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

Zhou, X.-X.; Zhou, Z.-Y.; Chen, J.-Q.; Lin, X.-M.; Cai, Y.-P.

doi:10.1107/S1600536807068493

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m328-m329

doi:10.1107/S1600536807068493

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

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

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510631, People's Republic of China
^*Correspondence e-mail: ypcai8@yahoo.com

(Received 11 July 2007; accepted 27 December 2007; online 9 January 2008)

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, P n a 2₁
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[F² > 2σ(F²)] = 0.034
wR(F²) = 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)

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)

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)

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
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ ; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z]$ .

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.

Supporting information

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

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

checkCIF report

Comment top

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.

Related literature top

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 top

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%.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Bruker, 1998) and local programs.

Figures top

	Fig. 1. The molecular structure of the title compound. Dispacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms have been omitted for clarity.
	Fig. 2. A view of the three-dimensional molecular network parallel to (010), formed by weak intermolecular C—H···S hydrogen bonds (dotted lines). Hydrogen atoms not involved in hydrogen bonds have been omitted.

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

Crystal data top

[Zn(C₈H₈N₃S₂)₂]	F(000) = 1000
M_r = 487.97	D_x = 1.525 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P2c-2n	Cell parameters from 5120 reflections
a = 18.630 (7) Å	θ = 2.8–26.8°
b = 9.160 (3) Å	µ = 1.56 mm⁻¹
c = 12.457 (4) Å	T = 293 K
V = 2125.8 (13) Å³	Block, colorless
Z = 4	0.25 × 0.22 × 0.17 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4584 independent reflections
Radiation source: fine-focus sealed tube	3257 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
ϕ and ω scans	θ_max = 27.1°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→13
T_min = 0.745, T_max = 0.777	k = −11→11
11500 measured reflections	l = −15→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.079	w = 1/[σ²(F_o²) + (0.0305P)² + 0.1243P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
4584 reflections	Δρ_max = 0.25 e Å⁻³
244 parameters	Δρ_min = −0.30 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 2122 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.013 (12)

Crystal data top

[Zn(C₈H₈N₃S₂)₂]	V = 2125.8 (13) Å³
M_r = 487.97	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 18.630 (7) Å	µ = 1.56 mm⁻¹
b = 9.160 (3) Å	T = 293 K
c = 12.457 (4) Å	0.25 × 0.22 × 0.17 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	4584 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3257 reflections with I > 2σ(I)
T_min = 0.745, T_max = 0.777	R_int = 0.028
11500 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	H-atom parameters constrained
wR(F²) = 0.079	Δρ_max = 0.25 e Å⁻³
S = 1.04	Δρ_min = −0.30 e Å⁻³
4584 reflections	Absolute structure: Flack (1983), 2122 Friedel pairs
244 parameters	Absolute structure parameter: 0.013 (12)
1 restraint

