Bis(2-amino-6-methyl-1,3-benzothia­zole-κN 3)bis­(4-nitro­benzoato-κO 1)zinc

Xue-Tong Sun; Xiu-Guang Wang; Xiao-Jun Zhao

doi:10.1107/S1600536811022331

. 2011 Jun 18;67(Pt 7):m933. doi: 10.1107/S1600536811022331

Bis(2-amino-6-methyl-1,3-benzothiazole-κN ³)bis(4-nitrobenzoato-κO ¹)zinc

Xue-Tong Sun ^a, Xiu-Guang Wang ^a, Xiao-Jun Zhao ^a,^*

PMCID: PMC3151824 PMID: 21836917

Abstract

In the title mononuclear complex, [Zn(C₇H₄NO₄)₂(C₈H₈N₂S)₂], the Zn^II atom is coordinated by two N atoms from two 2-amino-6-methyl-1,3-benzothiazole and by two carboxylate O atoms from two 4-nitrobenzoate ligands, adopting a slightly distorted tetrahedral coordination geometry. In the crystal, intermolecular N—H⋯O hydrogen bonds between the amino group of 2-amino-6-methyl-1,3-benzothiazole and the carboxylate group of 4-nitrobenzoate link these discrete mononuclear units into a one-dimensional supramolecular chain extending parallel to [100].

Related literature

For the properties of metal complexes with aminobenzothiazole and its derivatives, see: Sun & Cui (2008 ▶); Chen et al. (2008 ▶); Kovalska et al. (2006 ▶); Batista et al. (2007 ▶); Marconato et al. (1998 ▶).

Experimental

Crystal data

[Zn(C₇H₄NO₄)₂(C₈H₈N₂S)₂]
M _r = 726.04
Monoclinic,
a = 13.2240 (8) Å
b = 10.7369 (7) Å
c = 21.8863 (13) Å
β = 96.099 (1)°
V = 3089.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.99 mm⁻¹
T = 296 K
0.05 × 0.04 × 0.03 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.952, T _max = 0.971
15119 measured reflections
5418 independent reflections
4724 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.101
S = 1.05
5418 reflections
426 parameters
H-atom parameters constrained
Δρ_max = 1.24 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); 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 ▶) and DIAMOND (Brandenburg & Berndt, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022331/go2014sup1.cif

e-67-0m933-sup1.cif^{(28.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022331/go2014Isup2.hkl

e-67-0m933-Isup2.hkl^{(265.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Zn1—O6	1.9489 (18)
Zn1—O1	1.9717 (18)
Zn1—N3	2.036 (2)
Zn1—N1	2.054 (2)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.86	2.27	3.008 (3)	144
N2—H2B⋯O5ⁱ	0.86	2.05	2.845 (3)	153
N4—H4A⋯O6	0.86	2.20	2.971 (3)	149
N4—H4B⋯O2ⁱⁱ	0.86	2.05	2.860 (3)	156

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

Acknowledgments

The authors gratefully acknowledge financial support from Tianjin Normal University.

supplementary crystallographic information

Comment

Organic compounds containing benzothiazole and their metal complexes are of optical, biological, and pharmaceutical importance used extensively as electroluminescent device, fluorescent probes for DNA and corrosion inhibitors (Kovalska et al. 2006; Batista et al. 2007; Marconato et al. 1998). As our continuing investigation on the coordination behavior of the benzothiazole ligand (Chen et al. 2008), herein, we report the structure of a mononuclear complex, I.

The molecular structure of the title mononuclear complex is shown in Fig.1 and selected bond lengths and angles are listed in Table 1. The Zn^II atom in the mononuclear stucture of I exhibits a slightly distorted tetrahedral coordination geometry involving two thiazole N atoms from two different 2-amino-6-methyl-1,3-benzothiazole ligands and two monodentate carboxylate O atoms from two separate 4-nitrobenzolate anions. Both ligands act as typically terminal ligands to coordinate to Zn^II ion in monodentate mode with the intramolecular N—H···O hydrogen bonds between amino group of neutral 2-amino-6-methyl-1,3-benzothiazole and anionic 4-nitrobenzolate ligand stabilized the molecular structure.

In the crystal structure, intermolecular N—H···O hydrogen bonds between amino group of neutral 2-amino-6-methyl-1,3-benzothiazole and anionic 4-nitrobenzolate ligands link the discrete mononuclear entities into a one-dimensional supramolecular chain (Fig.2 and Table 2).

Experimental

To an ethanol solution (6.0 ml) containing 2-amino-6-methyl-1,3-benzothiazole (32.8 mg, 0.2 mmol) and 4-nitrobenzoic acid (33.4 mg, 0.2 mmol) was dropwise added an aqueous solution (4.0 ml) of ZnCl₂ (13.6 mg, 0.1 mmol) with constant stirring. The reaction was stirred at room temperature for about 20 min and the precipitate was filtered off, leaving the filtrate to evaporate at room temperature. Yellow block-shaped crystals were obtained with five days. Yield: 50% based on Zn^II salt. Anal. Calcd. for C₃₀H₂₄N₆O₈S₂Zn: C, 49.63; H, 3.33; N, 11.57%. Found: C, 49.60; H, 3.31; N, 11.61%.