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

Peng Wang; Rong Wan; Bin Wang; Feng Han; Yao Wang

doi:10.1107/S1600536809032073

. 2009 Aug 19;65(Pt 9):m1086. doi: 10.1107/S1600536809032073

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

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

PMCID: PMC2970057 PMID: 21577437

Abstract

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,
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[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 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

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.

Supplementary Material

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

e-65-m1086-sup1.cif^{(23.5KB, cif)}

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

e-65-m1086-Isup2.hkl^{(231.9KB, hkl)}

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

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)

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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)

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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

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

Acknowledgments

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.

supplementary crystallographic information

Comment

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.

Experimental

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.