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.056290 (19)	0.37624 (4)	−0.00480 (4)	0.05017 (12)
S1	0.06703 (6)	0.16722 (11)	−0.12754 (9)	0.0649 (3)
S2	0.16269 (7)	0.12965 (14)	−0.30631 (10)	0.0782 (4)
S3	0.15974 (5)	0.33863 (11)	0.11758 (9)	0.0641 (3)
S4	0.16648 (8)	0.15980 (16)	0.30963 (11)	0.0885 (4)
N1	0.05862 (16)	0.6151 (3)	0.0248 (2)	0.0548 (9)
N2	0.11660 (15)	0.4672 (3)	−0.1347 (2)	0.0494 (7)
N3	0.14624 (17)	0.3833 (4)	−0.2142 (2)	0.0587 (8)
H3A	0.1757	0.4172	−0.2611	0.070*
N4	−0.06136 (14)	0.3920 (3)	−0.0321 (2)	0.0527 (8)
N5	0.00813 (14)	0.2761 (3)	0.1317 (2)	0.0468 (7)
N6	0.04532 (16)	0.2141 (3)	0.2144 (2)	0.0563 (8)
H6A	0.0252	0.1636	0.2642	0.068*
C1	0.0304 (2)	0.6883 (5)	0.1059 (4)	0.0695 (11)
H1A	−0.0021	0.6405	0.1504	0.083*
C2	0.0468 (3)	0.8328 (5)	0.1276 (4)	0.0782 (13)
H2A	0.0268	0.8802	0.1864	0.094*
C3	0.0925 (3)	0.9028 (5)	0.0616 (4)	0.0806 (13)
H3B	0.1043	0.9998	0.0746	0.097*
C4	0.1219 (2)	0.8307 (4)	−0.0255 (4)	0.0708 (12)
H4A	0.1532	0.8780	−0.0723	0.085*
C5	0.1034 (2)	0.6868 (4)	−0.0407 (3)	0.0519 (9)
C6	0.13319 (19)	0.6008 (4)	−0.1282 (3)	0.0540 (9)
H6B	0.1638	0.6431	−0.1783	0.065*
C7	0.1259 (2)	0.2492 (5)	−0.2121 (3)	0.0513 (10)
C8	0.2232 (3)	0.2385 (6)	−0.3797 (5)	0.123 (2)
H8A	0.2461	0.1801	−0.4337	0.185*
H8B	0.2589	0.2776	−0.3320	0.185*
H8C	0.1976	0.3172	−0.4133	0.185*
C9	−0.0957 (2)	0.4483 (5)	−0.1153 (4)	0.0715 (11)
H9A	−0.0695	0.4984	−0.1670	0.086*
C10	−0.1684 (2)	0.4357 (5)	−0.1283 (4)	0.0832 (14)
H10A	−0.1906	0.4778	−0.1876	0.100*
C11	−0.2080 (2)	0.3619 (5)	−0.0549 (4)	0.0846 (15)
H11A	−0.2573	0.3521	−0.0632	0.102*
C12	−0.1735 (2)	0.3019 (5)	0.0324 (4)	0.0729 (12)
H12A	−0.1993	0.2519	0.0848	0.087*
C13	−0.09986 (19)	0.3174 (4)	0.0405 (3)	0.0529 (9)
C14	−0.05961 (18)	0.2558 (4)	0.1289 (3)	0.0543 (9)
H14A	−0.0826	0.2026	0.1824	0.065*
C15	0.1136 (2)	0.2385 (4)	0.2107 (3)	0.0535 (10)
C16	0.1042 (3)	0.0692 (7)	0.3960 (4)	0.131 (2)
H16A	0.1298	0.0223	0.4533	0.197*
H16B	0.0781	−0.0027	0.3558	0.197*
H16C	0.0713	0.1393	0.4253	0.197*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0438 (2)	0.0553 (2)	0.0514 (2)	−0.00346 (17)	0.0087 (2)	0.0044 (2)
S1	0.0754 (7)	0.0579 (6)	0.0615 (6)	−0.0133 (5)	0.0076 (6)	−0.0041 (5)
S2	0.0750 (8)	0.0874 (9)	0.0721 (7)	0.0010 (6)	0.0107 (6)	−0.0295 (6)
S3	0.0393 (5)	0.0865 (7)	0.0665 (6)	0.0000 (5)	0.0002 (5)	−0.0022 (6)
S4	0.0793 (9)	0.0942 (9)	0.0921 (9)	0.0049 (7)	−0.0400 (8)	0.0142 (7)
N1	0.0497 (16)	0.0497 (16)	0.065 (3)	0.0043 (15)	0.0092 (15)	−0.0022 (14)
N2	0.0492 (16)	0.053 (2)	0.0462 (16)	−0.0006 (14)	0.0097 (14)	0.0008 (15)
N3	0.0558 (19)	0.071 (2)	0.0496 (18)	−0.0080 (16)	0.0192 (15)	−0.0006 (16)
N4	0.0441 (16)	0.0578 (18)	0.056 (2)	−0.0011 (14)	0.0030 (14)	0.0111 (14)
N5	0.0418 (17)	0.0534 (17)	0.0451 (15)	−0.0013 (13)	0.0030 (14)	0.0051 (14)
N6	0.057 (2)	0.065 (2)	0.0474 (17)	−0.0068 (15)	−0.0047 (15)	0.0106 (15)
C1	0.066 (3)	0.073 (3)	0.070 (3)	0.007 (2)	0.016 (2)	−0.002 (2)
C2	0.097 (3)	0.068 (3)	0.070 (3)	0.021 (2)	0.008 (3)	−0.011 (2)
C3	0.101 (4)	0.058 (3)	0.083 (3)	0.007 (3)	−0.005 (3)	−0.009 (2)
C4	0.080 (3)	0.057 (2)	0.076 (4)	−0.004 (2)	0.002 (2)	0.005 (2)
C5	0.051 (2)	0.044 (2)	0.060 (2)	0.0033 (17)	−0.0019 (17)	0.0037 (16)
C6	0.056 (2)	0.052 (2)	0.055 (2)	−0.0081 (17)	0.0097 (19)	0.0076 (18)
C7	0.051 (2)	0.058 (3)	0.045 (2)	−0.0007 (19)	−0.0046 (16)	−0.0083 (18)
C8	0.119 (4)	0.148 (5)	0.103 (4)	−0.015 (4)	0.053 (4)	−0.024 (4)
C9	0.060 (3)	0.079 (3)	0.076 (3)	0.000 (2)	−0.003 (2)	0.026 (3)
C10	0.066 (3)	0.089 (3)	0.095 (3)	0.001 (2)	−0.026 (3)	0.032 (3)
C11	0.047 (2)	0.093 (4)	0.114 (4)	−0.004 (2)	−0.018 (3)	0.023 (3)
C12	0.048 (2)	0.090 (3)	0.080 (3)	−0.019 (2)	0.002 (2)	0.016 (2)
C13	0.039 (2)	0.060 (2)	0.059 (2)	0.0024 (17)	0.0026 (17)	0.0065 (18)
C14	0.045 (2)	0.069 (2)	0.049 (2)	−0.0080 (17)	0.0058 (19)	0.0063 (18)
C15	0.051 (2)	0.056 (3)	0.054 (2)	0.0061 (19)	−0.0101 (19)	−0.0152 (17)
C16	0.158 (6)	0.146 (5)	0.090 (4)	−0.045 (4)	−0.054 (4)	0.052 (4)

