ORI GIN AL PA PER

Synthesis, Crystal Structure, Vibrational and OpticalProperties of (Hdea)4(V7O19F)•0.42H2O, an Original(V7O19F)42 Cluster Oxyfluoride

Issam Omri • Mohsen Graia • Tahar Mhiri

Received: 7 May 2014

� Springer Science+Business Media New York 2014

Abstract Synthesis, crystal structure, IR and Raman spectroscopies and optical

analysis are reported for a new fluorovanadate with organic cations (Hdea)4(V7

O19F)•0.42H2O (dea: diethylamine). The title compound crystallizes in ortho-

rhombic system, space group P212121, a = 11.486 (5) A, b = 14.779 (5) A,

c = 23.243 (5) A, Z = 4, V = 3,946 (2) A3, R = 0.025 with 6,936 reflections. The

atomic arrangement can be described as an alternation of inorganic and organic

layers. The anionic layer is built up of original clusters (V7O19F)4- which are

composed of three VO5F octahedra and four VO4 tetrahedra combined via shared

edges and corners. The cohesion between the fluorovanadate groups, organic cations

and water molecules is provided by a network hydrogen-bonding. The IR and

Raman spectra exhibit characteristic bands of all groups present in the structure. The

optical band gap is determined to be 2.5 eV by UV–Vis-T90? diffuse reflectance

spectra, which revealed the nature of semiconductor.

Keywords Fluorovanadate � X-ray diffraction � IR and Raman spectroscopies �Diethylamine

Electronic supplementary material The online version of this article (doi:10.1007/s10876-014-0768-3)

contains supplementary material, which is available to authorized users.

I. Omri (&) � T. Mhiri

Laboratoire physico-chimie de l’etat solide, Faculte de Sciences, Universite de Sfax, BP 1171,

3038 Sfax, Tunisia

e-mail: issamomri@yahoo.fr

M. Graia

Laboratoire de Materiaux et Cristallochimie, Faculte des Sciences, Universite de Tunis El Manar,

El Manar, 2092 Tunis, Tunisia

123

J Clust Sci

DOI 10.1007/s10876-014-0768-3

Introduction

The interest in coordination chemistry of vanadium has increased in the last decades

because of its catalytic and medicinal importance [1–4]. A wide range of structural

variations associated with their diverse reactivity are also making them the center of

continuous research activities [5–7]. Oxide-fluoride transition metal compounds have

been interesting for magnetism [8–12], nonlinear properties such as piezoelectricity

[12]. Detailed studies of the vanadium fluorides and oxyfluorides by Lightfoot,

Zubieta and others demonstrate a complex structural chemistry, including oligomeric,

chain and ladder building blocks [9–29]. Vanadium complexes with organic ligands

are often less toxic and can have improved aqueous solubility and lipophilicity [30].

The most important oxidation states of vanadium are ?3, ?4 and ?5 and the V

(V) compounds are the most commonly observed in the form of compounds of the

vanadate ion, VO43- [31–37]. The investigation of the structure and properties of

these compounds and their similarities are interested. In this work we present here the

synthesis, characterization, crystal structure and optical properties of a new

fluorovanadate (Hdea)4(V7O19F)•0.42H2O.

Experimental

Materials and Physical Measurements

The chemicals and solvents used in this work were of analytical grade, available

commercially, and were used without further purification.

The infrared spectrum was recorded at room temperature on a Perkin Elmer

SpectrumTM 100 FT-IR spectrometer in the 4,000–400 cm-1 region. A Raman

spectrum was measured with a LABRAM HR 800 triple monochromator in the

region 4,000–50. The Optical absorption spectra were measured at room temper-

ature using a T90?-UV–Vis spectrometer within the range of 300–700 nm. BaSO4

was used as a reference material. Optical absorption of the films was determined

from direct transmission measurements performed using a conventional UV–visible

spectrophotometer (HITACHI, U-3300).

Synthesis of (Hdea)4(V7O19F)•0.42H2O

The title compound was synthesized through the reaction of 0.6 ml of diethylamine,

0.190 g of vanadium (V) oxide and 0.063 g of fumaric acid in 20 ml of water. The

reaction mixture is stirred until homogenized. The pH of this mixture was adjusted

to nine using a hydrofluoric acid. Red crystals were separated after four months by

slow evaporation at room temperature. The initial objective was the formation of a

complex of vanadium with fumaric acid ligand. After analysis of the obtained

compound, it appears that the fumaric acid was not reacted. Yet in the absence of

this acid the studied phase is not obtained. This acid may be playing a catalytic role

in the formation of this compound. We cannot be explained this eventual role.

