(Dimethyl sulfoxide-κO)bis­(thio­semicarbazide-κ2 N 1,S)zinc dipicrate dimethyl sulfoxide solvate monohydrate

R Shanthakumari; Ramu Hema; K Ramamurthy; Balasubramnian Sridar; Helen Stoeckli-Evans

doi:10.1107/S160053681005378X

. 2011 Jan 8;67(Pt 2):m133–m134. doi: 10.1107/S160053681005378X

(Dimethyl sulfoxide-κO)bis(thiosemicarbazide-κ² N ¹,S)zinc dipicrate dimethyl sulfoxide solvate monohydrate

R Shanthakumari ^a, Ramu Hema ^b, K Ramamurthy ^c, Balasubramnian Sridar ^d, Helen Stoeckli-Evans ^e

PMCID: PMC3051735 PMID: 21522821

Abstract

The title complex, [Zn(CH₅N₃S)₂(C₂H₆OS)](C₆H₂N₃O₇)₂·C₂H₆OS·H₂O, is composed of a [Zn(thiosemicarbazide)₂(DMSO)]²⁺ cation (where DMSO is dimethyl sulfoxide), and two picrate anions. In the asymmetric unit, there is also a solvent molecule of DMSO and a water molecule of crystallization. In the cation, the Zn^II atom is five-coordinated in a distorted square–pyramidal geometry. It coordinates to the O atom of a DMSO molecule and to the S and one N atom of two thiosemicarbazide molecules, which behave as bidentate ligands coordinating in a trans arrangement. In the crystal, a number of N—H⋯O, O—H⋯O and N—H⋯S hydrogen bonds link the molecules into two-dimensional networks. These networks are further linked via weak C—H⋯O interactions, forming a three-dimensional arrangement. Positional disorder in one methyl group of the coordinated DMSO molecule and in the two picrate anions was observed.

Related literature

For the biological activity of thiosemicarbazides, see: Gowda & Mahadevappa (1977) ▶; Pillai et al. (1977 ▶). For the use of thiosemicarbazide as a masking agent, see: Kirkbright & Taddia (1978 ▶). For the crystal structure of a similar five-coordinate zinc(II)–thiosemicarbazide complex, see: Babb et al. (2003 ▶). For a description of five-coordinate metal atoms, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Zn(CH₅N₃S)₂(C₂H₆OS)](C₆H₂N₃O₇)₂·C₂H₆OS·H₂O
M _r = 878.13
Triclinic,
a = 10.8762 (11) Å
b = 11.2559 (12) Å
c = 14.4859 (15) Å
α = 81.124 (2)°
β = 77.063 (2)°
γ = 81.168 (2)°
V = 1694.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.06 mm⁻¹
T = 294 K
0.24 × 0.24 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
18781 measured reflections
7719 independent reflections
6573 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.095
S = 1.05
7719 reflections
546 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97 and PLATON.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681005378X/hg2775sup1.cif

e-67-0m133-sup1.cif^{(45.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681005378X/hg2775Isup2.hkl

