Dichloridobis(5-heptyl-1,3,4-thia­diazol-2-amine-κN3)zinc(II)

Wang, P.; Wan, R.; Wang, B.; Han, F.; Wang, Y.

doi:10.1107/S1600536809032073

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page m1086

doi:10.1107/S1600536809032073

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Dichloridobis(5-heptyl-1,3,4-thiadiazol-2-amine-κN³)zinc(II)

Peng Wang,^a Rong Wan,^a ^* Bin Wang,^a Feng Han ^a and Yao Wang ^a

^aDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, No. 5 Xinmofan Road, Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: rwan@njut.edu.cn

(Received 24 July 2009; accepted 13 August 2009; online 19 August 2009)

In the title compound, [ZnCl₂(C₉H₁₇N₃S)₂], the Zn^II atom is four-coordinated by two N atoms from two 5-heptyl-1,3,4-thiadiazol-2-amine ligands and two Cl atoms in a distorted tetrahedral geometry. The thiadiazole rings are oriented at a dihedral angle of 84.87 (4)°. Intramolecular N—H⋯Cl interactions result in the formation of two six-membered rings having envelope and planar conformations. In the crystal structure, intermolecular N—H⋯N and N—H⋯Cl interactions link the molecules into a three-dimensional network. π–π contacts between thiadiazole rings [centroid–centroid distance = 3.602 (1) Å] may further stabilize the structure.

Related literature

For general background to thiadiazoles and their derivatives, see: Alzuet et al. (2003 ); Shen et al. (2004 ).

Experimental

Crystal data

[ZnCl₂(C₉H₁₇N₃S)₂]
M_r = 534.94
Triclinic, $[P \overline 1]$
a = 8.1750 (16) Å
b = 11.663 (2) Å
c = 14.666 (3) Å
α = 73.150 (17)°
β = 77.83 (2)°
γ = 88.81 (3)°
V = 1307.0 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.32 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.693, T_max = 0.879
5096 measured reflections
4734 independent reflections
3303 reflections with I > 2σ(I)
R_int = 0.054
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.177
S = 1.02
4734 reflections
256 parameters
H-atom parameters constrained
Δρ_max = 1.17 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Zn—Cl1	2.2283 (16)
Zn—Cl2	2.2626 (17)
Zn—N1	2.037 (4)
Zn—N4	2.026 (4)

Cl1—Zn—Cl2	114.97 (7)
N1—Zn—Cl1	109.00 (12)
N1—Zn—Cl2	106.06 (13)
N4—Zn—Cl1	112.65 (12)
N4—Zn—Cl2	108.05 (13)
N4—Zn—N1	105.49 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯Cl1	0.86	2.58	3.374 (5)	154
N3—H3B⋯Cl2ⁱ	0.86	2.77	3.503 (5)	144
N6—H6A⋯Cl2	0.86	2.49	3.289 (5)	155
N6—H6B⋯N2ⁱⁱ	0.86	2.19	3.018 (3)	163
Symmetry codes: (i) -x, -y+2, -z+1; (ii) -x, -y+1, -z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032073/hk2748sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809032073/hk2748Isup2.hkl

checkCIF report

Comment top

As a series of superior ligands, thiadiazoles and their derivatives can coordinate to many metal ions with N or S atoms of the five-membered ring. In particular N,N'-linkage ligands, such as 1,3,4-thiadiazoles, are very versatile compounds that are able to bridge a wide range of inter-metallic separations through two close adjacent N donors (Alzuet et al., 2003). These complexes have received considerable attention in past few years, due to their certain antibacterial and antifungal activities (Shen et al., 2004).

In the molecule of the title compound, (Fig. 1), Zn^II atom is four-coordinated by two N atoms from two 5-heptyl-[1,3,4]thiadiazol-2-ylamine ligands and two Cl atoms in a distorted tetrahedral geometry (Table 1). Rings A (S1/N1/N2/C8/C9) and B (S2/N4/N5/C10/C11) are, of course, planar and they are oriented at a dihedral angle of A/B = 84.87 (4)°. The intramolecular N-H···Cl interactions (Table 2) result in the formations of two six-membered rings C (Zn/Cl1/N1/N3/C9/H3A) and D (Zn/Cl2/N4/N6/C10/H6A). Ring C adopts envelope conformation with atom Zn displaced by -0.318 (3) Å from the plane of the other ring atoms, while ring D is planar and it is oriented with respect to the adjacent ring B at a dihedral angle of B/D = 1.08 (4)°. So, they are almost coplanar.

