Bis(2-amino­benzothia­zole-κN 1)bis­(thio­cyanato-κN)zinc(II)

Seung Wook Suh; Chong-Hyeak Kim; Inn Hoe Kim

doi:10.1107/S1600536809030931

. 2009 Aug 8;65(Pt 9):m1054. doi: 10.1107/S1600536809030931

Bis(2-aminobenzothiazole-κN ¹)bis(thiocyanato-κN)zinc(II)

Seung Wook Suh ^a, Chong-Hyeak Kim ^b, Inn Hoe Kim ^a,^*

PMCID: PMC2969946 PMID: 21577414

Abstract

The Zn^II ion in the title complex, [Zn(NCS)₂(C₇H₆N₂S)₂], is tetrahedrally coordinated within an N₄ donor set defined by two N atoms of two terminal isothiocyanate ligands and by two heterocyclic N atoms of two different 2-aminobenzothiazole ligands. This arrangement is stabilized by intramolecular N—H⋯N hydrogen bonds. In the crystal structure, molecules are linked through N—H⋯S hydrogen bonds to form a two-dimensional array.

Related literature

For related literature on organic–inorganic hybrid supramolecular complexes, see: Batten & Robson (1998 ▶); Braga et al. (1998 ▶); Iwamoto (1996 ▶). For the use of pseudo-halides in the construction of supramolecular assemblies, see: Vrieze & Koten (1987 ▶); Cortes et al. (1997 ▶); Yun et al. (2004 ▶); Kim et al. (2001 ▶, 2008 ▶). For the coordination chemistry of imidazole and thiazole derivatives, see: Balch et al. (1993 ▶); Costes et al. (1991 ▶); Suh et al. (2005 ▶, 2007 ▶).

Experimental

Crystal data

[Zn(NCS)₂(C₇H₆N₂S)₂]
M _r = 481.93
Triclinic,
a = 8.4379 (1) Å
b = 9.4900 (1) Å
c = 13.3037 (2) Å
α = 97.735 (1)°
β = 107.302 (1)°
γ = 94.232 (1)°
V = 1000.52 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.66 mm⁻¹
T = 296 K
0.41 × 0.28 × 0.21 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi scan (SADABS; Bruker, 2001 ▶) T _min = 0.550, T _max = 0.722
19351 measured reflections
4901 independent reflections
4238 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.079
S = 1.05
4901 reflections
244 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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 Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030931/tk2521sup1.cif

e-65-m1054-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030931/tk2521Isup2.hkl

e-65-m1054-Isup2.hkl^{(240KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N20—H20A⋯N1	0.86	2.24	3.027 (3)	152
N20—H20B⋯S1ⁱ	0.86	2.70	3.5015 (19)	156
N30—H30A⋯N2	0.86	2.21	3.002 (3)	152
N30—H30B⋯S2ⁱⁱ	0.86	2.57	3.404 (2)	162

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

supplementary crystallographic information

Comment

Organic-inorganic hybrid supramolecular complexes of 1-, 2-, and 3-D frameworks has attracted great interest recently (Iwamoto, 1996; Batten & Robson, 1998), as they have useful properties, viz. electronic, magnetic, optical, catalytic, etc. (Braga et al., 1998). For designing novel multi-dimensional frameworks, we (Kim et al., 2001; Kim et al., 2008) and others (Cortes et al., 1997; Yun et al., 2004) have used the coordination properties of various pseudohalide ions and complementary organic ligands. Pseudo-halide ions, e.g. CN^-, SCN^-, N₃^-, are known to build up 1-, 2- and 3-D structures by bridging metal centers (Vrieze & Koten, 1987). The of use of complementary organic ligands, such as aliphatic and aromatic amines is also known to play an important role in stabilizing multi-dimensional structures. In particulae, aromatic heterocycles such as imidazole and thiazole derivatives represent an important class of ligands in coordination chemistry (Balch et al., 1993; Costes et al., 1991). However, frameworks of metal complexes containing thiazole derivatives have been considerably less investigated. Our research is focused on the development of novel supramolecular framework structures utilizing the terminal and bridging properties of pseudo-halide ions, and the coordination behaviour of thiazole derivatives as complementary organic ligands (Suh et al., 2005, 2007). Herein, we present the synthesis and structure determination of the title complex, (I), with 2-aminobenzothiazole, Fig. 1.

Experimental

A water-methanolic (1:1) solution (20 ml) of potassium thiocyanate (2 mmol, 0.19 g) was added to a water-methanolic (1:1) solution (20 ml) of Zn(NO₃)₂.6H₂O (1 mmol, 0.30 g). To this mixture, a water-methanolic (1:1) solution (20 ml) of 2-aminobenzothiazole (3 mmol, 0.45 g) was introduced, with stirring. The small amount of precipitates formed from the resulting solution were filtered off. The filtered solution was allowed to stand at room temperature. After a few days silver blocks were obtained. Elemental analysis found: C 40.41, H 2.67, N 18.11, S 26.59, Zn 13.60%; C₁₆H₁₂N₆S₄Zn requires: C 39.87, H 2.51, N 17.44, S 26.61, Zn 13.56%.