e-67-0m133-Isup2.hkl^{(377.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1NA⋯O1Wⁱ	0.87 (2)	2.20 (2)	2.974 (3)	148 (2)
N2—HN2⋯O15Aⁱ	0.80 (2)	2.41 (3)	3.01 (2)	133 (2)
N2—HN2⋯O16ⁱ	0.80 (2)	1.96 (2)	2.693 (2)	152 (2)
N3—H3NA⋯O10ⁱ	0.87 (3)	2.44 (3)	3.166 (2)	141 (2)
N3—H3NA⋯O16ⁱ	0.87 (3)	2.03 (3)	2.790 (3)	146 (3)
N3—H3NB⋯O5ⁱⁱ	0.77 (2)	2.24 (2)	3.004 (3)	173 (2)
N5—H5N⋯O7ⁱⁱⁱ	0.84 (2)	2.37 (2)	3.007 (3)	133 (2)
N5—H5N⋯O9Aⁱⁱⁱ	0.84 (2)	1.94 (3)	2.698 (17)	150 (2)
N4—H4NA⋯O2ⁱⁱⁱ	0.88 (2)	2.20 (2)	2.933 (3)	141 (2)
N4—H4NB⋯S1^iv	0.84 (3)	2.63 (3)	3.457 (2)	170 (2)
N6—H6NA⋯O6ⁱⁱⁱ	0.82 (3)	2.41 (3)	3.081 (3)	140 (2)
N6—H6NA⋯O9Aⁱⁱⁱ	0.82 (3)	2.05 (5)	2.76 (3)	145 (3)
N6—H6NB⋯O11^v	0.82 (3)	2.22 (3)	3.034 (3)	172 (3)
O1W—H1WA⋯O8	0.819 (19)	2.27 (2)	3.059 (3)	163 (3)
O1W—H1WB⋯O2	0.80 (2)	2.02 (2)	2.806 (3)	171 (3)
C6—H6B⋯O2ⁱⁱⁱ	0.96	2.52	3.347 (3)	145
C8—H8⋯O4^vi	0.93	2.47	3.390 (3)	168
C4A—H4A2⋯O1W	0.96	2.48	3.430 (7)	170

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

RS thanks the University Grants Commission of India for the award of a minor research project (File No. MRP 2976/2009). HSE thanks the staff of the XRD Application Lab., CSEM, Neuchâtel, for access to the X-ray diffraction equipment.

supplementary crystallographic information

Comment

Thosemicarbazide, a well known chelating agent, is used to characterize aldehydes, ketones, and polysaccharides. Some thiosemicarbazide derivatives are potential anti-tumor, anti-hypertensive agents, and are active against influenza, protozoa and smallpox (Gowda & Mahadevappa, 1977; Pillai et al., 1977). Thiosemicarbazide is also used as a masking agent to minimize interference from metals such as copper, nickel and platinum in the determination of arsenic by atomic absorption methods (Kirkbright & Taddia, 1978). The conformational preferences of thiosemicarbazide in metal-complex formation are therefore of some interest. The reaction of zinc chloride with thiosemicarbazide in the presence of picric acid gave a yellow powder that was recrystallized using DMSO. This lead to the formation of yellow crystals of the title compoud, a DMSO-water solvate.

The molecular structure of the title complex is illustrated in Fig. 1. In the cation [Zn(thiosemicarbazide)₂(DMSO)]²⁺ the thiosemicarbazide ligands coordinate in a bidentate mode, bonding to atom Zn1 through atoms S1, N1 and S2, N4, in a trans arrangment. Atom Zn1 is also coordinated to a DMSO molecule through the O-atom, O1. The zinc atom has a distorted square pyramidal coordination sphere with a τ value of 0.17 [τ = 0 for square pyramidal, τ = 1 for trigonal bipyramidal; Addison et al., 1984]. The bond distances are comparable to those in a related penta-coordinated complex, (Citraconato-O)-bis(thiosemicarbazide-N,S)-zinc(II) monohydrate (Babb et al., 2003). Interestingly, here the thiosemicarbazide ligands are in a cis disposition, and the zinc coordination sphere has a τ value of 0.72, hence it can be described as a distorted trigonal bipyramid.

In the crystal a sheet-like network is formed, propagating in the ac-plane, as a result of a number of intermolecular N—H···O, O—H···O and N—H···S hydrogen bonds. These sheets are then linked via weak C—H···O interactions to form a three-dimensional arrangement (Table 1 and Fig. 2).

Experimental

A mixture of supersaturated solutions of thiosemicarbazide, picric acid and zinc chloride were added in the molar ratio of 1:1:1 (0.9 g: 2.5 g: 2.8 g). The calculated amount of thiosemicarbazide and zinc chloride were dissolved in distilled water and picric acid dissolved in acetone was added. Within a few minutes, the solution became turbid. The reaction was ensured with continuous stirring and after 1 h a yellow product was deposited at the bottom of the beaker, it was filtered off and dried. This yellow solid was recrystallized from DMSO to afford yellow block-like crystals of the title compound (yield: 4 g, 66.6%)