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Characterization and Crystal Structure of Trans-Dichloro(Bis-Thiocarbohydrazide) Cadmium(II).

Byline: MOHAMMAD HAKIMI, NOUROLLAH FEIZI, FATEMEH ABBASI, REZA TAKJOO, ESTHER SCHUH AND FABIAN MOHR

Summary

The preparation and spectroscopic characterization of trans-dichloro(bis- thiocarbohydrazide) cadmium(II) using UV-Vis, Raman and IR spectroscopies is reported is reported in this paper. Molecular structure of the complex was determined by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic crystal system, space group P21/n, Z = 4, V = 594.91(5) A3 with unit cell parameters a = 8.6136(4) A, b = 5.7881(3) A, c = 12.0980(6) A and b = 99.487(5) o. The cadmium (II) ion is bound to sulfur and nitrogen atoms of two thiocarbohydrazide ligands as well as two chloride ions in an octahedral geometry about Cd.

Keywords: Thiocarbohydrazide; Cadmium (II); Hydrogen bonding; Crystal structure.

Introduction

Thiocarbohydrazides constitute an important class of N, S-donor ligands with interesting chemical, biological, antibacterial and medicinal properties [1- 8]. In addition, thiocarbohydrazides have been used as analytical reagents in metal analysis [9] and as reagent for the synthesis of heterocycles [10]. Thio- carbohydrazide H2NNHC(S)NHNH2 (abbreviated here as tch), the next higher homologue of thiosemi- carbazide, typically acts as a neutral bidentate ligand coordinating to a metal through the sulfur atom and one of the terminal nitrogen atoms, forming five- membered chelate rings [11]. In order to explore further the coordination chemistry of tch, we prepared and characterized the Cd(II) complex which is reported we report herein.

Results and Discussion

This preparation of trans-dichloro(bis- thiocarbazide)cadmium(II) has previously been reported but characterization was limited to IR spectroscopy [12]. The compound was prepared from the reaction of CdCl2 and thiocarbazide in water under acidic conditions as shown in scheme 1.

A comparative study of IR and Raman spectra of [Cd(tch)2Cl2]complex gives significant information about binding sites. Table-1 lists the assignments of main IR bands of compounds in 400-4000 cm[?]1 region. FT-IR spectrum of the complex showed bands at 3232 and 3200 cm-1 which can be assigned to nas(NH2) and ns(NH2) of primary amine groups. The band at 3075 cm-1 is attributed to v(NH). The d(NH2) and v(CS)+d(CNN)+v(CN) are observed at 1637 and 1552 cm-1, respectively. The bands at 1338 and 758 cm-1 belong to n(CS)+v(CN) and d(CS), respectively. The presence of two bands at 450 and 400 cm-1 in IR and Raman spectra (which are absent in free thiocarbazide) are due to n(Cd-N) and n(Cd-S) indicating that coordination occurs through the primary amine nitrogen atom and the sulfur atom of the thione. The molar conductivity of the cadmium complex in water is 15 ohm-1 cm2 mol-1 indicating that it behaves as a 1:1 electrolyte in solution.

The UV-Vis spectrum of the compound in water shows an n-p centred band at 241 nm (e=2.3x104 dm3 mol[?]1 cm[?]1). To confirm the proposed structure, we subjected crystals of the compound to an X-ray diffraction study. The compound crystallizes in the space group P21/n. A perspective view with the atomic numbering scheme of the complex and its packing arrangement is shown in Fig. 1 and Fig. 2, respectively, selected bond distances and angles are given in Table-2. The two thiocarbohydrazides are coordinated to the cadmium ion as neutral charged bidentate chelating agents via the hydrazone nitrogen atom and the thione sulfur atom, forming a five- membered ring. The structure reveals a six- coordinate cadmium(II) ion in a distorted octahedral environment involving the thione sulfur atoms and the N1 nitrogen atoms trans to each other with the apical positions being occupied by chloride anions. The Cd-S and Cd-N bond distances are 2.605 (1), 2.351 (3) A, respectively.

Table-1: Infrared and Raman absorptions (cm[?]1) of trans-dichloro(bisthiocarbazide)cadmium(II) (KBr).

###v(CS)+d(CNN)###v(CS)###[?]###N###N###N

[Cd(tch)2Cl2]###nas(NH2)###ns(NH2)###n(NH)###+v(CN)###++v(CN)###(C=S)###(Cd-N)###(Cd-S)###(Cd-Cl)###

FT-IR###3284###3200###3075###1552###1338###758###449###400###-

Raman###-###-###3074###1545###1330###750###450###400###357

Table-2: Crystallographic and refinement details for [Cd(tch)2Cl2].

