Bis[methyl 2-(2-pyridylmethyl­idene)hydrazinecarbodithio­ato]zinc(II)

Xiu-Xia Zhou; Zheng-Yuan Zhou; Jian-Qiao Chen; Xiao-Ming Lin; Yue-Peng Cai

doi:10.1107/S1600536807068493

. 2008 Jan 9;64(Pt 2):m328–m329. doi: 10.1107/S1600536807068493

Bis[methyl 2-(2-pyridylmethylidene)hydrazinecarbodithioato]zinc(II)

Xiu-Xia Zhou ^a, Zheng-Yuan Zhou ^a, Jian-Qiao Chen ^a, Xiao-Ming Lin ^a, Yue-Peng Cai ^a,^*

PMCID: PMC2960303 PMID: 21201296

Abstract

In the title compound, [Zn(C₈H₈N₃S₂)₂], the Zn atom is coordinated by the two ligands in a tridentate manner, via the pyridyl N, the azomethine N and the thiolate S atom; the coordination geometry is distorted octahedral, with the two ligands in the mer configuration (two S atoms and two pyridyl N atoms are cis with respect to each other and the azomethine N atoms is trans). The molecules are linked by C—H⋯S hydrogen bonds, forming a three-dimensional network structure.

Related literature

For general background, see: Akbar Ali et al. (2001 ▶); Casas et al. (2000 ▶); Kasuga et al. (2001 ▶); Tarafder et al. (2003 ▶). For related structures, see: Chen et al. (2003a ▶,b ▶); Lin et al. (2007 ▶).

Experimental

Crystal data

[Zn(C₈H₈N₃S₂)₂]
M _r = 487.97
Orthorhombic,
a = 18.630 (7) Å
b = 9.160 (3) Å
c = 12.457 (4) Å
V = 2125.8 (13) Å³
Z = 4
Mo Kα radiation
μ = 1.56 mm⁻¹
T = 293 (2) K
0.25 × 0.22 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.745, T _max = 0.777
11500 measured reflections
4584 independent reflections
3257 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.079
S = 1.04
4584 reflections
244 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.30 e Å⁻³
Absolute structure: Flack (1983 ▶), 2122 Friedel pairs
Flack parameter: 0.013 (12)

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Bruker, 1998 ▶); software used to prepare material for publication: SHELXTL and local programs.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068493/wn2230sup1.cif

e-64-0m328-sup1.cif^{(18.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068493/wn2230Isup2.hkl

e-64-0m328-Isup2.hkl^{(224.6KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Zn1—N5	2.130 (3)
Zn1—N2	2.139 (3)
Zn1—N1	2.219 (3)
Zn1—N4	2.223 (3)
Zn1—S1	2.4584 (13)
Zn1—S3	2.4814 (13)

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N5—Zn1—N2	173.15 (11)
N5—Zn1—N1	107.46 (11)
N2—Zn1—N1	74.43 (11)
N5—Zn1—N4	74.61 (10)
N2—Zn1—N4	112.15 (11)
N1—Zn1—N4	88.90 (11)
N5—Zn1—S1	101.26 (8)
N2—Zn1—S1	77.89 (8)
N1—Zn1—S1	150.43 (8)
N4—Zn1—S1	92.05 (8)
N5—Zn1—S3	77.11 (8)
N2—Zn1—S3	96.37 (9)
N1—Zn1—S3	91.11 (8)
N4—Zn1—S3	150.32 (8)
S1—Zn1—S3	102.17 (4)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯Slⁱ	0.93	2.94	3.715 (3)	142
C12—H12A⋯S3ⁱⁱ	0.93	2.79	3.526 (4)	138

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The work was supported by the National Natural Science Foundation of China (No. 20772037) and the National Natural Science Foundation of Guangdong Province, China (No. 06025033).

supplementary crystallographic information

Comment

The wide variety of biological activity exhibited by thiosemicarbazones (Kasuga et al., 2001) and Schiff bases derived from S-alkyldithiocarbazates (Akbar Ali et al., 2001) and their interesting coordination chemistry have stimulated considerable research interest in these compounds (Casas et al., 2000). Some Schiff bases of S-alkyl esters of dithiocarbazic acid and their complexes were found to display antifungal and antibacterial properties (Tarafder et al., 2003). Recently we reported the Co(II) complex of the S-containing Schiff base ligand methyl 2-pyridylmethylidenehydrazinecarbodithioate (NNS^-) (Lin et al., 2007). As a part of structural studies of compounds containing the sulfur-nitrogen chelating ligand (Chen et al., 2003a,b), we report here the synthesis and structure of the compound, bis(methyl 2-pyridylmethylidenehydrazinecarbodithioato)zinc(II), Zn(NNS)₂.

The Zn atom is six-coordinated by the two tridentate NNS^- anions in a distorted octahedral geometry (Fig. 1). The ligands chelate the Zn(II) ion via the pyridyl N, the azomethine N, and the thiolate S atoms in a mer-configuration with four five-membered rings. The two azomethine N atoms (N2 and N5) are trans to each other, while the sulfur atoms (S1 and S3) and pyridyl N atoms (N1 and N4) are in cis positions. The two almost planar ligands [maximum deviation from their least-squares planes is 0.038 (3) Å] approach the central Zn(II) atom in an orthogonal orientation. The pyridyl ring and the two five-membered chelate rings formed by each ligand display very small dihedral angles between the planes. For each ligand, the maximum dihedral angle of 2.5 (1)° is between two neighbouring five-membered chelate rings (viz. Zn1—S1—C7—N3—N2 and Zn1—N1—C5—C6—N2).

The molecules are linked by C—H···S hydrogen bonds. As shown in Fig. 2, each molecular unit forms four acceptor/donor hydrogen bonds with four neighboring molecular units. resulting in a three-dimensional network structure.

Experimental

A solution of Zn(ClO₄)₂ (363 mg, 1.00 mmol) in CH₃OH (20 ml) was slowly added to a solution of methyl 2-pyridylmethylidenehydrazinecarbodithioate (HNNS) (410 mg, 1.95 mmol) in CH₃OH (10 ml). The resultant black-purple solution was stirred under N₂ for 2 h at 323 K and then filtered. After addition of diethyl ether (20 ml), the filtrate was cooled to 253 K. A microcrystalline solid was collected after 24 h and dried under vacuum (yield: 264 mg, 55%). Brown block-shaped crystals suitable for X-ray diffraction were obtained in 2 d by slow diffusion of diethyl ether into a dilute solution of the title complex in methanol. The assigned structure was substantiated by elemental analysis; calculated for C₁₆H₁₆N₆ZnS₄: C 39.51, H 3.30, N 17.29%; found: C 39.46, H 3.38, N 17.23%.