Indian Journal of ChemistryVol. 21A, November 1982, pp. 1074-1075

Some Novel Adducts of N-{Substituted-pheny ljcyclo hex y1)-2-merca ptoacetamide

with Tin{II) Chloride

R C MEHROTRA. (Miss) HEMANT SHARMA,ANIL KUMAR. VINOD SHARMA & B P BACHLAS'

Department of Chemistry, University of Rajasthan,Jaipur 302004

Received 24 March 1982; revised and accepted 20 May 1982

Addition products of the type SnClz.L and SnCI2.2L, where L=ArNHCOCH2SH [Ar=C6H,. p-CIC6H4, p-CH3C"H •. 3,6-(CH')2C6H3, 3,5-(CH,l2C.H" 2,6-{CH.l),C"H3,p-OCH,C"H. andC6H, ,] have been synthesised by the reaction of anhydrousstannous chloride and the ligand (L) in I: I and I: 2 molar ratios inmethanol. The products have been characterised on the basis ofelemental analyses. conductance measurements in nitrobenzene andinfrared studies.

Numerous adducts of tin(ll) halides with nitrogen andoxygen donor ligands are known I -3, but only scantyyet interesting studies have been made with sulphurdonor ligands" -6, using Mossbauer spectroscopy. Inview of this we have synthesised adducts of stannouschloride with the sulphur donor ligands X-NHCOCHzSH, where X = C6H5; p-CIC6H4; p-CH3C6H4; 2,6-(CH)zC6H3; 3,6-(CH3)zC6H3; 3,5-(CH3}zC6H3; p-(OCH3)C6H4 and C6H II'

Reagent grade (BDH) tin dichloride dihydrate wasdehydrated as recommended by Vogel? and stored invacuo. Methanol was dried and distilled overmagnesium methoxide 7.

Syntheses of ligands- The ligands were synthesisedand recrystallised before use using the literaturemethod". Their purities were checked by TLC usingiodine as a developer. Mercapto group was estimatediodometrically. Of the ligands used in the presentstudy, N-(isomeric xylyl)- and N-(cyclohexyl)-2-mercaptoacetamides are new ones.

Syntheses of tin(/l) adducts+ These adducts weresynthesised by adding methanolic solution ofanhydrous stannous chloride to the methanolicsolution of the ligand, in varying molar ratios (I : I andI : 2). The reaction mixture was invariably refluxedunder nitrogen for I hr. The product was precipitatedby the addition of either dried petroleum ether orbenzene and then filtered and dried in vacuo andanalysed" for sulphur, nitrogen, tin and chlorine. Theresults are listed in Table I. IR spectra were scanned ona double beam Perkin-Elmer 577 IR spectrophoto-meter. Conductance measurements were carried outon a conductivity bridge type 302 S.R. No. 471.

The reactions between stannous chloride and N-(substituted aryl or cyclohexyl)-2-mercaptoacetamide

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in I: I and I: 2 molar ratios gave correspondingad ducts, Initially the products are soluble in methanolbut once the solvent is stripped off they becomeinsoluble in polar and non-polar solvents. They arenon-conducting in nitrobenzene and decomposearound 200c without melting. They are polymeric andhydrolytically and thermally stable.

In all the derivatives both I'NH and I'C =0 shift tolower wave numbers in comparison to their positionsin ligand spectra indicating coordination through NHand C = 0 groups of ligands in the complexes.Normally Sn-N bond is weaker relative to Sn-O andSn-S bonds: therefore, in the presence of both carbonyl

Table \ ..Characterisation Data' of N-Substituted-2-mercaptoacetarnide Adducts with SnCl1

Product(Molar ratio of reactants)

SnCI2·C.H,NHCOCH2SH(I : I)

SnCI2.p-CIC6H4NHCOCH1SH(I: Ii

SnCil·p-CH3C6H4NHCOCH2SH(I: I)

SnCI2·3,5-(CH3hC.H3NHCOCHzSH(I : I)

SnCil·2.6,{CH3)2C"H3NHCOCH'lSH(I : I)

SnCI2·2.5-(CH3hC.H3NIKOCH2SH(1 : I)

SnCI2·p-(OCH 3)C6H4N HCOCH 2SH(I : I)

SnClz·C6H" NHCOCH1Sli(I : I)

SnCi2·2(C6H,NHCOCH2SH)(I: 2)

SnCI2·2(p-CIC.H4NHCOCH2SH)(I: 2)

SnCI1·2(p-CH3C.H4NHCOCH1SH)(1 : 2)

SnCi1·2[3.5-(CH3)lC6H,NHCOCH2SH](I: 2)

SnClz·2[2,6-{CH3)lC.H3NHCOCHzSH](1 : 2)

SnClz·2[2.5-(CH3)lC.H,NHCOCHzSH](I: 2)

SnClz·2[p-(OCH3)C6H,NHCOCHzSH](I: 2)

SnCI2.2[C.H, ,NHCOCH1SH](I: 2)

colour Dec.,'(yield. m.p.

~;,) (T)

Yellow 218(80)

White 226(82)

Yellow 221(75)

White 225(80)

White 227(85)

White 223(85)

White 225(90)

Yellow 215(85)

White 231(85)

White 228(85)

White 221(85)

White 230(85)

White 231(85)

White 228(85)

White 232(85)

Light- 236yellow

(90)

·Satisfactory elemental analyses were obtained for all thecomplexes.

oxygen and mercapto sulphur, the possibility ofcoordination through nitrogen is ruled out at least insolution state. But, in the solid state extendedinteraction involving coordination through nitrogenmay predominate.

In 1: 1 and 1: 2 adducts slight lowering in the vNHmode by 10-40 cm" 1 has been observed in the N-(phenyl)-, N-(p-chlorophenyl)-, N-(3,5-xylyl)-, N-(2,5-xylyi)-, and N-(cyciohexyi)-2-mercaptoacetamideadducts of stannous chloride. However, in N-(p-tolyl)-2-mercaptoacetamide adduct, no change in the vNHhas been observed. The I'NH mode moves towards ahigher wave number (5-30 cm I) in N-(2,6-xylyl)- andN-(p-methoxyphenyl)-2-mercaptoacetamide adductsor stannous chloride. Also no I'SH vibrations havebeen observed in most of the chelated complexes,although in the unchelated ligands very weakvibrations around 2550-2580 cm :" have been

NOTES

observed. Further, a lowering of 20-90 ern -I has beenobserved in vC = 0 frequency relative to unchelatedligands.

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151.3 Hsu C C & Geanangel R A, Inorg Chern, 16 (1977) 2529.4 Cassidy J E, Moser W. Donaldson J D, Jelen A & Nicholson D

G, J chem Soc (A), (1970) 173.

5 Donaldson J D & Nicholson D G. J chem Soc(A), (1970) 145.

6 Cusack P A, Smith P J & Donaldson J D. Inorg chim Acta, 46(1980) L73.

7 Vogel A I, A text book of practical organic chemistry (Longrnans,London), 1955.

8 Vogel A I. A text book of quantitative inorganic chemistry(Longmans, London), 1961.

9 Bateja S, Ph.D Thesis, University of Rajasthan, Jaipur, 1978.

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