Diaqua­bis(2,2′-biimidazole)cobalt(II) 4,4′-dicarboxy­biphenyl-3,3′-di­car­boxylate

Jie Kang; Chang-Cang Huang; Lai-Sheng Zhai; Xiao-Huan Qin; Zhong-Qian Liu

doi:10.1107/S1600536809007764

. 2009 Mar 11;65(Pt 4):m380–m381. doi: 10.1107/S1600536809007764

Diaquabis(2,2′-biimidazole)cobalt(II) 4,4′-dicarboxybiphenyl-3,3′-dicarboxylate

Jie Kang ^a,^b,^*, Chang-Cang Huang ^b, Lai-Sheng Zhai ^b, Xiao-Huan Qin ^b, Zhong-Qian Liu ^b

PMCID: PMC2968794 PMID: 21582332

Abstract

In the title compound, [Co(C₆H₆N₄)₂(H₂O)₂](C₁₆H₈O₈), the Co^II cation and the organic anion occupy different crystallographic inversion centres and, as a consequence, the asymmetric unit comprises two half-molecules. The benzene groups are coplanar. The four coordinating N atoms of the two bidentate biimidazole ligands define the equatorial plane of a slightly distorted octahedral CoO₂N₄ geometry, and the water O atoms lie in the axial coordination sites. Translational (a, Inline graphic ) and inversion-related symmetry operations link the Co complex molecules and the negatively charged carboxylate anions via intermolecular N—H⋯O and O—H⋯O hydrogen bonds into sheets parallel to (01). The coordinated water molecules connect the sheets through O—H⋯O hydrogen bonds, forming a three-dimensional framework. In addition, two intramolecular O—H⋯O hydrogen bonds are observed between the carboxyl and carboxylate groups.

Related literature

For a review on organic–inorganic hybrid materials, see: Hagrman et al. (1999 ▶). For a tetranuclear cobalt complex with a 1,2,4-benzenetricarboxylate linker, see: Jia et al. (2007 ▶). For a highly porous metal-organic framework with a benzenedicarboxylate linker, see: Li et al. (1999 ▶). For coordination polymers of Ag(I), Cd(II) and Zn(II) with the flexible 2-(1H-imidazole-1-yl)acetic acid linker, see: Wang et al. (2007 ▶). For the structure of 1,1′-biphenyl-2,3,3′,4′-tetracarboxylic acid monohydrate and related structures cited therein, see: Jiang et al. (2008 ▶).

Experimental

Crystal data

[Co(C₆H₆N₄)₂(H₂O)₂](C₁₆H₈O₈)
M _r = 691.48
Triclinic,
a = 8.2272 (16) Å
b = 9.772 (2) Å
c = 10.484 (2) Å
α = 63.81 (3)°
β = 67.93 (3)°
γ = 84.03 (3)°
V = 699.0 (2) Å³
Z = 1
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 293 K
0.42 × 0.26 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.760, T _max = 0.874
4982 measured reflections
2603 independent reflections
2527 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.087
S = 1.01
2603 reflections
227 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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/S1600536809007764/si2153sup1.cif

e-65-0m380-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809007764/si2153Isup2.hkl

e-65-0m380-Isup2.hkl^{(127.8KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Co1—O5	2.0882 (19)
Co1—N1	2.1412 (16)
Co1—N3	2.1579 (16)

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O5—Co1—N1	88.32 (7)
N1—Co1—N3ⁱ	100.77 (6)
O5—Co1—N3	87.82 (7)

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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
N2—H2A⋯O1ⁱⁱ	0.92 (2)	1.87 (2)	2.791 (3)	178.8 (18)
N4—H4A⋯O2ⁱⁱ	0.920 (18)	1.897 (19)	2.808 (3)	170.3 (19)
O5—H1W⋯O1ⁱⁱⁱ	0.82 (2)	1.93 (2)	2.739 (3)	169 (2)
O5—H2W⋯O4ⁱ	0.81 (2)	1.88 (2)	2.673 (3)	163 (2)
O3—H3⋯O2	0.82	1.62	2.432 (3)	172

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

Acknowledgments

This work was supported by the Foundation of the Education Committee of Fujian Province (grant No. JA08103), and the Foundation of Daiichi Pharmaceutical (Beijing) Co, Ltd (grant No. 06B004).

supplementary crystallographic information

Comment

Design and construction of metal-organic frameworks (MOFs) have attracted considerable attention in recent years, not only for their intriguing structural motifs (Wang et al. 2007), but also for their potential applications, e. g. as organic-inorganic hybrid materials (Hagrman et al., 1999), highly porous metal-organic framework (Li et al., 1999), magnetochemistry (Jia et al., 2007). In contrast, the two ionic components of the title structure interact with N—H···O and O—H···O hydrogen bonds to form a three-dimensional framework.

As shown in Fig. 1, the Co atom (site symmetry 1) is bonded to two aqua and two bidentate biimidizole ligands, to result in a slightly distorterd octahedral CoO₂N₄ geometry for the central metal. The Co^II cation and the organic anion occupy different crystallographic inversion centres, and as a consequence the asymmetric unit of the cell comprises two half molecules (Z' = 1/2), and the benzene groups are co-planar. The four nitrogen atoms belonging to two biimidizole ligands lie in the equatorial plane and the two aqua oxygen atoms lie in the axial coordination sites. Selected bond lengths and angles around Co are listed in Table 1. The 1,1'-biphenyl-3,3'-dicarboxylate-4,4'-dicarboxylic acid acts as a negative electron balance. With three kinds of hydrogen bonds (Table 2) of N2—H2A···O1, N4—H4A···O2, and O5—H1W···O1, two-dimensional planes are formed. Furthermore, a three-dimensional framework (Fig. 2) is generated with the intermolecular hydrogen bonding contact O5—H2W···O4 along the [-1 0 1] direction. The organic anion has two intramolecular O3—H3···O2 hydrogen bonds between the carboxylic acid units and the carboxylate acceptors (Table 2). In contrast to the co-planar biphenyl group of the title compound, a dihedral angle of 42.30 (11)° between the two benzene rings was observed in the structure of 1,1'-biphenyl-2,3,3',4'-tetracarboxylic acid monohydrate (Jiang et al. 2008).

Experimental

All chemicals and Teflon-lined stainless steel autoclave were purchased from Jinan Henghua Sci. & Tec. Co. Ltd. A mixture of 3,3',4,4'-biphenyl tetracarboxylic acid (0.1 mmoL), cobalt(II) acetate (0.1 mmoL), and diimdazole (0.1 mmoL) in 10 ml distilled water sealed in a 25 ml Teflon-lined stainless steel autoclave was kept at 433 K for three days. Yellow crystals suitable for the X-ray experiment were obtained.