Empirical formula###CH6N4Cd0.5SCl

Formula weight###197.81

Temperature/K###150.0

Crystal system###Monoclinic

Space group###P21/n

a###8.6136(4) A

b###5.7881(3) A

c###12.0980(6) A

(alpha)###90.00 o

b###99.487(5) o

g###90.00 o

Volume###594.91(5) A3

Z###4

rcalc###2.209 mg/mm3

M###2.618 mm-1

F(000)###388

Crystal size###0.1 x 0.1 x 0.05 mm3

Theta range for data collection###3.16 to 29.06deg

Index ranges###-9 [?] h [?] 11, -7 [?] k [?] 7, =16 [?] 1

###[?] 14

Reflections collected###2356

Independent reflections###1343[R(int) = 0.0317]

Data/restraints/parameters###1343/0/94

Goodness-of-fit on F2###1.109

Final R indexes [I greater than 2s (I)]###R1 = 0.0361, wR2 = 0.0964

Final R indexes [all data]###R1 = 0.0415, wR2 = 0.0994

Largest diff. peak/hole###0.966/-1.522 eA-3

The C-S bond length (1.711 (4) A) is longer than a pure double bond (1.61 A) and is compatible with analogous compound (1.710 (3) A) [13]. The C1-N2 and C1-N3 bond distances of the molecule are 1.327 (5) and 1.334 (4) A, respectively, which are intermediate between those expected for single and double C-N bonds (1.47 and 1.27 A) [14]. The N1-N2 bond length (1.408 (5) A) is smaller than the N3-N4 distance (1.409 (4) A), while both of them are longer than those of the free ligand [15]. The mean plane of the tch ligand is almost coplanar, the maximum deviation being 0.045 (2) A for N3. In this compound the angle between the S1-Cd1-N1and S1-C1-N2-N1 planes is 29.28o which is considerably different from that observed in complex (6.49o) [15].

This discrepancy may be due to the large cadmium ion radius as well as the presence of the larger chloride ions. An intramolecular hydrogen bond N3- H3*S1 of 2.550 A can be observed in the Cd- complex. In addition, there is further intermolecular hydrogen bonding interactions between the molecules. The hydrogen bonds N1-H*Cl(1) connects [Cd(tch)2Cl2] molecules along the b axis with 45o angle to adjacent molecules (Fig. 3). Furthermore, there is a similar chain in an opposite direction with an angle of 63.80deg to the previous chain. These two chains are linked by N3-H3AA*Cl1 hydrogen bonds. These two-chain structures grow in the same plane successively (Fig. 4).

These 2D sheets are connected to each other via N4*H2AA-N2, N1-H1AA*Cl1 and N4-H4AA*S1 interactions results in attachment of two-dimensional sheet to each other along ac plane to complete the third dimension of crystal network (Fig.5).

Experiment

General

All chemicals were purchased from Merck and used as received. FT-IR spectrum was recorded on a FT-IR 8400-Shimadzu spectrophotometer over the range of 400-4000 cm-1 as KBr pellets, at spectral resolution of 2 cm-1, with 400 scans. A Thermo Finnegan flash-1112 EA CHNS microanalyzer was utilized for the elemental analysis. The Raman spectrum was performed using a Nicolet Fourier transform spectrometer (model 910). The excitation of the Raman spectrum in the instrument was by the near-IR line at 1.064 um (or 9398.5 cm-1) from a 3 W cw Nd:YAG laser. About 2000 scans at a resolution of 2 cm-1 were needed to ensure high signal-to-noise ratio. The UV spectrum was obtained on a Shimadzu model 2550 instrument over the range of 200-900 nm. The molar conductivity was recorded using a Herisau Metrohm model CH-9101 instrument. Melting points (m.p.) were determined using an Electrothermal digital melting point apparatus.

Synthesis of Trans-dichloro (bisthiocarbazide) Cadmium(II) CdCl2. 4H2O (0.064 g, 0.25 mmol) dissolved in water (25 ml) was added to a solution of thiocarbohydrazide (0.028 g, 0.26 mmol) in water (20 ml) and 5 ml of HCl (0.025 M). On standing for several days, the mixture yielded colorless crystals of the compound which were filtered, washed with water and dried. Crystals suitable for X-ray diffraction were selected from the bulk sample.