In the crystal structure, intermolecular N-H···N and N-H···Cl interactions (Table 2) link the molecules into a three-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contact between the thiadiazole rings, Cg2—Cg2ⁱ, [symmetry code: (i) 1 - x, 1 - y, 1 - z, where Cg2 is centroid of the ring B (S2/N4/N5/C10/C11)] may further stabilize the structure, with centroid-centroid distance of 3.602 (1) Å.

Related literature top

For general background to thiadiazoles and their derivatives, see: Alzuet et al. (2003); Shen et al. (2004).

Experimental top

For the preparation of the title compound, ZnCl₂ ethanol solution (0.5 mmol) was slowly added into a solution of 5-heptyl-[1,3,4]thiadiazol-2-ylamine (1 mmol) in ethanol (20 ml), and then heated under reflux for 2 h. The reaction mixture was left to cool to room temperature, filtrated, and the solid was recrystallized from ethanol to give the title compound (m.p. 426 K). Crystals suitable for X-ray analysis were obtained by slow evaporation of an acetone solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.

Dichloridobis(5-heptyl-1,3,4-thiadiazol-2-amine-κN³)zinc(II) top

Crystal data top

[ZnCl₂(C₉H₁₇N₃S)₂]	Z = 2
M_r = 534.94	F(000) = 560
Triclinic, P1	D_x = 1.359 Mg m⁻³
Hall symbol: -P 1	Melting point: 426 K
a = 8.1750 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.663 (2) Å	Cell parameters from 25 reflections
c = 14.666 (3) Å	θ = 10–14°
α = 73.150 (17)°	µ = 1.32 mm⁻¹
β = 77.83 (2)°	T = 294 K
γ = 88.81 (3)°	Block, yellow
V = 1307.0 (5) Å³	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	3303 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.054
Graphite monochromator	θ_max = 25.3°, θ_min = 1.5°
ω/2θ scans	h = 0→9
Absorption correction: ψ scan (North et al., 1968)	k = −14→14
T_min = 0.693, T_max = 0.879	l = −17→17
5096 measured reflections	3 standard reflections every 120 min
4734 independent reflections	intensity decay: 1%

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)] = 0.062	H-atom parameters constrained
wR(F²) = 0.177	w = 1/[σ²(F_o²) + (0.1P)² + 0.5P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
4734 reflections	Δρ_max = 1.17 e Å⁻³
256 parameters	Δρ_min = −1.27 e Å⁻³
Primary atom site location: structure-invariant direct methods

Crystal data top

[ZnCl₂(C₉H₁₇N₃S)₂]	γ = 88.81 (3)°
M_r = 534.94	V = 1307.0 (5) Å³
Triclinic, P1	Z = 2
a = 8.1750 (16) Å	Mo Kα radiation
b = 11.663 (2) Å	µ = 1.32 mm⁻¹
c = 14.666 (3) Å	T = 294 K
α = 73.150 (17)°	0.30 × 0.20 × 0.10 mm
β = 77.83 (2)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	3303 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.054
T_min = 0.693, T_max = 0.879	3 standard reflections every 120 min
5096 measured reflections	intensity decay: 1%
4734 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	256 parameters
wR(F²) = 0.177	H-atom parameters constrained
S = 1.02	Δρ_max = 1.17 e Å⁻³
4734 reflections	Δρ_min = −1.27 e Å⁻³

