Bis(μ-3,5-dimethyl-4H-1,2,4-triazol-4-amine-κ2N1:N2)bis­[bis­(thio­cyanato-κN)zinc]–bis­(3,5-dimethyl-4H-1,2,4-triazol-4-amine-κN1)bis­(thio­cyanato-κN)zinc (1/2)

Ge, H.-Y.; Li, B.-L.

doi:10.1107/S1600536811027887

Volume 67
Part 8
Pages m1100-m1101
August 2011

Received 17 June 2011
Accepted 12 July 2011
Online 16 July 2011

Key indicators
Single-crystal X-ray study
T = 223 K
Mean (C-C) = 0.006 Å
Disorder in main residue
R = 0.042
wR = 0.090
Data-to-parameter ratio = 14.2
Details

Bis(-3,5-dimethyl-4H-1,2,4-triazol-4-amine-²N¹:N²)bis[bis(thiocyanato-N)zinc]-bis(3,5-dimethyl-4H-1,2,4-triazol-4-amine-N¹)bis(thiocyanato-N)zinc (1/2)

Hai-Yan Ge ^a and Bao-Long Li ^b ^*

^aCollege of Chemical Engineering, Taishan Medical College, Taian 271016, People's Republic of China, and ^bCollege of Chemistry, Chemical Engineering and Materials Science, The Key Laboratory of Organic Synthesis of Jiangsu Province, Soochow University, Suzhou 215123, People's Republic of China
Correspondence e-mail: libaolong@suda.edu.cn

In the crystal structure of the title 1:2 adduct, [Zn₂(NCS)₄(C₄H₈N₄)₂]·2[Zn(NCS)₂(C₄H₈N₄)₂] or (Ia)·2(Ib), each Zn^II atom is coordinated in a distorted tetrahedral geometry by four N atoms from two triazole rings of two 4-amino-3,5-dimethyl-1,2,4-triazole (admt) ligands and two NCS^- ligands. In (Ia), double N¹:N²-bridging admt ligands connect two Zn^II atoms, forming a dimer with a Zn₂(admt)₂ six-membered metallacycle located on a crystallographic inversion center. In (Ib), the admt ligands exhibit monodentate N¹-coordination modes. Weak N-HN, N-HS and C-HS hydrogen bonds play an important role in the intermolecular packing. The S and C atoms of two thiocyanato ligands are disordered over two sets of sites in ratios of 0.57 (3):0.43 (3) and 0.63 (3):0.37 (3), respectively.

Related literature

For background to transition metal complexes of 1,2,4-triazole derivatives, see: Haasnoot (2000); Liu et al. (1999, 2003); Zhao et al. (2002); Yi et al. (2004); Lavrenova et al. (1992); Zhang et al. (2007, 2011). For related structures, see: Lavrenova et al. (1992); Zhang et al. (2007, 2011).

Experimental

Crystal data

[Zn₂(NCS)₄(C₄H₈N₄)₂]·2[Zn(NCS)₂(C₄H₈N₄)₂]
M_r = 1399.08
Triclinic, $[P \overline 1]$
a = 8.7665 (8) Å
b = 9.3100 (5) Å
c = 20.661 (3) Å
= 92.560 (9)°
= 95.926 (2)°
= 115.427 (6)°
V = 1507.3 (3) Å³
Z = 1
Mo K radiation
= 1.91 mm^-1
T = 223 K
0.34 × 0.30 × 0.14 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998) T_min = 0.564, T_max = 0.776
14831 measured reflections
5484 independent reflections
4550 reflections with I > 2(I)
R_int = 0.034

Refinement

R[F² > 2(F²)] = 0.042
wR(F²) = 0.090
S = 1.04
5484 reflections
387 parameters
30 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.55 e Å^-3
_min = -0.36 e Å^-3

Table 1
Selected bond lengths (Å)

Zn1-N5	1.914 (3)
Zn1-N6	1.954 (3)
Zn1-N2ⁱ	2.011 (3)
Zn1-N1	2.012 (3)
Zn2-N16	1.926 (3)
Zn2-N15	1.962 (3)
Zn2-N7	1.990 (3)
Zn2-N11	2.000 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N4-HW1S2ⁱⁱ	0.89 (2)	2.83 (3)	3.495 (3)	133 (3)
N4-HW2N12	0.88 (2)	2.31 (2)	3.157 (4)	162 (3)
N10-HW3N12ⁱⁱⁱ	0.85 (2)	2.47 (2)	3.251 (4)	152 (3)
N10-HW4S4ⁱⁱⁱ	0.87 (2)	2.80 (2)	3.641 (4)	163 (3)
N14-HW5N8^iv	0.88 (2)	2.20 (2)	3.061 (4)	167 (3)
N14-HW6S3A^v	0.87 (2)	2.83 (3)	3.617 (9)	151 (3)
N14-HW6S3B^v	0.87 (2)	2.83 (3)	3.542 (18)	140 (3)
C13-H13BS3A^v	0.97	2.82	3.458 (7)	124
Symmetry codes: (ii) x-1, y-1, z; (iii) x, y-1, z; (iv) x-1, y, z; (v) -x+1, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZQ2110 ).

Acknowledgements

This work was supported by the Funds of the Key Laboratory of Organic Synthesis Chemistry of Jiangsu Province and the Youth Foundation of Taishan Medical College, People's Republic of China.

References

Haasnoot, J. G. (2000). Coord. Chem. Rev. 200-202, 131-185.
Jacobson, R. (1998). REQAB. Private communication to the Rigaku Corporation, Tokyo, Japan.
Lavrenova, L. G., Baidina, I. A., Ikorskii, V. N., Sheludjkova, L. A. & Larionov, S. V. (1992). Zh. Neorg. Khim. 37, 630-634.
Liu, J. C., Guo, G. C., Huang, J. S. & You, X. Z. (2003). Inorg. Chem. 42, 235-243.
Liu, J. C., Xu, Y., Duan, C. Y., Wang, S. L., Liao, F. L., Zhuang, J. Z. & You, X. Z. (1999). Inorg. Chim. Acta, 295, 229-233.
Rigaku (2000). CrystalClear. Rigaku Corporation, Tokyo, Japan.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Yi, L., Ding, B., Zhao, B., Cheng, P., Liao, D. Z., Yan, S. P. & Jiang, Z. H. (2004). Inorg. Chem. 43, 33-43.
Zhang, R., Chen, Q., Yang, X. & Wu, X. (2011). Acta Cryst. E67, m26.
Zhang, Y.-M., Zhang, Y.-P., Li, B.-L. & Zhang, Y. (2007). Acta Cryst. C63, m120-m122.
Zhao, Q. H., Li, H. F., Chen, Z. D. & Fang, R. B. (2002). Inorg. Chim. Acta, 36, 142-146.