

X-ray by the planes of complex The interplanar spacing (119889)has been calculated by using Braggrsquos equation 119899120582 = 2119889 sin 120579The calculated interplaner 119889-spacing together with relativeintensities with respect to most intense peak have beenrecorded and depicted in Table 6 The unit cell calculationshave been calculated for cubic symmetry from the entireimportant peaks and ℎ2+1198962+1198972 values were determinedTheobserved interplaner 119889-spacing values have been comparedwith the calculated ones and it was found to be in goodagreement The ℎ2 + 1198962 + 1198972 values are 1 3 5 6 10 15 17 3947 83 90 109 and 138 It was observed that the presence offorbidden numbers such as 15 and 47 indicates that the Ni(II)complex may belong to hexagonal or tetragonal systems

Similar calculations were performed for Zn(II) complexwhich showed 15 reflections in the range 5ndash80∘ (2120579) Theimportant peaks have been indexed and observed interpla-nar 119889-spacing values have been compared with the calculatedones The unit cell calculations were performed for cubicsystem and the ℎ2+1198962+1198972 values were determinedThe valuesare 1 2 3 4 5 7 9 11 13 22 29 41 46 and 72 The presenceof forbidden number such as 7 indicates the Zn(II) complexmay belong to hexagonal or tetragonal systems (Table 7)

39 Electrochemical Study Electron transfer plays a vitalrole in governing the pathway of chemical reactions Cyclicvoltammetry is the most versatile electroanalytical techniquefor the study of electroactive species The electrochemicalbehaviour of Cu(II) complex was investigated in DMF(10minus3M) solution containing 005M n-Bu

4NndashClO

4as a

supporting electrolyte by cyclic voltammetry and it is themost versatile electroanalytical technique for the study ofelectroactive species The cyclic voltammogram of Cu(II)complex (Figure 4) in DMF at a scan rate of 100mVs showswell-defined redox process corresponding to the formationof Cu(II)Cu(I) couple at 119864pa = 076V and 119864pc = 047Vversus AgAgCl The peak separation of this couple is foundto be quasi-reversible with Δ119864

119901= 029V and the ratio

of anodic to cathodic peak height was less than one Thedifference between forward and backward peak potential canprovide a rough evaluation of the degree of the reversibilityof one electron transfer reaction Thus the analysis of cyclicvoltammetric response to 100mVs 200mVs and 300mVsscan rates gives the evidence for quasi-reversible one electronredox processThe ratio of anodic to cathodic peak heightwasless than one and peak current increases with the increase ofsquare root of the scan rates establishing diffusion controlledelectrode process [52] From the peak separation value Δ119864

119901

and peak potential increases with higher scan rates we cansuggest that the electrode processes are consistent with thequasi-reversibility of Cu(II)Cu(I) couple [53]

310 Pharmacological Results

3101 In Vitro Antimicrobial Activity The in vitro antimicro-bial activity of all the synthesized compounds were screenedagainst E coli S typhi B subtilis and S aureus bacteriaand C albicans C oxysporum and A niger fungal strainsby minimum inhibitory concentration (MIC) method The


Table 5 Thermal decomposition of the complexes

Complex number Decomposition temp (∘C) Weight loss Metal oxide InferenceObsd Cald Obsd Cald

Cu complex

100 151 187 mdash mdash Loss of lattice water molecule335 6155 5947 mdash mdash Loss due to two indole (2C15H10N3OCl) species519 2788 2787 mdash mdash Loss due to 2C4H4

Upto 750 mdash mdash 828 810 Loss due to remaining organic moiety

Co complex100 188 159 mdash mdash Loss of lattice water molecule348 6155 5947 mdash mdash Loss due to two indole (2C15H10N3OCl) species


Zn complex110 309 322 mdash mdash Loss of lattice water molecule340 4815 4825 mdash mdash Loss due to C15H10N2OCl

Upto 750 mdash mdash 1496 1429 Loss due to organic moiety

Hg complex330 531 533 mdash mdash Loss due to HCl354 4946 4846 mdash mdash Loss due to C19H13ONCl species


Table 6 Powder X-ray diffraction data of Ni(II) complex

Peak 2120579 120579 Sin 120579 Sin2120579 ℎ2+ 1198962+ 1198972 (Sin2120579CF) h k l 119889

119886 in ACald Obsd

1 6086 3043 00530 000281 1000 (1) 1 0 0 145333 1453 14532 7385 3692 00643 000414 1473 (1) 1 1 0 119797 1453 14533 11123 5561 00969 000939 3341 (3) 1 1 1 79494 1453 14534 12964 6482 01128 001274 4533 (5) 2 1 0 68289 1453 14535 14863 7431 01293 001672 5950 (6) 2 1 1 59574 1453 14536 19509 9754 01694 002870 10213 (10) 3 1 0 45472 1453 14537 23902 11951 02070 004288 15259 (15) mdash 37212 1453 14538 25570 12785 02212 004897 17427 (17) 3 2 2 34823 1453 14539 38460 19230 03293 010847 38601 (39) mdash 23392 1453 145310 42710 21355 03641 013260 47188 (47) mdash 21156 1453 145311 57670 28835 04822 023260 82775 (83) mdash 15974 1453 145312 60383 30191 05028 025289 90000 (90) 7 5 4 15320 1453 145313 67305 33652 05541 030707 10927 (109) mdash 13901 1453 145314 77026 38513 06226 038774 13798 (138) 8 7 5 12372 1453 1453

minimum inhibitory concentration (MIC) profiles of all thecompounds against bacteria and fungi are summarized inTable 8 The MIC values indicated that all the complexesexhibited promising results than the ligand against men-tioned microorganisms and this activity enhanced on coor-dinationwith themetal ionsThis enhancement in the activitymay be rationalized on the basis that ligands mainly possessC=N bond The enhanced activity of the complexes over theligand can be explained on the basis of chelation theory [5455] It is observed that in a complex the positive charge of themetal is partially shared with the donor atoms present in theligand and there may be 120587-electron delocalization over thewhole chelating [56]This increases the lipophilic character ofthemetal chelate and favors its permeation through the lipoidlayer of the bacterial membranes The heterocyclic Schiffbases with different functional groups have greater tendencyto interact with nucleoside bases even after complexationwith metal ion or with the essential metal ions present in thebiosystem can act as a promising bactericides because they

always tend to interact with enzymatic functional groups inorder to achieve higher coordination numbers [57] Thereare also other factors which increase the activity namelysolubility conductivity and bond length between the metaland the ligand