I. Omri et al.

123

X-Ray Crystallography

A suitable single crystal of the title compound was chosen for the structure

determination and refinement. It was selected under a polarizing microscope and

was mounted on a glass fibre. The data collected at room temperature using a Bruker

APEX II Kappa CCD diffractometer with graphite-monochromated MoKa radiation

[38]. The structure was determined by direct methods, completed by Fourier

difference syntheses with SIR97 [39], and refined against F2 using SHELX-2013

[40] included in the WingX software package [41]. No higher symmetry or unit

cells were found by examination with PLATON [42]. Before taken account the

presence of water molecule the final R and wR2 were 0.032 and 0.083, respectively

and the difference Fourier map reveals a residual peaks Q1 with a significant

intensity (Q1 = 1.77, Q2 = 0.38). The assignment of this residual peak to an

oxygen atom (Ow) with full occupancy leads to a final R1 = 0.027 and

wR2 = 0.069. Because of high thermal motion of Ow (Uiso = 0.318) atom, the

ratio occupation of Ow was refined. This refinement leads to a partial occupation

(s = 0.42) and the final R1 and wR2 values were 0.025 and 0.061, respectively.

Concerning the vanadium coordination, at first we assumed that it’s only surrounded

by oxygen atoms. This hypothesis doesn’t lead to the electrical neutrality of the

compound and the calculated valence sums for each cation (V1, V3, and V5) differs

to (?V) value. Indeed, the vanadium sums for the hypothetical VO6 octahedra are

5.157, 5.174 and 5.120 for V1, V3 and V5, respectively. This calculation leads to a

better convergence and the electrical neutrality considering the studied compound

(Hdea)4(V7O19F)•0.42H2O. Non-hydrogen atoms were refined anisotropically.

Hydrogen atoms were located from the difference Fourier map and refined. Crystal

data and details on data collection and refinement are summarized in Table 1. The

atomic coordinates and the displacement parameters are reported in Tables S1 and

S2. DIAMOND-2 [43] package was used for molecular graphics.

Result and Discussion

Structural Study

(Hdea)4(V7O19F)•0.42H2O crystallizes in the space group P212121. The asymmetric

unit contains four diethylammonium cations, one fluorovanadate anion (V7O19F)4-

and one water molecule having 0.42 occupancy. The structure consists of alternating

of anionic and cationic layers perpendicular to the c-axis (Fig. 1). The anionic layers

contain the fluorovanadate (V7O19F)4- clusters and water molecules. This

(V7O19F)4- anions are located in the (a, c) planes at y = 0 and y = 0.5 and those

for organic groups at y = 0.25 and 0.75. In addition, the (V7O19F)4- polyanions and

water molecules are located in tunnels parallel along c-axis delimited by the organic

groups (Fig. 2). The original (V7O19F)4- cluster is non-centrosymmetric and is

composed of three distorted VO5F octahedra and four fairly regular VO4 tetrahedra

combined via shared edges and corners (Fig. 3). The distortion indexes of these

polyhedra groups confirm these results and vary between 8.79 and 8.89 % for VO5F

Properties of (Hdea)4(V7O19F)•0.42H2O

123

octahedra and between 3.26 and 3.81 % for VO4 tetrahedra [44]. The V–Oterminal

bond distances range between 1.589 (3) and 1.629 (3) A, while the V–Obridging bond

distances are longer, with an observed range of 1.707 (3)–1.995 (3) A. The V–F

distances vary from 2.319 (2) to 2.336 (2) A. The V–F bonds are longer than those

in related compounds [14, 45]. The O–V–O angles for cis and trans bonds are in the

range of 83.8 (1)–114.4 (1)� and 155.6 (1)–157.0 (1)�, respectively. The V–O bonds

and O–V–O angles of the (V7O19F)4- are in agreement with those reported in

literature [46]. The oxidation state of vanadium is ?5 in (VO5F)6- and in (VO4)3-.