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
Zn	0.20470 (7)	0.74792 (5)	0.52670 (5)	0.0475 (2)
Cl1	0.42266 (17)	0.84281 (12)	0.54632 (13)	0.0631 (4)
Cl2	−0.00212 (19)	0.68349 (12)	0.66162 (11)	0.0612 (4)
S1	−0.04746 (18)	1.03689 (11)	0.32771 (11)	0.0531 (4)
S2	0.32968 (18)	0.40780 (12)	0.43889 (11)	0.0548 (4)
N1	0.0979 (5)	0.8621 (3)	0.4239 (3)	0.0457 (10)
N2	−0.0286 (5)	0.8113 (4)	0.3960 (3)	0.0487 (11)
N3	0.2131 (6)	1.0514 (4)	0.4083 (3)	0.0555 (12)
H3A	0.2872	1.0198	0.4407	0.067*
H3B	0.2106	1.1281	0.3862	0.067*
N4	0.2722 (5)	0.6065 (3)	0.4752 (3)	0.0451 (10)
N5	0.3971 (5)	0.6318 (4)	0.3912 (3)	0.0523 (11)
N6	0.1068 (6)	0.4464 (4)	0.5882 (3)	0.0559 (12)
H6A	0.0580	0.4913	0.6222	0.067*
H6B	0.0802	0.3710	0.6061	0.067*
C1	−0.8999 (12)	1.1163 (10)	0.0104 (8)	0.136 (3)
H1A	−0.9142	1.1855	−0.0415	0.204*
H1B	−0.9989	1.1008	0.0615	0.204*
H1C	−0.8808	1.0481	−0.0141	0.204*
C2	−0.7616 (13)	1.1374 (11)	0.0474 (8)	0.139 (4)
H2B	−0.7931	1.1902	0.0879	0.167*
H2C	−0.6715	1.1776	−0.0065	0.167*
C3	−0.6975 (13)	1.0203 (10)	0.1083 (8)	0.136 (3)
H3C	−0.7895	0.9770	0.1593	0.163*
H3D	−0.6578	0.9699	0.0666	0.163*
C4	−0.5561 (9)	1.0448 (6)	0.1542 (5)	0.0778 (19)
H4A	−0.4670	1.0909	0.1026	0.093*
H4B	−0.5979	1.0943	0.1963	0.093*
C5	−0.4821 (8)	0.9362 (5)	0.2128 (5)	0.0627 (15)
H5B	−0.5695	0.8910	0.2661	0.075*
H5C	−0.4418	0.8853	0.1717	0.075*
C6	−0.3420 (8)	0.9659 (5)	0.2535 (5)	0.0655 (16)
H6C	−0.3843	1.0133	0.2972	0.079*
H6D	−0.2580	1.0152	0.2003	0.079*
C7	−0.2584 (7)	0.8582 (5)	0.3084 (5)	0.0642 (16)
H7A	−0.3416	0.8100	0.3627	0.077*
H7B	−0.2189	0.8095	0.2653	0.077*
C8	−0.1135 (7)	0.8886 (4)	0.3469 (4)	0.0468 (12)
C9	0.1032 (6)	0.9821 (4)	0.3923 (4)	0.0443 (12)
C10	0.2237 (6)	0.4937 (4)	0.5079 (4)	0.0419 (11)
C11	0.4388 (7)	0.5392 (5)	0.3641 (4)	0.0522 (13)
C12	0.5716 (8)	0.5407 (7)	0.2756 (5)	0.0735 (19)
H12A	0.5794	0.6204	0.2299	0.088*
H12B	0.6781	0.5271	0.2953	0.088*
C13	0.5476 (8)	0.4520 (6)	0.2231 (4)	0.0669 (17)
H13A	0.4385	0.4615	0.2063	0.080*
H13B	0.5493	0.3716	0.2663	0.080*
C14	0.6806 (9)	0.4664 (7)	0.1313 (5)	0.082 (2)
H14A	0.7892	0.4545	0.1486	0.098*
H14B	0.6813	0.5478	0.0893	0.098*
C15	0.6560 (10)	0.3794 (7)	0.0742 (5)	0.088 (2)
H15A	0.6645	0.2982	0.1144	0.106*
H15B	0.5438	0.3866	0.0617	0.106*
C16	0.7804 (9)	0.3996 (7)	−0.0220 (5)	0.083 (2)
H16A	0.7723	0.4809	−0.0623	0.100*