3102 DNA Cleavage Activity The representative Schiff baseHL and its metal complexes are studied for their DNA cleav-age activity by the agarose gel electrophoresis method againstDNA of E coli The characterization of DNA recognitionby transition metal complex has been aided by the DNAcleavage chemistry that is associated with redox-active orphotoactivated metal complexes [58] The electrophoresisanalysis clearly revealed that the Schiff base and their metalcomplexes have acted on DNA as there was a difference inmolecular weight between the control and the treated DNAsamples The difference was observed in the bands of lanesof complexes compared with the control DNA of E coli


Table 7 Powder X-ray diffraction data of Zn(II) complex

Peak 2120579 120579 Sin 120579 Sin2120579 ℎ2+ 1198962+ 1198972 (Sin2120579CF) h k l d a in A

Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271

Table 8 Minimum inhibitory concentration (MIC 120583gmLminus1) of ligand and its metal complexes

Compounds MIC value in 120583gmLminus1 (zone of inhibition in mm)E coli S aureus B subtilis S typhi C albicans C oxysporum A niger

HL 50 75 50 100 75 50 50Cu complex 1250 25 25 50 25 1250 1250Co complex 25 50 1250 50 1250 25 25Ni complex 1250 25 25 50 25 1250 25Zn complex 25 50 25 75 50 25 25Cd complex 1250 1250 1250 25 1250 25 1250Hg complex 25 1250 25 50 25 25 1250Gentamycin 1250 1250 1250 1250 mdash mdash mdashFluconazole mdash mdash mdash mdash 1250 1250 1250HL= ligand

(Figure 5) which is due to the relaxation of circular DNAinto linear form This shows that the control DNA alonedoes not show any apparent cleavage whereas the Schiff baseand its complexes do show The lane Cu shows completecleavage of DNA of E coli whereas the other complexes haveshown partial cleavage The result indicates the importantrole of coordination of nitrogen and oxygen to the metal inthese isolated DNA cleavage reactions As the compound wasobserved to cleave the DNA it can be concluded that thecompounds inhibit the growth of the pathogenic organismby cleaving the DNA of E coli

3103 Antioxidant Assay (DPPH Free Radical ScavengingActivity) The newly synthesized Schiff base and its metalcomplexes were screened for free radical scavenging activityby DPPH method Antioxidant activity of these compoundswas investigated by measuring radical scavenging effect ofDPPH radicals The results of the free radical scavengingactivity of the compounds at different concentrations areshown in Figure 6 It is evident from the results that the

M C HL Zn Cu Ni Co Cd

2313 kb94166557

43612322

Figure 5 DNA cleavage of E coli genome M standard molecularweight marker C control Lane HL Zn Cu Ni Co and Cd treatedDNA of E coli genome with respective compounds

free radical scavenging activity of these compounds wasconcentration dependent Among the examined compoundsCu(II) Cd(II) Ni(II) and Co(II) complexes have exhibitedgood scavenging activity Whereas Hg(II) and Zn(II) have


0

10

20

30

40

50

60

70

80

HL Cu Co Ni Zn Cd Hg BHA

Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g

Figure 6 Antioxidant results of ligand and its complexes

Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH

Figure 7 Proposed structures of metal complexes

shown moderate activity All the metal complexes haveexhibited higher scavenging activity than the Schiff baseHLThe marked antioxidant activity of the metal complexes incomparison to free Schiff base HL could be due to thecoordination of metal with azomethine nitrogen carbonyloxygen of amide function attached to the 2-position of indoleand oxygen of enolized amide function of quinolinonemoietyvai deprotonation In case of the above test compounds thehydrogen of azomethine is more acidic than the hydrogenof the indole NH Hence hydrogen of azomethine could beeasily donated to theDPPH free radical and convert itself intothe stable free radical

4 Conclusions

On the basis of the above results the Schiff base HL actsas tridentate (ONO) chelating agent coordinate with metal

ions through the carbonyl group of amide function attachedto 2-position of indole azomethine nitrogen and oxygenatom of the enolized amide function of quinolinone moietyvia deprotonation Analytical spectral and magnetic studiesrevealed mononuclear nature of the complexesThe probablestructures of the metal complexes are shown in Figure 7 TheCu(II) Co(II) and Ni(II) complexes exhibited octahedralgeometry whereas Zn(II) Cd(II) and Hg(II) complexesexhibited tetrahedral geometry The antimicrobial activityof the Schiff base HL is enhanced upon complexation withmetal ions particularly Cu(II) Co(II) and Ni(II) showedpromising activity compared to Schiff base and proved to beessential for the growth-inhibitor effect The DNA cleavagestudies revealed that the Cu(II) complex has shown completecleavage of genomic DNA of E coliThe results of antioxidantactivity experiment clearly indicate that among the test


compoundsCu(II) Cd(II) Ni(II) andCo(II) complexes haveexhibited good scavenging activity compared to the standard

Acknowledgments

The authors are thankful to the Professor and ChairmanDepartment of Chemistry GulbargaUniversity Gulbarga forproviding the laboratory facilities The authors are thankfulto STIC Cochin University SAIF IISC Bangalore CDRI Luc-know Chairman Department of Material Science GulbargaUniversity Gulbarga for providing spectral data and theBioGenics Research and Training Centre in BiotechnologyHubli for biological activities

References

[1] U Misra A Hitkari A K Saxena S Gurtu and K ShankerldquoBiologically active indolylmethyl-134-oxadiazoles 134-thiadiazoles 4H-134-triazoles and 124-triazinesrdquo EuropeanJournal of Medicinal Chemistry vol 31 no 7-8 pp 629ndash6341996

[2] P Rani V K Srivastava and A Kumar ldquoSynthesis and anti-inflammatory activity of heterocyclic indole derivativesrdquo Euro-pean Journal of Medicinal Chemistry vol 39 no 5 pp 449ndash4522004