This assignement of oxidation state is consistent with the overall charge balance of

the compound and confirmed by the bond strength calculations around vanadium

atoms using the following equation proposed by Brown for vanadium oxide

compound: Si = exp [(R0 - Ri)/B], where Si is the bond valence of bond ‘i’, R0 is a

constant dependent upon the bonded elements, Ri is the bond length of bond ‘i’, and

Table 1 Crystal data, structure solutions and refinements for (Hdea)4(V7O19F)•0.42H2O

Compound (Hdea)4(V7O19F)•0.42H2O

Empirical formula C16H48.84 F4O19.42V7

Formula weight 983.73 g mol-1

Temperature 293 (2) K

Wavelength k = 0.71073 A

Crystal system Orthorhombic

Space group P212121

Unit cell dimensions a = 11.486 (5) A

b = 14.779 (5) A

c = 23.243 (5) A

Volume 3946 (2) A3

Z 4

Calculated density 1.656 g cm-3

l 1.66 mm-1

F(000) 1993

h range for data collection 3.3�–25.3�Limiting indices -13 B h B 13

-17 B k B 17

-11 B l B 27

No. of coll. ref 17438

No. of indep. ref. 6936 (Rint = 0.022)

No. of ref. with [I [ 2r(I)] 6481

Goodness-of-fit 1.02

Final R indices [I [ 2r(I)] R1 = 0.025; wR = 0.061

Parameters 441

Dqmax/Dqmin 0.35/-0.23 eA-3

Measurement Bruker APEX II Kappa CCD

CCDC ID 989142

I. Omri et al.

123

B equals 0.37. R0 (VV–O) = 1.803 and R0 (VV–F) = 1.71 [47, 48]. Selected bond

lengths and bond angles are listed in Table 2.

The cationic layers contain non-centrosymmetric diethylammonium (C4H12N)?

with a range of C–C and C–N bond lengths from 1.463 (9) to 1.51 (1) A and from

1.402 (8) to 1.524 (8) A, respectively. An extended hydrogen-bonding network is

observed between the (V7O19F)4- clusters, (C4H12N)? cations and water molecules

via N–H–O and O–H–O hydrogen bonds. All hydrogen bonds are weak with a range

of N–O bond lengths from 2.735 to 2.980 A [49] (Table S3). Figure S1 indicate that

each fluorovanadate (V7O19F)4- anions is surrounded by eight organic cations and

one water molecule.

Spectroscopic Study

To gain more information on the crystal structure, we have undertaken a spectroscopic

study using infrared and Raman spectroscopies. The FTIR spectrum of the title

compound (Hdea)4(V7O19F)•0.42H2O is shown in Fig. S2. The bands centered

between 500 and 1,000 cm-1 can be attributed to various vibration of V–O and V–F

types. Indeed, the band located at 952 cm-1 corresponds to V=O stretching mode. The

bridging asymmetric vibrations of V–O–V possibly appear in the range 686 and

824 cm-1, while the band at 564 cm-1 is assigned to the symmetric V–O–V stretching

and the vibrations of (V–F) [50–53]. The presence of protonated amines and water

molecules is shown by the bands within 3,458–3,603 cm-1 region and around

1,607 cm-1, which may be attributed to (N–H, O–H) stretching and bending,

respectively. Additional bands in the region 1,046–1,388 cm-1 are characteristic for

the stretching vibrations of C–N and C–C. The bands in the range 2,719–2,980 cm-1

Fig. 1 Crystal packing of (Hdea)4(V7O19F)•0.42H2O compound along the c-axis. The drawing show theintermolecular hydrogen bonds contacts which are represented by dotted line

Properties of (Hdea)4(V7O19F)•0.42H2O

123

and around 1,472 cm-1 possibly correspond to C–H stretching and bending,

respectively [54, 55].

The structure information was further provided by Raman spectroscopy, as

shown in Fig. S3. Two low-frequency Raman peaks at 180 and 209 cm-1 are

assigned to the bending mode of (O2V2)n. The bands located in the range

235–413 cm-1 are assigned to the bending vibration of the V=O bonds. The

bridging asymmetric vibrations of V–O–V are located at 613 and 867 cm-1 while

the low band at 938 cm-1 is assigned to the ms (V–O–V) stretching mode. Three

bands within 951–1,002 cm-1 region are attributed to the terminal oxygen (V=O)

stretching mode [50, 56]. The Raman spectrum reveals absorptions in the range

1,416–1,462 cm-1 and 2,893–2,944 cm-1, which could be attributed respectively to

Fig. 2 a Projection along the c-axis of the cationic layers and b crystal packing along the c-axis showingthe tunnels parallel of (V7O19F)4- clusters and water molecules delimited by the organic groups

Fig. 3 a View of fluorovanadate cluster with atom labeling for the compound (Hdea)5(HV10O28). b Apolyhedral representation of the polyanion

I. Omri et al.

123

Table 2 Selected bond and angle lengths and BVS calculations for (Hdea)4(V7O19F)•0.42H2O

Bond length (A) Bond angles (�)