H16B	0.8928	0.3920	−0.0097	0.100*
C17	0.7537 (11)	0.3134 (8)	−0.0773 (6)	0.101 (3)
H17A	0.6398	0.3183	−0.0871	0.121*
H17B	0.7672	0.2324	−0.0384	0.121*
C18	0.8756 (11)	0.3384 (8)	−0.1771 (6)	0.112 (3)
H18A	0.8566	0.2788	−0.2076	0.168*
H18B	0.9888	0.3357	−0.1682	0.168*
H18C	0.8574	0.4164	−0.2178	0.168*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn	0.0495 (4)	0.0276 (3)	0.0700 (5)	0.0037 (2)	−0.0124 (3)	−0.0214 (3)
Cl1	0.0533 (8)	0.0424 (7)	0.1056 (12)	0.0043 (6)	−0.0236 (8)	−0.0354 (8)
Cl2	0.0691 (9)	0.0387 (7)	0.0739 (10)	−0.0038 (6)	−0.0015 (7)	−0.0231 (7)
S1	0.0633 (9)	0.0291 (6)	0.0693 (10)	0.0029 (6)	−0.0160 (7)	−0.0168 (6)
S2	0.0619 (9)	0.0385 (7)	0.0755 (10)	0.0096 (6)	−0.0170 (7)	−0.0332 (7)
N1	0.051 (2)	0.031 (2)	0.059 (3)	0.0020 (18)	−0.009 (2)	−0.0206 (19)
N2	0.051 (3)	0.032 (2)	0.065 (3)	−0.0010 (19)	−0.009 (2)	−0.019 (2)
N3	0.061 (3)	0.030 (2)	0.078 (3)	0.000 (2)	−0.020 (2)	−0.016 (2)
N4	0.046 (2)	0.034 (2)	0.059 (3)	0.0023 (18)	−0.012 (2)	−0.019 (2)
N5	0.055 (3)	0.043 (3)	0.063 (3)	−0.002 (2)	−0.011 (2)	−0.022 (2)
N6	0.067 (3)	0.028 (2)	0.075 (3)	0.003 (2)	−0.013 (3)	−0.021 (2)
C1	0.126 (4)	0.151 (5)	0.134 (5)	0.016 (4)	−0.042 (4)	−0.035 (4)
C2	0.137 (7)	0.161 (7)	0.126 (7)	0.010 (6)	−0.061 (6)	−0.026 (6)
C3	0.126 (4)	0.151 (5)	0.134 (5)	0.016 (4)	−0.042 (4)	−0.035 (4)
C4	0.089 (4)	0.070 (4)	0.075 (4)	0.001 (3)	−0.013 (3)	−0.026 (3)
C5	0.068 (4)	0.056 (4)	0.067 (4)	0.003 (3)	−0.019 (3)	−0.019 (3)
C6	0.074 (4)	0.054 (3)	0.072 (4)	0.001 (3)	−0.023 (3)	−0.018 (3)
C7	0.064 (4)	0.054 (3)	0.080 (4)	0.002 (3)	−0.021 (3)	−0.024 (3)
C8	0.051 (3)	0.037 (3)	0.056 (3)	0.003 (2)	−0.007 (3)	−0.021 (2)
C9	0.050 (3)	0.029 (2)	0.054 (3)	0.002 (2)	−0.001 (2)	−0.019 (2)
C10	0.044 (3)	0.030 (2)	0.061 (3)	0.006 (2)	−0.019 (3)	−0.022 (2)
C11	0.048 (3)	0.052 (3)	0.068 (4)	0.006 (2)	−0.017 (3)	−0.032 (3)
C12	0.066 (4)	0.090 (5)	0.072 (4)	−0.010 (3)	−0.001 (3)	−0.044 (4)
C13	0.084 (4)	0.065 (4)	0.057 (4)	0.008 (3)	−0.008 (3)	−0.032 (3)
C14	0.088 (5)	0.093 (5)	0.080 (5)	0.013 (4)	−0.012 (4)	−0.053 (4)
C15	0.107 (6)	0.085 (5)	0.077 (5)	−0.006 (4)	0.008 (4)	−0.051 (4)
C16	0.094 (5)	0.073 (5)	0.089 (5)	0.003 (4)	−0.003 (4)	−0.045 (4)
C17	0.126 (7)	0.105 (6)	0.083 (5)	−0.001 (5)	−0.003 (5)	−0.060 (5)
C18	0.143 (8)	0.104 (6)	0.086 (6)	−0.002 (6)	0.014 (5)	−0.050 (5)