[3] A El-Gendy Adel A Abdou Naida Z Sarhan El-Taher andA El-Banna Hosney ldquoSynthesis and biological activity of somenew spio-[indoline-321015840-thiazolidine]-24-dionesrdquo AlexandriaJournal of Pharmaceutical Science vol 7 pp 99ndash103 1993

[4] N Karali A Gursoy F Kandemirli et al ldquoSynthesis andstructure-antituberculosis activity relationship of 1H-indole-23-dione derivativesrdquo Bioorganic andMedicinal Chemistry vol15 no 17 pp 5888ndash5904 2007

[5] A Dandia V Sehgal and P Singh ldquoSynthesis of fluorine con-taining 2-aryl-3-pyrazolylpyranylisoxazolinyl-indole deriva-tive as antifungal and antibacterial agentsrdquo Indian Journal ofChemistry Section B vol 32 pp 1288ndash1291 1993

[6] A S Kalgutkar B C Crews S Saleh D Prudhomme and L JMarnett ldquoIndolyl esters and amides related to indomethacin areselective COX-2 inhibitorsrdquo Bioorganic and Medicinal Chem-istry vol 13 no 24 pp 6810ndash6822 2005

[7] S Olgen and D Nebioglu ldquoSynthesis and biological evaluationof N-substituted indole esters as inhibitors of cyclo-oxygenase-2 (COX-2)rdquo Farmaco vol 57 no 8 pp 677ndash683 2002

[8] I A Leneva N I Fadeeva and I T Fedykina Proceedings of the7th International Conference on Antiviral Research Abstract 1871994

[9] A Y Merwade S B Rajur and L D Basanagoudar ldquoSyn-thesis and antiallergic acitivities of 10-substituted-4-chloro-12-methyl(or phenyl)-12-dihydroquinoxalino[12-a]indolesrdquo Indi-an Journal of Chemistry B vol 29 no 12 pp 1113ndash1117 1990

[10] A E Fernandez and V A Monge ldquoSpanish Patent 400436rdquoChemical Abstract 83 1142059 Spanish Patent and TrademarkOffice 1975

[11] N Ergenc N S Gunay and R Demirdamar ldquoSynthesis andantidepressant evaluation of new 3-phenyl-5-sulfonamidoin-dole derivativesrdquo European Journal of Medicinal Chemistry vol33 no 2 pp 143ndash148 1998

[12] R E Moore C Cheuk X Q G Yang et al ldquoHapalindolesantibacterial and antimycotic alkaloids from the cyanophyte

Hapalosiphon fontinalisrdquo Journal of Organic Chemistry vol 52no 6 pp 1036ndash1043 1987

[13] V K Pandey S Tusi R Misra and R Shukla ldquoA chemicalstrategy for the construction of quinoline isoquinoline coreunitsrdquo Indian Journal of Chemistry B vol 49 no 1 pp 107ndash1112010

[14] A Mital V S Negi and U Ramachandran ldquoSynthesis andantimycobacterial activities of certain trifluoromethyl-amino-quinoline derivativesrdquo Arkivoc vol 2006 no 10 pp 220ndash2272006

[15] R U Pokalwar R V Hangarge P V Maske and M S Shin-gare ldquoSynthesis and antibacterial activities of 120572-hydroxy-phosphonates and 120572-acetyloxyphosphonates derived from 2-chloroquinoline-3-carbaldehyderdquo Arkivoc vol 2006 no 11 pp196ndash204 2006

[16] A Srivastava A Chandra and R M Singh ldquoThiophene-fusedquinoline analogues facile synthesis of 3-amino-2-cyanothieno[23-b] quinolines from 2-chloro-3-cyanoquinolinesrdquo IndianJournal of Chemistry B vol 44 no 10 pp 2077ndash2081 2005

[17] P K Dubey S Srinivas Rao and V Aparna ldquoSynthesis of somenovel 3-(2-chloro-3-quinolyl)-5-phenyl [13] thiazolo [23-c][124] triazolesrdquo Heterocyclic Communications vol 9 no 3 pp281ndash286 2003

[18] P R Reddy K S Rao and B Satyanarayana ldquoSynthesis andDNA cleavage properties of ternary Cu(II) complexes contain-ing histamine and amino acidsrdquo Tetrahedron Letters vol 47 no41 pp 7311ndash7315 2006

[19] A P Kourounakis D Galanakis K T Siakitzis E A Rekka andP N Kourounakis ldquoSynthesis and pharmacological evaluationof novel derivatives of anti-inflammatory drugs with increasedantioxidant and anti-inflammatory activitiesrdquo Drug Develop-ment Research vol 47 pp 9ndash16 1999

[20] M E Buyukokuroglu I Gulcin M Oktay and O I Kufre-vioglu ldquoIn vitroantioxidant properties of dantrolene sodiumrdquoPharmacological Research vol 44 no 6 pp 491ndash494 2001

[21] M E Bravo-Gomez J C Garcıa-Ramos I Gracia-Mora andL Ruiz-Azuara ldquoAntiproliferative activity and QSAR study ofcopper(II) mixed chelate [Cu(N-N)(acetylacetonato)]NO

3and

[Cu(N-N)(glycinato)]NO3complexes (Casiopeınas)rdquo Journal

of Inorganic Biochemistry vol 103 no 2 pp 299ndash309 2009[22] S B Bukhari S Memon M M Tahir and M I Bhanger

ldquoSynthesis characterization and investigation of antioxidantactivity of cobalt-quercetin complexrdquo Journal of MolecularStructure vol 892 no 1ndash3 pp 39ndash46 2008

[23] Y Jadegoud O B Ijare N N Mallikarjuna S D Angadi andB H M Mruthyunjayaswamy ldquoSynthesis and antimicrobialactivity of copper- cobalt- and nickel(II) complexes with Schiffbasesrdquo Journal of the Indian Chemical Society vol 79 no 12 pp921ndash924 2002

[24] B H M Mruthyunjayaswamy Y Jadegoud O B Ijare SG Patil and S M Kudari ldquoSynthesis characterization andantimicrobial activity of macrocylic phenoxo-bridged di- andtetra-nuclear complexes from NN-bis[26-diiminomethyl-4-methyl-1-hydroxyphenyl]succinoylsebacoyldicarboxamidesrdquoTransition Metal Chemistry vol 30 no 2 pp 234ndash242 2005