Octahedron V(1)O5F

V1–O2 1.597 (3) O2–V1–O19 103.5 (1) O3–V1–O6 156.4 (1)

V1–O19 1.821 (2) O2–V1–O3 103.5 (1) O2–V1–O4 100.2 (1)

V1–O3 1.827 (3) O19–V1–O3 90.6 (1) O19–V1–O4 156.0 (1)

V1–O6 1.963 (3) O2–V1–O6 99.9 (1) O3–V1–O4 87.5 (1)

V1–O4 1.970 (3) O19–V1–O6 86.9 (1) O6–V1–O4 85.3 (1)

V1–F 2.336 (2)

Rsi = 5.104

Tetrahedron V(2)O4

V2–O1 1.629 (3) O1–V2–O13 108.2 (1) O1–V2–O14 103.7 (1)

V2–O13 1.713 (3) O1–V2–O6 107.5 (1) O13–V2–O14 113.3 (1)

V2–O6 1.715 (3) O13–V2–O6 109.3 (1) O6–V2–O14 114.4 (1)

V2–O14 1.836 (3)

Rsi = 5.058

Octahedron V(3)O5F

V3–O5 1.589 (3) O5–V3–O3 103.7 (2) O8–V3–O11 155.6 (1)

V3–O3 1.821 (2) O5–V3–O8 102.8 (1) O5–V3–O10 99.1 (1)

V3–O8 1.839 (3) O3–V3–O8 90.6 (1) O3–V3–O10 157.0 (1)

V3–O11 1.956 (3) O5–V3–O11 101.0 (1) O8–V3–O10 87.2 (1)

V3–O10 1.995 (3) O3–V3–O11 88.9 (1) O11–V3–O10 83.8 (1)

V3–F 2.319 (2)

Rsi = 5.092

Tetrahedron V(4)O4

V4–O12 1.611 (3) O12–V4–O11 108.2 (2) O12–V4–O15 104.5 (1)

V4–O11 1.706 (3) O12–V4–O4 106.0 (1) O11–V4–O15 114.5 (1)

V4–O4 1.733 (3) O11–V4–O4 109.6 (1) O4–V4–O15 113.4 (1)

V4–O15 1.847 (3)

Rsi = 5.076

Octahedron V(5)O5F

V5–O18 1.592 (3) O18–V5–O19 103.6 (1) O8–V5–O13 156.6 (1)

V5–O19 1.826 (2) O18–V5–O8 102.0 (1) O18–V5–O16 100.0 (1)

V5–O8 1.841 (3) O19–V5–O8 90.1 (1) O19–V5–O16 156.4 (1)

V5–O13 1.950 (3) O18–V5–O13 101.1 (1) O8–V5–O16 86.5 (1)

V5–O16 1.995 (3) O19–V5–O13 88.6 (1) O13–V5–O16 85.4 (1)

V5–F 2.328 (2)

Rsi = 5.066

Tetrahedron V(6)O4

V6–O7 1.624 (3) O7–V6–O10 107.8 (2) O7–V6–O9 104.8 (1)

V6–O10 1.709 (3) O7–V6–O16 108.4 (1) O10–V6–O9 113.0 (1)

V6–O16 1.727 (3) O10–V6–O16 110.2 (1) O16–V6–O9 112.4 (1)

V6–O9 1.831 (3)

Rsi = 5.066

Properties of (Hdea)4(V7O19F)•0.42H2O

123

Table 2 continued

Tetrahedron V(7)O4

V7–O17 1.607 (3) O17–V7–O14 106.3 (2) O17–V7–O15 104.2 (2)

V7–O14 1.742 (3) O17–V7–O9 108.0 (2) O14–V7–O15 111.8 (1)

V7–O9 1.744 (3) O14–V7–O9 113.8 (1) O9–V7–O15 112.1 (1)

V7–O15 1.759 (3)

Rsi = 5.176

N1–C2 1.478 (6) C2–N1–C3 114.6 (4)

N1–C3 1.496 (6) C7–N2–C6 115.6 (5)

N2–C7 1.447 (7) C11–N3–C10 114.4 (4)

N2–C6 1.524 (8) C14–N4–C15 113.0 (6)

N3–C11 1.478 (6) N3–C11–C12 111.4 (5)

N3–C10 1.496 (6) C4–C3–N1 113.1 (5)

N4–C14 1.402 (8) C9–C10–N3 111.0 (5)

N4–C15 1.528 (9) C1–C2–N1 112.1 (5)

C11–C12 1.485 (8) N2–C7–C8 110.9 (5)