Geometric parameters (Å, º) top

Zn—Cl1	2.2283 (16)	C4—H4B	0.9700
Zn—Cl2	2.2626 (17)	C5—C6	1.487 (8)
Zn—N1	2.037 (4)	C5—H5B	0.9700
Zn—N4	2.026 (4)	C5—H5C	0.9700
S1—C8	1.747 (5)	C6—C7	1.518 (8)
S1—C9	1.712 (6)	C6—H6C	0.9700
S2—C10	1.721 (5)	C6—H6D	0.9700
S2—C11	1.737 (6)	C7—C8	1.504 (7)
N1—N2	1.390 (6)	C7—H7A	0.9700
N1—C9	1.339 (6)	C7—H7B	0.9700
N2—C8	1.274 (7)	C11—C12	1.502 (8)
N3—C9	1.321 (6)	C12—C13	1.495 (8)
N3—H3A	0.8600	C12—H12A	0.9700
N3—H3B	0.8600	C12—H12B	0.9700
N4—N5	1.385 (6)	C13—C14	1.511 (9)
N4—C10	1.301 (6)	C13—H13A	0.9700
N5—C11	1.273 (6)	C13—H13B	0.9700
N6—C10	1.332 (7)	C14—C15	1.530 (9)
N6—H6A	0.8600	C14—H14A	0.9700
N6—H6B	0.8600	C14—H14B	0.9700
C1—C2	1.408 (13)	C15—C16	1.514 (9)
C1—H1A	0.9600	C15—H15A	0.9700
C1—H1B	0.9600	C15—H15B	0.9700
C1—H1C	0.9600	C16—C17	1.508 (9)
C2—C3	1.548 (13)	C16—H16A	0.9700
C2—H2B	0.9700	C16—H16B	0.9700
C2—H2C	0.9700	C17—C18	1.539 (10)
C3—C4	1.525 (12)	C17—H17A	0.9700
C3—H3C	0.9700	C17—H17B	0.9700
C3—H3D	0.9700	C18—H18A	0.9600
C4—C5	1.505 (9)	C18—H18B	0.9600
C4—H4A	0.9700	C18—H18C	0.9600