Geometric parameters (Å, º) top

Zn1—N5	2.130 (3)	C1—H1A	0.9300
Zn1—N2	2.139 (3)	C2—C3	1.346 (7)
Zn1—N1	2.219 (3)	C2—H2A	0.9300
Zn1—N4	2.223 (3)	C3—C4	1.384 (6)
Zn1—S1	2.4584 (13)	C3—H3B	0.9300
Zn1—S3	2.4814 (13)	C4—C5	1.376 (5)
S1—C7	1.697 (4)	C4—H4A	0.9300
S2—C7	1.744 (4)	C5—C6	1.456 (5)
S2—C8	1.761 (5)	C6—H6B	0.9300
S3—C15	1.710 (4)	C8—H8A	0.9600
S4—C15	1.735 (4)	C8—H8B	0.9600
S4—C16	1.786 (6)	C8—H8C	0.9600
N1—C1	1.321 (5)	C9—C10	1.368 (5)
N1—C5	1.339 (4)	C9—H9A	0.9300
N2—C6	1.264 (4)	C10—C11	1.356 (6)
N2—N3	1.370 (4)	C10—H10A	0.9300
N3—C7	1.286 (5)	C11—C12	1.377 (6)
N3—H3A	0.8600	C11—H11A	0.9300
N4—C9	1.323 (5)	C12—C13	1.384 (5)
N4—C13	1.341 (4)	C12—H12A	0.9300
N5—C14	1.276 (4)	C13—C14	1.447 (5)
N5—N6	1.365 (4)	C14—H14A	0.9300
N6—C15	1.293 (4)	C16—H16A	0.9600
N6—H6A	0.8600	C16—H16B	0.9600
C1—C2	1.385 (6)	C16—H16C	0.9600

