catena-Poly[[diaqua­bis(1H-imidazole-κN 3)cobalt(II)]-μ-2,3,5,6-tetra­chloro­tereph­thal­ato-κ2 O 1:O 4]

Chang-Ge Zheng; Peng Zhang; Ping Li; Pei-Pei Zhang

doi:10.1107/S1600536812005429

. 2012 Mar 3;68(Pt 4):m368. doi: 10.1107/S1600536812005429

catena-Poly[[diaquabis(1H-imidazole-κN ³)cobalt(II)]-μ-2,3,5,6-tetrachloroterephthalato-κ² O ¹:O ⁴]

Chang-Ge Zheng ^a,^*, Peng Zhang ^a, Ping Li ^a, Pei-Pei Zhang ^a

PMCID: PMC3343789 PMID: 22589763

Abstract

In the title compound, [Co(C₈Cl₄O₄)(C₃H₄N₂)₂(H₂O)₂]_n, the Co^II ion displays a distorted octahedral coordination geometry with two O atoms from two monodentate tetrachloroterephthalate dianions, two N atoms from two imidazole molecules and two O atoms from two water molecules. The Co^II ions are connected via the tetrachloroterephthalate dianions into a chain running along the crystallographic [110] direction. Adjacent chains are linked into a two-dimensional network arranged parallel to (010) by classical N—H⋯O and O—H⋯O hydrogen bonds.

Related literature

For magnetism, gas storage and electrooptic properties, see: Kumar et al. (2009 ▶); Farha et al. (2009 ▶); Zhou et al. (2006 ▶); Mulder et al. (2005 ▶); Zhang et al. (2007 ▶). For the geometric parameters of related compounds, see: Murugavel et al. (2002 ▶); Rogan et al. (2006 ▶); Tong et al. (2002 ▶); Zhang & Lu (2004 ▶).

Experimental

Crystal data

[Co(C₈Cl₄O₄)(C₃H₄N₂)₂(H₂O)₂]
M _r = 533.01
Monoclinic,
a = 18.646 (4) Å
b = 12.068 (2) Å
c = 10.741 (2) Å
β = 120.76 (3)°
V = 2076.9 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.38 mm⁻¹
T = 295 K
0.58 × 0.52 × 0.31 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.677, T _max = 1.000
6189 measured reflections
2342 independent reflections
1959 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.078
S = 1.06
2342 reflections
133 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812005429/rk2332sup1.cif

e-68-0m368-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812005429/rk2332Isup2.hkl

e-68-0m368-Isup2.hkl^{(115.2KB, 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
O3—H3A⋯O1ⁱ	0.85	1.94	2.7681 (19)	166
O3—H3B⋯O2ⁱⁱ	0.85	2.01	2.696 (2)	137
N2—H2B⋯O2ⁱⁱⁱ	0.86	1.96	2.803 (2)	167

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

Acknowledgments

This work was supported by the Center of Analysis and Testing of Jiangnan University and the Research Institute of Elemento–Organic Chemistry of Suzhou University.

supplementary crystallographic information

Comment

The design and synthesis of coordination polymers has attracted great interest in functional solid–state materials, owing to their excellent properties in magnetism, gas storage and electrooptic materials (Kumar et al., 2009; Farha et al., 2009; Zhou et al., 2006). Herein, compared with 1,4–benzenedicarboxylic acid, tetrachloroterephthalic acid can be used to construct materials which have different properties. Computational study suggests that 1,4–benzenedicarboxylic acid with chemical modification have better adsorption property in gas storage (Mulder et al., 2005; Zhang et al., 2007).

Single–crystal X–ray structural analysis reveals that the title cobalt(II) complex in crystal built from one–dimensional linear chains running along the crystallographic direction [1 1 0]. As shown in Fig. 1, the coordination geometry around the Co(II) atom is a slightly distorted octahedron with N₂O₄ binding set. In the octahedron unit, two O atoms from the tetrachloroterephthalate dianions ligands and two N atoms from the imidazole molecules form the equatorial plane and the axial position is occupied by O atoms from two water molecules. The Co—O bond lengths are 2.1653 (14)Å and 2.0865 (14)Å and agree well with the reported (Murugavel et al., 2002; Rogan et al., 2006). The Co—N bond length are 2.0896 (17)Å, which are comparable with the reported values in the similar complexes (Tong et al., 2002; Zhang & Lu, 2004). In addition, the imidazole and water molecules act as donors in N—H···O and O—H···O hydrogen bonds (Table 1). Adjacent one–dimensional chains are linked into a two–dimensional network arranged along the crystallographic b axis by classical N2—H2B···O2ⁱⁱⁱ and O3—H3A···O1ⁱ hydrogen bonds with the angles of 167° and 166°, respectivly. Symmetry codes: (i) -x+1, y, -z+1/2; (iii) -x+1/2, y+1/2, -z+1/2.

Experimental

All the reagents and solvents employed were commercially available. Tetrachloroterephthalic acid was purified by recrystallization. In a 15 cm long tube, a solution of sodium tetrachloroterephthalate (0.0346 g, 0.1 mmol) and imidazol (0.0068 g, 0.1 mmol) in 5 mL methanol was carefully layered on top of a bilayer solution comprised of a solution of Co(NO₃)₂×6H₂O (0.0291 g, 0.10 mmol) in 5 mL water on the bottom and a buffer solvent of 6 mL ethyl acetate on the top at room temperature. Half a month later, pink block–shaped crystals were obtained, washed with water, and dried on air (0.0618 g, yield: 58% based on Co). Elemental analysis(%) calcd. for C₁₄H₁₂Cl₄CoN₄O₆: C, 31.52; H, 2.25; N, 10.51. Found: C, 31.37; H, 2.24; N, 10.47%.