Cl1—Zn—Cl2	114.97 (7)	C8—C7—H7A	108.6
N1—Zn—Cl1	109.00 (12)	C6—C7—H7A	108.6
N1—Zn—Cl2	106.06 (13)	C8—C7—H7B	108.6
N4—Zn—Cl1	112.65 (12)	C6—C7—H7B	108.6
N4—Zn—Cl2	108.05 (13)	H7A—C7—H7B	107.6
N4—Zn—N1	105.49 (16)	N2—C8—C7	124.3 (5)
C9—S1—C8	87.9 (2)	N2—C8—S1	113.7 (4)
C10—S2—C11	86.9 (3)	C7—C8—S1	121.9 (4)
N2—N1—Zn	115.5 (3)	N3—C9—N1	124.0 (5)
C9—N1—Zn	130.8 (4)	N3—C9—S1	123.2 (4)
C9—N1—N2	112.2 (4)	N1—C9—S1	112.8 (4)
C8—N2—N1	113.4 (4)	N4—C10—N6	124.4 (5)
C9—N3—H3A	120.0	N4—C10—S2	113.5 (4)
C9—N3—H3B	120.0	N6—C10—S2	122.1 (4)
H3A—N3—H3B	120.0	N5—C11—C12	123.8 (5)
N5—N4—Zn	115.2 (3)	N5—C11—S2	114.3 (4)
C10—N4—Zn	132.0 (4)	C12—C11—S2	121.9 (4)
C10—N4—N5	112.8 (4)	C13—C12—C11	116.6 (5)
C11—N5—N4	112.5 (4)	C13—C12—H12A	108.1
C10—N6—H6A	120.0	C11—C12—H12A	108.1
C10—N6—H6B	120.0	C13—C12—H12B	108.1
H6A—N6—H6B	120.0	C11—C12—H12B	108.1
C2—C1—H1A	109.5	H12A—C12—H12B	107.3
C2—C1—H1B	109.5	C12—C13—C14	112.7 (5)
H1A—C1—H1B	109.5	C12—C13—H13A	109.0
C2—C1—H1C	109.5	C14—C13—H13A	109.0
H1A—C1—H1C	109.5	C12—C13—H13B	109.0
H1B—C1—H1C	109.5	C14—C13—H13B	109.0
C1—C2—C3	112.5 (10)	H13A—C13—H13B	107.8
C1—C2—H2B	109.1	C13—C14—C15	113.9 (6)
C3—C2—H2B	109.1	C13—C14—H14A	108.8
C1—C2—H2C	109.1	C15—C14—H14A	108.8
C3—C2—H2C	109.1	C13—C14—H14B	108.8
H2B—C2—H2C	107.8	C15—C14—H14B	108.8
C4—C3—C2	112.1 (9)	H14A—C14—H14B	107.7
C4—C3—H3C	109.2	C16—C15—C14	114.3 (6)
C2—C3—H3C	109.2	C16—C15—H15A	108.7
C4—C3—H3D	109.2	C14—C15—H15A	108.7
C2—C3—H3D	109.2	C16—C15—H15B	108.7
H3C—C3—H3D	107.9	C14—C15—H15B	108.7
C5—C4—C3	116.1 (7)	H15A—C15—H15B	107.6
C5—C4—H4A	108.3	C17—C16—C15	113.5 (6)
C3—C4—H4A	108.3	C17—C16—H16A	108.9
C5—C4—H4B	108.3	C15—C16—H16A	108.9
C3—C4—H4B	108.3	C17—C16—H16B	108.9
H4A—C4—H4B	107.4	C15—C16—H16B	108.9
C6—C5—C4	113.5 (5)	H16A—C16—H16B	107.7
C6—C5—H5B	108.9	C16—C17—C18	113.1 (7)
C4—C5—H5B	108.9	C16—C17—H17A	109.0
C6—C5—H5C	108.9	C18—C17—H17A	109.0
C4—C5—H5C	108.9	C16—C17—H17B	109.0
H5B—C5—H5C	107.7	C18—C17—H17B	109.0
C5—C6—C7	114.8 (5)	H17A—C17—H17B	107.8
C5—C6—H6C	108.6	C17—C18—H18A	109.5
C7—C6—H6C	108.6	C17—C18—H18B	109.5
C5—C6—H6D	108.6	H18A—C18—H18B	109.5
C7—C6—H6D	108.6	C17—C18—H18C	109.5
H6C—C6—H6D	107.5	H18A—C18—H18C	109.5
C8—C7—C6	114.6 (5)	H18B—C18—H18C	109.5

