catena-Poly[[(2-amino-1,3-benzothia­zole-6-carboxyl­ato-κ2 O,O′)(2,2′-bipyridyl-κ2 N,N′)cadmium]-μ-2-amino-1,3-benzothia­zole-6-carboxyl­ato-κ3 N 1:O,O′]

Dan Gao; Xin Fang; Ke-Ke Zhang; Li-Mao Cai; Jun-Dong Wang

doi:10.1107/S160053681201642X

. 2012 Apr 21;68(Pt 5):m641–m642. doi: 10.1107/S160053681201642X

catena-Poly[[(2-amino-1,3-benzothiazole-6-carboxylato-κ² O,O′)(2,2′-bipyridyl-κ² N,N′)cadmium]-μ-2-amino-1,3-benzothiazole-6-carboxylato-κ³ N ¹:O,O′]

Dan Gao ^a, Xin Fang ^a,^*, Ke-Ke Zhang ^a, Li-Mao Cai ^a, Jun-Dong Wang ^a

PMCID: PMC3344366 PMID: 22590132

Abstract

In the title coordination polymer, [Cd(C₈H₅N₂O₂S)₂(C₁₀H₈N₂)]_n, the Cd^II ion is coordinated by a bidentate 2,2-bipyridyl ligand, two O,O′-chelating 2-amino-1,3-benzothiazole-6-carboxylate (ABTC) ligands and one N-bonded ABTC ligand. The resulting CdN₃O₄ coordination polyhedron approximates to a very distorted pentagonal bipramid with one O and one N atom in axial positions. One of the ABTC ligands is bridging to an adjacent metal atom, generating an infinite chain propagating in [100]. A three-dimensional network is constructed from N—H⋯O and N—H⋯N hydrogen bonds and aromatic π–π stacking interactions [centroid–centroid separations = 3.641 (2) and 3.682 (3) Å].

Related literature

For our recent work on the design and sythesis of benzothiazole coordination networks, see: Fang et al. (2010 ▶); Lei et al. (2010 ▶). For the synthesis of the ligand, see: Das et al. (2003 ▶).

Experimental

Crystal data

[Cd(C₈H₅N₂O₂S)₂(C₁₀H₈N₂)]
M _r = 640.87
Triclinic,
a = 9.977 (2) Å
b = 11.715 (2) Å
c = 11.734 (2) Å
α = 65.28 (3)°
β = 77.52 (3)°
γ = 77.15 (3)°
V = 1202.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 173 K
0.27 × 0.18 × 0.13 mm

Data collection

Rigaku Saturn 724 CCD area-detector diffractometer
Absorption correction: numerical (NUMABS; Higashi, 2000 ▶) T _min = 0.837, T _max = 1.000
10158 measured reflections
5296 independent reflections
5015 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.088
S = 1.08
5296 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 1.50 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: CrystalClear (Rigaku, 2007 ▶); 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: ORTEX (McArdle, 1995 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681201642X/hb6715sup1.cif

e-68-0m641-sup1.cif^{(29.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201642X/hb6715Isup2.hkl

e-68-0m641-Isup2.hkl^{(259.3KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cd1—N3	2.345 (3)
Cd1—O3ⁱ	2.372 (2)
Cd1—O1	2.381 (3)
Cd1—N1	2.391 (3)
Cd1—O2	2.415 (3)
Cd1—O4ⁱ	2.422 (2)
Cd1—N2	2.484 (3)

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Symmetry code: (i) Inline graphic .

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6A⋯O3ⁱⁱ	0.88	2.10	2.917 (4)	155
N6—H6B⋯O3ⁱⁱⁱ	0.88	2.12	2.996 (4)	173
N4—H4A⋯O4ⁱ	0.88	2.25	3.101 (4)	162
N4—H4B⋯N5^iv	0.88	2.21	3.066 (4)	163

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

Acknowledgments

The authors gratefully acknowledge financial support from the Foundations of Fuzhou University (2010-XQ-06) and the Education Department of Fujian Province (JA11020).

supplementary crystallographic information

Comment

As part of our ongoing studies of benzothiaole-based coordination networks (Fang et al., 2010; Lei et al., 2010), we now report the structure of a coordination polymer of cadmium and 2-amino-1,3-benzothiazole-6-carboxylate (ABTC) with 2,2'-bipyridine (bpy) as second ligand.

The polymer is a triclinic system crystal and it crystallizes in the space group of P-1. In the asymmetric unit (Fig. 1), center Cd (II) is seven-coordinated with (κ1, κ2)-µ2 coordination model, where one bpy provides two N atoms, one ABTC affords two O atoms, and the another ABTC affords two O atoms and one N atom of thiazole. The four Cd—O bonds are Cd1—O1, Cd1—O2, Cd1—O3, and Cd1—O4, with distance of 2.380 (7) Å, 2.415 (7) Å, 2.371 (3) Å, and 2.422 (6) Å, respectively. The three Cd—N bonds are Cd1—N1, Cd1—N2, and Cd1—N3, with distance of 2.390 (8) Å, 2.484 (1) Å, and 2.345 (6) Å, respectively, where the Cd1—N2 distance is slightly longer than common distance of Cd and N.

The asymmetric units are forming chains extending along the a axis (Fig. 2), through the one ABTC coordinated to two Cd(II) simultaneously by O from carboxylate and N from thiazole ring, respectively. Furthermore, three-dimensional supermolecular net (Fig. 3) are constructed by hydrogen bonds, as listed in Table 1, and π-π interactions [between thiazole and benzene rings (with certroid-centroid distance of 3.682 (3) Å and centroid-ring plane distance of 3.350 (9) and 3.404 (3) Å), and between the thiazole and bpy rings (with certroid-centroid distance of 3.641 (2) Å and centroid-ring plane distance of 3.478 (9) and 3.331 (7) Å)].

Experimental

The 2-aminobenzothiazole-6-carboxylic acid ligand was obtained by hydrolyzing of ethyl-2-amion-1,3-benzothiazole-6-carboxylate (Das et al. 2003). The mixture of cadmium carbonate (0.0172 g, 0.1 mol), 2-aminobenzothiazole-6-carboxylic acid (0.0388 g, 0.2 mol), 2,2'-bipyridine (0.0160 g, 0.1 mol) and H₂O (8 ml) was sealed in a 23 ml stainless-steel reactor with Teflon liner and heated (283 K per hour) from room temperature to 423 K and kept at 423 K for 4 days, then cooled (279 K per hour) to room temperature. Colorless prisms were obtained.