C3–C4 1.463 (9) C5–C6–N2 111.9 (5)

C10–C9 1.486 (9) C16–C15–N4 110.7 (6)

C2–C1 1.476 (7) N4–C14–C13 109.7 (7)

C7–C8 1.48 (1)

C6–C5 1.47 (1)

C15–C16 1.49 (1)

C14–C13 1.51 (1)

Table 3 Assignments of the IR and Raman wave-numbers for (Hdea)4(V7O19F)•0.42H2O

FT-IR (cm-1) Assignment Raman (cm-1) Assignment

564 ms (O–V2) ? m (V–F) 180 d (O2V2)

686 mas (O–V2) 209

779 235 d (O–V)

824 276

952 m (V–Oterminal) 321 d (O2V)

1,046 m (C–N) 413 d (O2V) ? m (V–F)

1,064 613 mas (O–V2)

1,160 867

1,388 m (C–C) 938 ms (O–V2)

1,472 d (CH) 951 m (V–Oterminal)

1,607 d (NH) ? d (OH) 977

1,691 1,002

2,719 m (CH) 1,165 m (C–C)

2,980 1,416 d (CH)

3,458 m (NH) ? mOH (H2O) 1,462

3,603 2,893 m (CH)

2,944

I. Omri et al.

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the bending and stretching modes of C–H. The band situated at 1,165 cm-1 is

assigned to stretching vibration of the C–C bonds [57]. The infrared and Raman

peaks frequencies are reported in Table 3.

Optical Properties

The UV–Vis–NIR diffuse reflectance spectrum of (Hdea)4(V7O19F)•0.42H2O in the

region 300–720 nm is displayed in Fig.S4a. Absorption (K/S) data are calculated

from the Kubelkae–Munk function: F = (1-R)2/2R = K/S, where R is the

reflectance, K is the absorption, and S is the scatteing [52]. In a K/S versus k(nm) plot, extrapolating the linear par of the rising curve to zero provides the onset

of absorption at 2.5 eV for (Hdea)4(V7O19F)•0.42H2O. The reflectance spectrum

measurement revealed the nature of semiconductor. The UV–Vis absorption

spectrum exhibits two absorption bands at 264 and 420 nm corresponding to an

octahedral environment such as in decavanadates [58] (Fig. S4b). Figure S5 shows

the UV/Vis transmission of the (Hdea)4(V7O19F)•0.42H2O film measured at room

temperature.The UV–Vis transmission spectrum mainly consists of two bands,

centered at 330 and 360 nm. These bands are observed in the analysis of solid

sample or dissolved sample in aqueous solution. These bands can be assigned to

charge-transfer (CT) transitions of the type p(O) ? d(V) (between 250 and

approximately 400 nm) [30]. This can be explain the solubility and stability of the

new polyanion in water.

Conclusion

A new fluorovanadate (Hdea)4(V7O19F)•0.42H2O has been synthesized by slow

evaporation from aqueous solutions and characterized by IR and Raman spectros-

copies. The structure consists of alternating of anionic and cationic layers

perpendicular to the c-axis. Recently, We have shown an original (V7O19F)4-

cluster which is composed of three distorted VO5F octahedra and four fairly regular

VO4 tetrahedra combined via shared edges and corners. The cohesion between the

(V7O19F)4- clusters, (C4H12N)? cations and water molecules is provided by a

network hydrogen bonding. The IR and Raman spectra exhibit characteristic bands

of all groups present in the structure. The optical band gap is determined to be

2.5 eV by UV–Vis-T90? diffuse reflectance spectra, which revealed the nature of

semiconductor.

Supplementary Data

CCDC 989142 contains the supplementary crystallographic data for this paper.

These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/

retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union

Road, Cambridge CB2 1EZ, UK; fax: (?44) 1223 336 033; or e-mail:

deposit@ccdc.cam.ac.uk.

Properties of (Hdea)4(V7O19F)•0.42H2O

123

Acknowledgments The crystal data collection of the title compound was done in the ‘‘Department of

Chemistry, Faculty of Sciences of Sfax, University of Sfax, BP 1171, 3038 Sfax, Tunisia’’. We are

grateful to Abdelhamid Ben Salah who supervised this experiment.The spectrum Raman was done in

‘‘Laboratory of ferroelectric materials, Faculty of Sciences of Sfax, University of Sfax, BP 1171, 3038

Sfax, Tunisia. We grateful to Hamadi Khemkhem who supervised this experiment.

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Properties of (Hdea)4(V7O19F)•0.42H2O

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