[25] B H M Mruthyunjayaswamy O B Ijare and Y JadegoudldquoSynthesis characterization and biological activity of symmet-ric dinuclear complexes derived from a novel macrocyclic com-partmental ligandrdquo Journal of the Brazilian Chemical Societyvol 16 no 4 pp 783ndash789 2005


[26] Y Jadegoud O B Ijare B S Somashekar G A N Gowdaand B H M Mruthyunjayaswamy ldquoSynthesis characteriza-tion and antimicrobial activity of homodinuclear complexesderived from 26-bis[31015840-methyl-21015840-carboxamidyliminometh-yl(6101584071015840)benzindole]-4-methylphenol an end-off compartmen-tal ligandrdquo Journal of Coordination Chemistry vol 61 no 4 pp508ndash527 2008

[27] F Rahaman B Hiremath S M Basavarajaiah B H MJayakumarswamy and B H M Mruthyunjayaswamy ldquoSyn-thetic spectral thermal and antimicrobial activity stud-ies of some transition metal complexes derived from 2-hydroxy-methylbenzaldehyde N-(41015840-phenyl-1101584031015840-thiazol-21015840-yl)semicarbazonerdquo Journal of the Indian Chemical Society vol 85no 4 pp 381ndash386 2008

[28] F Rahaman O B Ijare Y Jadegoud and B H M Mru-thyunjayaswamy ldquoPhenoxo-bridged symmetrical homobinu-clear complexes derived from an ldquoend-offrdquo compartmental lig-and 26-bis[51015840-chloro-31015840-phenyl-1H-indole-21015840-carboxamidyl-iminomethyl]-4-methylphenolrdquo Journal of CoordinationChemistry vol 62 no 9 pp 1457ndash1467 2009

[29] A I Vogel A Text Book of Quantitative Inorganic AnalysisLongman ELBS London UK 3rd edition 1968

[30] S P Hiremath B H M Mruthyunjayaswamy and M GPurohit ldquoSynthesis of substituted 2-aminoindolees and 2-(21015840-Phenyl-110158403101584041015840-oxadiazolyl)aminoindolesrdquo Indian Journalof Chemistry Section B vol 16 pp 789ndash792 1978

[31] A K Sadana Y Mirza K R Aneja and O Prakash ldquoHyper-valent iodine mediated synthesis of 1-arylhetryl-124-tri-azolo[43-a] pyridines and 1-arylhetryl 5-methyl-124-tri-azolo[43-a]quinolines as antibacterial agentsrdquo European Jour-nal of Medicinal Chemistry vol 38 no 5 pp 533ndash536 2003

[32] T A Brown Essential Molecular Biology A Practical Approachvol 1 Oxford University Press New York NY USA 1990

[33] J Sambrook E F Fritsch and T Maniatis Molecular CloningA Laboratory Manual Cold Spring Harbor Laboratory ColdSpring Harbor New York USA 2nd edition 1989

[34] R P Singh K N Chidambara Murthy and G K JayaprakashaldquoStudies on the antioxidant activity of pomegranate (Punicagranatum) peel and seed extracts using in vitromodelsrdquo Journalof Agricultural and Food Chemistry vol 50 no 1 pp 81ndash862002

[35] W J Geary ldquoThe use of conductivity measurements in organicsolvents for the characterisation of coordination compoundsrdquoCoordination Chemistry Reviews vol 7 no 1 pp 81ndash122 1971

[36] B Srinivas N Arulsamy and P S Zacharias ldquoCatalytic andmagnetic properties of a new series of binuclear copper(II)complexesrdquo Polyhedron vol 10 no 7 pp 731ndash736 1991

[37] C Jayabalakrishnan andKNatarajan ldquoRuthenium(II) carbonylcomplexes with tridentate Schiff bases and their antibacterialactivityrdquo Transition Metal Chemistry vol 27 no 1 pp 75ndash792002

[38] S Chandra and L K Gupta ldquoEPR mass IR electronic andmagnetic studies on copper(II) complexes of semicarbazonesand thiosemicarbazonesrdquo Spectrochimica Acta A vol 61 no 1-2pp 269ndash275 2005

[39] V B Rana P C Jain M P Swami and A K SrivastavaldquoThiosemicabazones as ligands-I Spectrochemical studieson trivalent metal complexes of 1-phenyl-orthohydroxy-4-benzamido thiosemicarbazonerdquo Journal of Inorganic andNuclear Chemistry vol 37 no 7-8 pp 1826ndash1828 1975

[40] K Abe K Matsufuji M Ohba and H Okawa ldquoSite specificityof metal ions in heterodinuclear complexes derived from an

ldquoend-offrdquo compartmental ligandrdquo Inorganic Chemistry vol 41no 17 pp 4461ndash4467 2002

[41] R A Rai ldquoMetal complexes of 5-(o)hydroxyphenyl-134-oxa-diazole-2-thionerdquo Journal of Inorganic and Nuclear Chemistryvol 42 no 3 pp 450ndash453 1980

[42] A E Underhill and D E Billing ldquoCalculations of the racahparameter B for nickel (II) and cobalt (II) compounds [11]rdquoNature vol 210 no 5038 pp 834ndash835 1966

[43] D N Satyanarayana Electronic Absorption Spectroscopy andRelated Techniques University Press India Limited New DelhiIndia 2001

[44] K Shivakumar S Shashidhar P Vithal Reddy and M B HallildquoSynthesis spectral characterization and biological activity ofbenzofuran Schiff bases with Co(II) Ni(II) Cu(II) Zn(II)Cd(II) and Hg(II) complexesrdquo Journal of Coordination Chem-istry vol 61 no 14 pp 2274ndash2287 2008

[45] D P Singh R Kumar V Malik and P Tyagi ldquoSynthesis andcharacterization of complexes of Co(II) Ni(II) Cu(II) Zn(II)and Cd(II) with macrocycle 341112-tetraoxo-12569101314-octaaza-cyclohexadeca-681416-tetraene and their biologicalscreeningrdquo Transition Metal Chemistry vol 32 no 8 pp 1051ndash1055 2007