Yield: (0.043 g) %. m.p.: 218 oC. molar conductivity: 15 ohm-1 cm2 mol-1. Microanalysis: Found (Calc.): C, 6.29 (6.07); H, 3.11 (3.06); N, 29.28 (28.32)%; FT-IR: cm-1 3284s, 3232s, 3200s, 3075m, 1637s, 1552m, 1338m, 758s, 449w, 401w; Raman: cm-1 3074w, 1600m, 1570s,1545m, 1470m, 1350m, 1330m, 1310m, 1270s, 1060m, 1030m, 920w, 780m, 450w, 400w, 357w; UV/Vis: 241 nm (e=2.3x104 dm3 mol[?]1 cm[?]1).

X-ray Crystallography

The selected crystal of the Cd(II) complex was attached to a cryoloop using a small amount of perfluorinated oil and cooled to 150 K. Data was collected using an Oxford Diffraction Gemini E Ultra diffractometer, equipped with an EOS CCD area detector and a four-circle kappa goniometer. For the data collection the Mo source emitting graphite- monochromated Mo-K(alpha) radiation (l = 0.71073 A)

was used. Data integration, scaling and empirical absorption correction was carried out using the CrysAlis Pro program package [16]. The structure was solved using Direct Methods and refined by Full- Matrix-Least-Squares against F2. The non-hydrogen atoms were refined anisotropically and hydrogen atoms were placed at idealised positions and refined using the riding model. All calculations were carried out using the program Olex2 [17-20]. Crys- tallographic and refinement details for the compound are given in Table-3.

Conclusions

In this work trans-dichloro(bis- thiocarbohydrazide)cadmium(II) complex has been characterized. The X-ray analysis show that the ligand act as neutral charged bidentate chelating agents via the hydrazone nitrogen atom and the thione sulfur atom, forming a five-member ring.

Supporting Information

All crystallographic data for this paper are deposited with the Cambridge Crystallographic Data Centre (CCDC-748154). The data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from Cambridge Crystallographic Data Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 (0) 1223-336033; deposit@ccdc.cam.ac.uk].

Table-3: Selected Bond Lengths (A) and Bond Angles (o).

Cd1-N1###2.351(3)###N1-Cd1-Cl1###92.66(9)

Cd1-N1###2.351(3)###N1 -Cd1-Cl1###87.34(9)

Cd1-S1###2.6048(9)###S1 -Cd1-Cl1###88.99(3)

Cd1-S1###2.6049(9)###S1-Cd1-Cl1###91.01(3)

Cd1-Cl1###2.7187(9)###N1-Cd1-Cl1###87.34(9)

Cd1-Cl1###2.7188(9)###N1 -Cd1-Cl1###92.66(9)

S1-C1###1.711(4)###S1 -Cd1-Cl1###91.01(3)

N3-C1###1.334(4)###S1-Cd1-Cl1###88.99(3)

N3-N4###1.414(5)###Cl1-Cd1-Cl1###179.999(1)

N1-N2###1.409(4)###C1-S1-Cd1###94.66(12)

N2-C1###1.327(5)###C1-N3-N4###119.7(3)

N1-Cd1-N1###180.0###N2-N1-Cd1###110.5(2)

N1-Cd1-S1###103.26(8)###C1-N2-N1###122.7(3)

N1 -Cd1-S1###76.74(8)###N2-C1-N3###116.5(3)

N1-Cd1-S1###76.74(8)###N2-C1-S1###125.2(3)

N1 -Cd1-S1###103.26(8)###N3-C1-S1###118.2(3)

-x,1-y,1-z

Acknowledgement

The authors acknowledge with thanks the financial assistance provided to them by the University of Payame Noor.

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1Chemistry Department, Payame Noor University, 19395-4697 Tehran, Iran., 2Department of Chemistry, School of Sciences, Ferdowsi University of Mashhad, Iran., 3Fachbereich C - Anorganische Chemie, Bergische Universitat Wuppertal, Germany., mohakimi@yahoo.com and noor_fiz2003@yahoo.com
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Author:Hakimi, Mohammad; Feizi, Nourollah; Abbasi, Fatemeh; Takjoo, Reza; Schuh, Esther; Mohr, Fabian
Publication:Journal of the Chemical Society of Pakistan
Article Type:Report
Geographic Code:9PAKI
Date:Jun 30, 2012
Words:2269
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