N4—Zn—N1—C9	−143.6 (4)	C9—S1—C8—N2	−0.1 (4)
Cl1—Zn—N1—C9	−22.4 (5)	C9—S1—C8—C7	179.6 (5)
Cl2—Zn—N1—C9	102.0 (4)	N2—N1—C9—N3	−179.2 (4)
N4—Zn—N1—N2	51.9 (3)	Zn—N1—C9—N3	15.9 (8)
Cl1—Zn—N1—N2	173.1 (3)	N2—N1—C9—S1	0.3 (5)
Cl2—Zn—N1—N2	−62.5 (3)	Zn—N1—C9—S1	−164.6 (3)
C9—N1—N2—C8	−0.3 (6)	C8—S1—C9—N3	179.4 (5)
Zn—N1—N2—C8	167.0 (4)	C8—S1—C9—N1	−0.1 (4)
N1—Zn—N4—C10	−116.4 (5)	N5—N4—C10—N6	179.1 (4)
Cl1—Zn—N4—C10	124.8 (4)	Zn—N4—C10—N6	1.5 (8)
Cl2—Zn—N4—C10	−3.3 (5)	N5—N4—C10—S2	0.8 (6)
N1—Zn—N4—N5	66.0 (3)	Zn—N4—C10—S2	−176.8 (3)
Cl1—Zn—N4—N5	−52.8 (4)	C11—S2—C10—N4	−0.7 (4)
Cl2—Zn—N4—N5	179.1 (3)	C11—S2—C10—N6	−179.1 (5)
C10—N4—N5—C11	−0.4 (6)	N4—N5—C11—C12	−179.7 (5)
Zn—N4—N5—C11	177.6 (4)	N4—N5—C11—S2	−0.1 (6)
C1—C2—C3—C4	−175.8 (9)	C10—S2—C11—N5	0.5 (4)
C2—C3—C4—C5	−178.5 (7)	C10—S2—C11—C12	−179.9 (5)
C3—C4—C5—C6	178.4 (7)	N5—C11—C12—C13	−148.2 (6)
C4—C5—C6—C7	−176.8 (5)	S2—C11—C12—C13	32.2 (8)
C5—C6—C7—C8	178.3 (5)	C11—C12—C13—C14	175.9 (6)
N1—N2—C8—C7	−179.5 (5)	C12—C13—C14—C15	−178.1 (6)
N1—N2—C8—S1	0.2 (6)	C13—C14—C15—C16	175.3 (6)
C6—C7—C8—N2	178.9 (5)	C14—C15—C16—C17	−179.8 (7)
C6—C7—C8—S1	−0.8 (7)	C15—C16—C17—C18	177.3 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1	0.86	2.58	3.374 (5)	154
N3—H3B···Cl2ⁱ	0.86	2.77	3.503 (5)	144
N6—H6A···Cl2	0.86	2.49	3.289 (5)	155
N6—H6B···N2ⁱⁱ	0.86	2.19	3.018 (3)	163

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

Experimental details

Crystal data
Chemical formula	[ZnCl₂(C₉H₁₇N₃S)₂]
M_r	534.94
Crystal system, space group	Triclinic, P1
Temperature (K)	294
a, b, c (Å)	8.1750 (16), 11.663 (2), 14.666 (3)
α, β, γ (°)	73.150 (17), 77.83 (2), 88.81 (3)
V (Å³)	1307.0 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.32
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.693, 0.879
No. of measured, independent and observed [I > 2σ(I)] reflections	5096, 4734, 3303
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.177, 1.02
No. of reflections	4734
No. of parameters	256
No. of restraints	?
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.17, −1.27

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Zn—Cl1	2.2283 (16)	Zn—N1	2.037 (4)
Zn—Cl2	2.2626 (17)	Zn—N4	2.026 (4)

Cl1—Zn—Cl2	114.97 (7)	N4—Zn—Cl1	112.65 (12)
N1—Zn—Cl1	109.00 (12)	N4—Zn—Cl2	108.05 (13)
N1—Zn—Cl2	106.06 (13)	N4—Zn—N1	105.49 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···Cl1	0.86	2.58	3.374 (5)	154
N3—H3B···Cl2ⁱ	0.86	2.77	3.503 (5)	144
N6—H6A···Cl2	0.86	2.49	3.289 (5)	155
N6—H6B···N2ⁱⁱ	0.86	2.19	3.018 (3)	163

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

Acknowledgements

The authors gratefully acknowledge Professor Hua-Qin Wang of the Analysis Center, Nanjing University, for providing the Enraf–Nonius CAD-4 diffractometer for this research project.

References

Alzuet, G., Borras, J., Estevan, F. & Liu-Gonzalez, M. (2003). Inorg. Chim. Acta, 343, 56–60. Web of Science CSD CrossRef CAS Google Scholar
Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shen, X.-Q., Zhong, H.-J. & Zheng, H. (2004). Polyhedron, 23, 1851–1857. Web of Science CSD CrossRef CAS Google Scholar