[46] N N Greenwood and A Earnshaw Chemistry of the ElementsHeimemann Oxford UK 2nd edition 1997

[47] T R Rao and A Prasad ldquoSynthesis and spectral studies on3d metal complexes of mesogenic schiff base ligands Part1 Complexes of N-(4-butylphenyl) salicylaldiminerdquo Synthesisand Reactivity in Inorganic Metal-Organic and Nano-MetalChemistry vol 35 no 4 pp 299ndash304 2005

[48] S Balasubramanian and C N Krishnan ldquoSynthesis andcharacterization of five-coordinate macrocyclic complexes ofnickel(II) and copper(II)rdquo Polyhedron vol 5 no 3 pp 669ndash6751986

[49] B T Thaker P K Tandel A S Patel C J Vyas M S Jesaniand D M Patel ldquoSynthesis and mesomorphic characterizationof Cu(II) Ni(II) and Pd(II) complexes with azomethine andchalcone as bridging grouprdquo Indian Journal of Chemistry A vol44 no 2 pp 265ndash270 2005

[50] D Kilveson ldquoPublications of Daniel Kivelsonrdquo Journal ofPhysical Chemistry B vol 101 pp 8631ndash8634 1997

[51] B J Hathaway and D E Billing ldquoThe electronic properties andstereochemistry of mono-nuclear complexes of the copper(II)ionrdquo Coordination Chemistry Reviews vol 5 no 2 pp 143ndash2071970

[52] A J Bard and L R Faulkner Electrochemical Methods WileyNew York NY USA 2nd edition 2001

[53] S A Patil V H Naik A D Kulkarni and P S BadamildquoSpectroscopic DNA cleavage and antimicrobial studies ofCo(II) Ni(II) and Cu(II) complexes of sulfur donor schiffbasesrdquo Journal of Sulfur Chemistry vol 31 no 2 pp 109ndash1212010

[54] A K Sharma and S Chandra ldquoComplexation of nitrogen andsulphur donor Schiff rsquos base ligand to Cr(III) and Ni(II) metalions synthesis spectroscopic and antipathogenic studiesrdquo Spec-trochimica Acta A vol 78 no 1 pp 337ndash342 2011

[55] Z H Chohan M Arif M A Akhtar and C T SupuranldquoMetal-based antibacterial and antifungal agents synthesischaracterization and in vitro biological evaluation of Co(II)Cu(II) Ni(II) and Zn(II) complexes with amino acid-derivedcompoundsrdquo Bioinorganic Chemistry and Applications vol2006 Article ID 83131 13 pages 2006


[56] Z H A El-Wahab M M Mashaly A A Salman B A El-Shetary and A A Faheim ldquoCo(II) Ce(III) and UO2(VI)bis-salicylatothiosemicarbazide complexes binary and ternarycomplexes thermal studies and antimicrobial activityrdquo Spec-trochimica Acta A vol 60 no 12 pp 2861ndash2873 2004

[57] K R K Reddy P Suneetha C S Karigar N H Manjunathand K NMahendra ldquoCobalt(II) Ni(II) Cu(II) Zn(II) CD(II)Hg(II) U02(VI) and th(IV) complexes fromONNN Schiff baseligandrdquo Journal of the Chilean Chemical Society vol 53 no 4pp 1653ndash1657 2008

[58] A Sitlani E C Long AM Pyle and J K Barton ldquoDNAphoto-cleavage by phenanthrenequinone diimine complexes ofrhodium(III) shape-selective recognition and reactionrdquoJournal of the American Chemical Society vol 114 no 7 pp2303ndash2312 1992

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


genotoxicity due to the oxidative stress which arises as a resultof imbalance between free radical generations [19 20] Theantioxidant activity of metal complex is found to be inducedby both the identity of the metal and the ligands bound to it[21] The development of new metal-containing antioxidantagents have been reported by several research groups [22]Based on these findings and in continuation of our researchwork on coordination chemistry [23ndash28] we describe thesynthesis of a new Schiff base and its metal complexes with 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide fused to 3-formyl-2-hydroxy-1H-quinoline with the aim of obtainingmore potent pharmacological active compounds

2 Experimental

21 Analysis and Physical Measurements IR Spectra of thesynthesized Schiff base and its metal complexes wererecorded in KBr pellets on a Perkin-Elmer FT-IR instrumentin the range 4000ndash350 cmminus1 1HNMR spectra were recordedin 1198896-DMSOusing a Bruker DRX-400MHz instrument UV-

Visible spectra of the Cu(II) Co(II) and Ni(II) complexeswere recorded on Elico-SL 164 spectrometer in the range200ndash1000 nm in DMF solution (1 times 10minus3M) The FAB massspectra of ligand and its Cu(II) and Zn(II) complexes wererecorded on a JEOL SX 102DA-6000mass spectrometerdatasystem using argonxenon (6 kV 10mA) as the FAB gasThe accelerating voltage was 10 kV and the spectra wererecorded at room temperature using m-nitrobenzyl alcohol(NBA) as the matrix Elemental analysis was obtained fromHERAEUS C H and NndashO rapid analyzer and metal analysiswas carried out by following the standard methods ESRmeasurement was carried out on a BRUKER BioSpin Gmbhspectrometer working at microwave frequency of 9903GHzElectrochemistry of the Cu(II) complex was recorded on a600D seriesmodel electrochemical analyzer inDMFusing n-Bu4NndashClO

4as a supporting electrolyte The experiment was

carried out by using DPPH as reference with field set at 3200gauss Magnetic susceptibility measurements were made atroom temperature on a Gouy balance using Hg[Co(NCS)

4]

as the calibrant

22 Methods All the chemicals used were of reagent gradeand procured from Hi-media and Sigma Aldrich Solventswere dried and distilled before use Melting points of thenewly synthesized compounds were determined by elec-trothermal apparatus using open capillary tubes The metaland chloride contents were determined as per standard pro-cedures [29] The precursors 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide and 3-formyl-2-hydroxy-1H-quinolinewere prepared by the literature methods [16 30]