N5—Zn1—N2	173.15 (11)	C5—C4—C3	117.7 (4)
N5—Zn1—N1	107.46 (11)	C5—C4—H4A	121.1
N2—Zn1—N1	74.43 (11)	C3—C4—H4A	121.1
N5—Zn1—N4	74.61 (10)	N1—C5—C4	122.9 (4)
N2—Zn1—N4	112.15 (11)	N1—C5—C6	115.4 (3)
N1—Zn1—N4	88.90 (11)	C4—C5—C6	121.7 (4)
N5—Zn1—S1	101.26 (8)	N2—C6—C5	118.6 (3)
N2—Zn1—S1	77.89 (8)	N2—C6—H6B	120.7
N1—Zn1—S1	150.43 (8)	C5—C6—H6B	120.7
N4—Zn1—S1	92.05 (8)	N3—C7—S1	128.7 (3)
N5—Zn1—S3	77.11 (8)	N3—C7—S2	118.1 (3)
N2—Zn1—S3	96.37 (9)	S1—C7—S2	113.2 (2)
N1—Zn1—S3	91.11 (8)	S2—C8—H8A	109.5
N4—Zn1—S3	150.32 (8)	S2—C8—H8B	109.5
S1—Zn1—S3	102.17 (4)	H8A—C8—H8B	109.5
C7—S1—Zn1	95.42 (14)	S2—C8—H8C	109.5
C7—S2—C8	104.2 (2)	H8A—C8—H8C	109.5
C15—S3—Zn1	95.79 (13)	H8B—C8—H8C	109.5
C15—S4—C16	104.6 (2)	N4—C9—C10	122.6 (4)
C1—N1—C5	117.7 (3)	N4—C9—H9A	118.7
C1—N1—Zn1	128.3 (3)	C10—C9—H9A	118.7
C5—N1—Zn1	113.2 (2)	C11—C10—C9	120.0 (4)
C6—N2—N3	119.4 (3)	C11—C10—H10A	120.0
C6—N2—Zn1	117.2 (2)	C9—C10—H10A	120.0
N3—N2—Zn1	122.7 (2)	C10—C11—C12	118.6 (4)
C7—N3—N2	113.8 (3)	C10—C11—H11A	120.7
C7—N3—H3A	123.1	C12—C11—H11A	120.7
N2—N3—H3A	123.1	C11—C12—C13	118.6 (4)
C9—N4—C13	117.9 (3)	C11—C12—H12A	120.7
C9—N4—Zn1	128.5 (3)	C13—C12—H12A	120.7
C13—N4—Zn1	113.0 (2)	N4—C13—C12	122.3 (4)
C14—N5—N6	117.5 (3)	N4—C13—C14	115.8 (3)
C14—N5—Zn1	117.2 (2)	C12—C13—C14	122.0 (4)
N6—N5—Zn1	124.6 (2)	N5—C14—C13	118.5 (3)
C15—N6—N5	113.6 (3)	N5—C14—H14A	120.8
C15—N6—H6A	123.2	C13—C14—H14A	120.8
N5—N6—H6A	123.2	N6—C15—S3	127.7 (3)
N1—C1—C2	123.1 (4)	N6—C15—S4	117.5 (3)
N1—C1—H1A	118.5	S3—C15—S4	114.8 (2)
C2—C1—H1A	118.5	S4—C16—H16A	109.5
C3—C2—C1	118.4 (4)	S4—C16—H16B	109.5
C3—C2—H2A	120.8	H16A—C16—H16B	109.5
C1—C2—H2A	120.8	S4—C16—H16C	109.5
C2—C3—C4	120.2 (4)	H16A—C16—H16C	109.5
C2—C3—H3B	119.9	H16B—C16—H16C	109.5
C4—C3—H3B	119.9

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x−1/2, −y+1/2, z.

Experimental details

Crystal data
Chemical formula	[Zn(C₈H₈N₃S₂)₂]
M_r	487.97
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	18.630 (7), 9.160 (3), 12.457 (4)
V (Å³)	2125.8 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.56
Crystal size (mm)	0.25 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.745, 0.777
No. of measured, independent and observed [I > 2σ(I)] reflections	11500, 4584, 3257
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.642

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.079, 1.04
No. of reflections	4584
No. of parameters	244
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.25, −0.30
Absolute structure	Flack (1983), 2122 Friedel pairs
Absolute structure parameter	0.013 (12)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1998) and local programs.

Selected geometric parameters (Å, º) top

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

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···Slⁱ	0.930	2.935	3.715 (3)	142.34
C12—H12A···S3ⁱⁱ	0.930	2.785	3.526 (4)	137.53

Symmetry codes: (i) x+1/2, −y+1/2, z; (ii) x−1/2, −y+1/2, z.

Acknowledgements

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).

References

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