23 Synthesis of the Schiff Base HL Equimolar mixture of 5-chloro-3-phenyl-1H-indole-2-carboxyhydrazide (0001mol)and 3-formyl- 2-hydroxy-1H-quinoline (0001mol) with acatalytic amount of glacial acetic acid (1-2 drops) in ethanol(20mL) was refluxed on a water bath for about 7-8 h Thereaction was monitored by TLC The pale yellow solidseparated was filtered washed with little ethanol dried and

Cl

Cl

NNH

NH

NH

NH

NH

C6H5

C6H5

CONHNH2

OHC

O

O O

EtOHAcOH

CHC

+

4-5hr reflux

Scheme 1 Synthesis of Schiff base ligand HL

recrystallized from dioxane (Scheme 1) Yield 65 mp314∘C Anal Calcd for C

25H17O2N4Cl (Mr = 440) C 6810

H 385 N 1271 Found C 6825 H 391 N 1289 IR(KBr cmminus1) 3311 3229 and 3162 (]NHNH) 1674 and 1661(]C=O) 1608 (]C=N)

1H NMR (DMSO-1198896) 120575 1220 and 1200

(s 2H two CONH) 1160 (s 1H indole NH) 840 (s 1HHC=N) 710ndash820 (m 13H ArH)

24 Preparation of Cu(II) Co(II) Ni(II) Zn(II) Cd(II) andHg(II) Complexes of Schiff Base HL To the hot solutionof 5-chloro-N-(21015840-dihydro-21015840-oxoquinolin-31015840-yl methylene)-3-phenyl-1H-indole-2-carbohydrazide (HL) (0002mol) inethanol (30mL)was added a hot ethanolic solution (15mL) ofrespective metal chlorides (0002mol) The reaction mixturewas refluxed on a steam bath for about 4 h during which nosolid separated out An aqueous alcoholic solution of sodiumacetate (05 g) was added to the reaction mixture to maintaina pH of about 60ndash70 and reflux was continued for about anhour The reaction mixture was poured in the distilled waterThe separated solid complexes were collected by filtrationwashed with sufficient quantity of distilled water then withhot ethanol to apparent dryness and dried in a vacuumover anhydrous calcium chloride in a desiccator The meltingpoints of all the compounds are reported in Table 1

241 Cu(II) Complex of Schiff Base HL

Green Solid Yield 70 mp gt 340∘C Anal Calcd for[Cu(C

50H32O4N8Cl2)]H2O (Mr = 95954) C 6246 H 353


2O) 3283 and 3221 (]NHNH) 1639 (]C=O) 1548 (]C=N)


2 13769ndash17463

242 Co(II) Complex of Schiff Base HL

Light Brown Solid Yield 77 mp gt 340∘C Anal Calcd for[Co(C

50H32O4N8Cl2)]H2O (Mr = 95493) C 6276 H 355


2O) 3271 and 3230 (]NHNH) 1629 (]C=O) 1551 (]C=N)


Table1Ph

ysicalanalytic

alm

agnetic

susceptib

ilityand

molar

cond

uctanced

atao

fligandHLandits

complexes

Com

poun

dsMolecular

form

ula

MolW

tMP

(∘ C)

(Yield

in)

Elem

entalanalysis

()C

alcd

(Fou

nd)

Magm

oment120583

eff(BM

)Molar

cond

(120583M)

ohmminus1 cm

2molminus1

Colou

rM

CH

NCl

HL

C 25H

17O

2N4C

l44

0314(65)

mdash6810

(6825)

385

(391)

1271(1289)

805

(812

)mdash

mdashYello

wCu

complex

[Cu(C 5

0H32O

4N8C

l 2)]H

2O9595

4gt340(70)

661

(671)

6246(6259)353

(332

)1166(1174)

739(721)

179

31Green

Cocomplex

[Co(C 5

0H32O

4N8C

l 2)]H

2O95493gt340(77)

616

(626)

6276

(6292)355

(382)

1171(1186)

742(762)

501

24Brow

nNicom

plex

[Ni(C

50H

32O

4N8C

l 2)]H

2O95469gt340(79)

614

(619

)6278(6292)355

(369)

1171(1191)

742(759)

290

27Brow

n

Zncomplex

[Zn(C 2

5H16O

2N4C

l)(C

l)]H

2O5574

0gt340(69)

1171(1162)

5372(5399)322

(335)

1002(1019)1271(1289)

mdash49

Light

yello

w

Cdcomplex

[Cd(C 2

5H16O

2N4C

l)(C

l)]H

2O60

441gt340(71)

1856(1865)

4955(497

1)297

(281)

924(935)

1172(119

0)mdash

60Pale

yello

w

Hgcomplex

[Hg(C 2

5H16O

2N4C

l)(C

l)]67459

330(68)

2969(297

5)44

40(4461)236

(242)

828

(836)

1050(1066)

mdash50

Light

Yello

wHL=ligand



1 7447 ]

2 15977 ]

3 19518



50H32O4N8Cl2)]H2O (Mr = 95469) C 6278 H 355


2O) 3305 and 3218 (]NHNH) 1638 (]C=O) 1555 (]C=N)


1 9680 ]

2 15604 ]

3 25634



25H16O2N4Cl)(Cl)]H

2O (Mr = 55740) C 5372 H


2O) 3305 and 3218 (]NHNH) 1634 (]C=O)


1H NMR (DMSO-1198896) 120575 1312 (s 1H




25H16O2N4Cl)(Cl)]H

2O (Mr = 60441) C 4955 H


2O) 3293 and 3221 (]NHNH) 1637 (]C=O)


1H NMR (DMSO-1198896) 120575 1314 (s 1H




25H16O2N4Cl)(Cl)] (Mr = 67459) C 4440 H 236


25 Pharmacology


















(1)



2]H2O for Cu(II)



















2O


2O 2Cl and C

15H9NO species



1g rarr2Eg

2B1g rarr

2B2g and

2B1g rarr




4T1g (F) rarr



[Mass spectrum]

Data 10FEB02E028




100

50

0

100 150 200 250 300 350 400 450 500 550

mz

107

136 154

176 228230

289 307

328 348 392 411 450461

498

503 552 578

Scan number (6 12)

Date Feb 02 2010 1116

Note mdash

(a)

1051591times3100

50

0

600 650 700 750 800 850 900 950 1000 1050 1100

mz

614 648 664741 743 786 861 907

939941

997 1045

(b)




2]1

LFSE (k cal)]1

lowast ]2

]3












100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L



Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)






gt 119892perpgt 20023



lies in the d119911


(2075) gt 119892








minus 2119892




Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Table1Ph

ysicalanalytic

alm

agnetic

susceptib

ilityand

molar

cond

uctanced

atao

fligandHLandits

complexes

Com

poun

dsMolecular

form

ula

MolW

tMP

(∘ C)

(Yield

in)

Elem

entalanalysis

()C

alcd

(Fou

nd)

Magm

oment120583

eff(BM

)Molar

cond

(120583M)

ohmminus1 cm

2molminus1

Colou

rM

CH

NCl

HL

C 25H

17O

2N4C

l44

0314(65)

mdash6810

(6825)

385

(391)

1271(1289)

805

(812

)mdash

mdashYello

wCu

complex

[Cu(C 5

0H32O

4N8C

l 2)]H

2O9595

4gt340(70)

661

(671)

6246(6259)353

(332

)1166(1174)

739(721)

179

31Green

Cocomplex

[Co(C 5

0H32O

4N8C

l 2)]H

2O95493gt340(77)

616

(626)

6276

(6292)355

(382)

1171(1186)

742(762)

501

24Brow

nNicom

plex

[Ni(C

50H

32O

4N8C

l 2)]H

2O95469gt340(79)

614

(619

)6278(6292)355

(369)

1171(1191)

742(759)

290

27Brow

n

Zncomplex

[Zn(C 2

5H16O

2N4C

l)(C

l)]H

2O5574

0gt340(69)

1171(1162)

5372(5399)322

(335)

1002(1019)1271(1289)

mdash49

Light

yello

w

Cdcomplex

[Cd(C 2

5H16O

2N4C

l)(C

l)]H

2O60

441gt340(71)

1856(1865)

4955(497

1)297

(281)

924(935)

1172(119

0)mdash

60Pale

yello

w

Hgcomplex

[Hg(C 2

5H16O

2N4C

l)(C

l)]67459

330(68)

2969(297

5)44

40(4461)236

(242)

828

(836)

1050(1066)

mdash50

Light

Yello

wHL=ligand



1 7447 ]

2 15977 ]

3 19518



50H32O4N8Cl2)]H2O (Mr = 95469) C 6278 H 355


2O) 3305 and 3218 (]NHNH) 1638 (]C=O) 1555 (]C=N)


1 9680 ]

2 15604 ]

3 25634



25H16O2N4Cl)(Cl)]H

2O (Mr = 55740) C 5372 H


2O) 3305 and 3218 (]NHNH) 1634 (]C=O)


1H NMR (DMSO-1198896) 120575 1312 (s 1H




25H16O2N4Cl)(Cl)]H

2O (Mr = 60441) C 4955 H


2O) 3293 and 3221 (]NHNH) 1637 (]C=O)


1H NMR (DMSO-1198896) 120575 1314 (s 1H




25H16O2N4Cl)(Cl)] (Mr = 67459) C 4440 H 236


25 Pharmacology


















(1)



2]H2O for Cu(II)



















2O


2O 2Cl and C

15H9NO species



1g rarr2Eg

2B1g rarr

2B2g and

2B1g rarr




4T1g (F) rarr



[Mass spectrum]

Data 10FEB02E028




100

50

0

100 150 200 250 300 350 400 450 500 550

mz

107

136 154

176 228230

289 307

328 348 392 411 450461

498

503 552 578

Scan number (6 12)

Date Feb 02 2010 1116

Note mdash

(a)

1051591times3100

50

0

600 650 700 750 800 850 900 950 1000 1050 1100

mz

614 648 664741 743 786 861 907

939941

997 1045

(b)




2]1

LFSE (k cal)]1

lowast ]2

]3












100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L



Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)






gt 119892perpgt 20023



lies in the d119911


(2075) gt 119892








minus 2119892




Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



1 7447 ]

2 15977 ]

3 19518



50H32O4N8Cl2)]H2O (Mr = 95469) C 6278 H 355


2O) 3305 and 3218 (]NHNH) 1638 (]C=O) 1555 (]C=N)


1 9680 ]

2 15604 ]

3 25634



25H16O2N4Cl)(Cl)]H

2O (Mr = 55740) C 5372 H


2O) 3305 and 3218 (]NHNH) 1634 (]C=O)


1H NMR (DMSO-1198896) 120575 1312 (s 1H




25H16O2N4Cl)(Cl)]H

2O (Mr = 60441) C 4955 H


2O) 3293 and 3221 (]NHNH) 1637 (]C=O)


1H NMR (DMSO-1198896) 120575 1314 (s 1H




25H16O2N4Cl)(Cl)] (Mr = 67459) C 4440 H 236


25 Pharmacology


















(1)



2]H2O for Cu(II)



















2O


2O 2Cl and C

15H9NO species



1g rarr2Eg

2B1g rarr

2B2g and

2B1g rarr




4T1g (F) rarr



[Mass spectrum]

Data 10FEB02E028




100

50

0

100 150 200 250 300 350 400 450 500 550

mz

107

136 154

176 228230

289 307

328 348 392 411 450461

498

503 552 578

Scan number (6 12)

Date Feb 02 2010 1116

Note mdash

(a)

1051591times3100

50

0

600 650 700 750 800 850 900 950 1000 1050 1100

mz

614 648 664741 743 786 861 907

939941

997 1045

(b)




2]1

LFSE (k cal)]1

lowast ]2

]3












100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L



Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)






gt 119892perpgt 20023



lies in the d119911


(2075) gt 119892








minus 2119892




Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of













(1)



2]H2O for Cu(II)



















2O


2O 2Cl and C

15H9NO species



1g rarr2Eg

2B1g rarr

2B2g and

2B1g rarr




4T1g (F) rarr



[Mass spectrum]

Data 10FEB02E028




100

50

0

100 150 200 250 300 350 400 450 500 550

mz

107

136 154

176 228230

289 307

328 348 392 411 450461

498

503 552 578

Scan number (6 12)

Date Feb 02 2010 1116

Note mdash

(a)

1051591times3100

50

0

600 650 700 750 800 850 900 950 1000 1050 1100

mz

614 648 664741 743 786 861 907

939941

997 1045

(b)




2]1

LFSE (k cal)]1

lowast ]2

]3












100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L



Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)






gt 119892perpgt 20023



lies in the d119911


(2075) gt 119892








minus 2119892




Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of















2O


2O 2Cl and C

15H9NO species



1g rarr2Eg

2B1g rarr

2B2g and

2B1g rarr




4T1g (F) rarr



[Mass spectrum]

Data 10FEB02E028




100

50

0

100 150 200 250 300 350 400 450 500 550

mz

107

136 154

176 228230

289 307

328 348 392 411 450461

498

503 552 578

Scan number (6 12)

Date Feb 02 2010 1116

Note mdash

(a)

1051591times3100

50

0

600 650 700 750 800 850 900 950 1000 1050 1100

mz

614 648 664741 743 786 861 907

939941

997 1045

(b)




2]1

LFSE (k cal)]1

lowast ]2

]3












100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L



Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)






gt 119892perpgt 20023



lies in the d119911


(2075) gt 119892








minus 2119892




Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


[Mass spectrum]

Data 10FEB02E028




100

50

0

100 150 200 250 300 350 400 450 500 550

mz

107

136 154

176 228230

289 307

328 348 392 411 450461

498

503 552 578

Scan number (6 12)

Date Feb 02 2010 1116

Note mdash

(a)

1051591times3100

50

0

600 650 700 750 800 850 900 950 1000 1050 1100

mz

614 648 664741 743 786 861 907

939941

997 1045

(b)




2]1

LFSE (k cal)]1

lowast ]2

]3












100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L



Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)






gt 119892perpgt 20023



lies in the d119911


(2075) gt 119892








minus 2119892




Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


100

50

0

684817

80 100 120 140 160 180 200 220 240 260 280 300 320

8690

107120

136

154

171 199 214219

250

270 289 307325

[Mass spectrum]

Data 10FEB02E028

Sample M5L



Scan number (1 2)

Date Feb 02 2010

Gulbarga number 827

mz

(a)

100

50

0

684817

340 360 380 400 420 440 460 480 500 520 540 560 580

350 369

440

469504

539

541

559576

(b)






gt 119892perpgt 20023



lies in the d119911


(2075) gt 119892








minus 2119892




Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Cl

Cl

Cl

Cl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

C

C

C

HC

HC

HC

O

C

C

O

O O

O

O

O

O

O

O

OO

minusH2O

Ni

Ni

Ni

Ni

mz 937 939 941 (25 50 70)

mz 498 500 (50 38)

minus

minus

HN

mz 244 (18)

+∙

+∙

+

M+∙

CO

+

O∙

955 957 959 (10 6 3)

H2O





15H10N3OCl

Cl

Cl

Cl

C6H5

C6H5

C6H5

C6H5

N

N

N

N

N

N

N

N

NH

NH

NH

NH

NH

NH

NH

HC

HC

HC

HC

C

CO

C

C

O

O

O

O

O

O

OH2O

minusH2O

Zn

Cl

Zn

Zn

Zn

mz 539 541 543 (48 72 20)

mz 469 (48)

minus

HN

mz 250 (60)

557 559 561 (10 18 15)

minus2 Cl

+∙

+∙

+∙

M+∙

∙







10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


10991

10

9

8

7

6

5

4

3

1933

Wei

ght (

mg)

Weight (mg)

3529 100 200 300 400 500 600 700 8061

Temperature (∘C)

0235100

minus05

minus10

minus15

minus20

minus25

minus2752

Der

ivat

ive w

eigh

t (m

gm

in)






12

09

06

03

0

minus03

minus06

minus09

minus12

minus15

minus18

minus21

Potential (V)100 090 080 070 060 050 040 030 020

Curr

ent (1e

minus6

A)












4NndashClO

4as a




119901







Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




Cu complex



















Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




Cald Obsd1 6953 34765 00606 000367 1000 (1) 1 0 0 127112 127028 12712 7786 38930 00678 000460 1253 (1) 1 0 0 113613 113461 12713 10094 50470 00879 000739 2013 (2) 1 1 0 87633 87561 12714 12115 60575 01055 001113 3032 (3) 1 1 1 73014 72995 12715 14757 73785 01284 001649 4493 (4) 2 0 0 59992 5998 12716 16104 80522 01400 001962 5346 (5) 2 1 0 55021 5499 12717 18325 91625 01592 002535 6907 (7) mdash 48385 48374 12718 20999 10199 01770 003135 8542 (9) 2 2 1 3 0 0 43519 43501 12719 23474 11737 02034 004137 11272 (11) 3 1 1 37871 37867 127110 25247 12623 02185 004776 13013 (13) 3 2 0 35254 35247 127111 32675 163375 02812 007912 21558 (22) 3 3 2 27393 27384 127112 38105 19052 03264 01065 29032 (29) 5 2 0 23599 23597 127113 45866 22933 03896 01518 41370 (41) 6 2 1 19771 19768 127114 48416 24208 04100 01681 45814 (46) 6 3 1 18780 18785 127115 61823 30911 05137 02639 71907 (72) 6 6 0 14995 14994 1271







2313 kb94166557

43612322




0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


0

10

20

30

40

50

60

70

80


Free

radi

cal s

cave

ngin

g ac

tivity

()

Compounds

10120583g50120583g100120583g


Cl

Cl

Cl

C6H5

C6H5

NH

NH

NH

NH

C

C

OO

OO

M

M = Cu Co and Ni

H2O

H2O

M = Zn and Cd

Hg

N

N

N

N

CH

Cl C6H5

NH

NH

CO

OM

N

N

CH

Cl

Cl C6H5

NH

NH

CO

O

N

N

CH

CH



4 Conclusions





Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Acknowledgments


References























3and




















































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of














































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of














Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of










Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Documents

Research Article Synthesis, Characterization, …downloads.hindawi.com/journals/bca/2013/315972.pdfResearch Article Synthesis, Characterization, Antimicrobial, DNA Cleavage, and Antioxidant