Aqua­[2,2′-(propane-1,3-di­yl)bis­(5-car­boxy-1H-imidazole-4-carboxyl­ato)-κ4 N 3,O 4:N 3′,O 4′](pyridine-κN)cobalt(II)–4,4′-bipyridine (1/1)

Wei Liu; Xia Li

doi:10.1107/S1600536812029856

. 2012 Jul 25;68(Pt 8):m1109–m1110. doi: 10.1107/S1600536812029856

Aqua[2,2′-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylato)-κ⁴ N ³,O ⁴:N ^3′,O ^4′](pyridine-κN)cobalt(II)–4,4′-bipyridine (1/1)

Wei Liu ^a,^*, Xia Li ^a

PMCID: PMC3414156 PMID: 22904763

Abstract

In the title compound, [Co(C₁₃H₁₀N₄O₈)(C₅H₅N)(H₂O)]·C₁₀H₈N₂, the asymmetric unit comprises half a Co^II complex located on a mirror plane and half a cocrystallized molecule of 4,4′-bipyridine located on an inversion center. The Co^II ion is six coordinate, with distorted octahedral geometry, ligated by two N atoms and two O atoms from a 2,2′-(propane-1,3-diyl)bis(5-carboxy-1H-imidazole-4-carboxylate) dianion, one N atom from a pyridine molecule and one coordinating water molecule. The Co—O bond lengths range from 2.076 (2) to 2.1441 (15) Å, while the Co—N bond lengths are 2.138 (3) and 2.1515 (17) Å. A two-dimensional network of N—H⋯O and O—H⋯N hydrogen bonds stabilizes the crystal packing. There are π–π interactions between the bipyridine and imidazole rings [centroid–centroid distance = 3.7694 (4) Å]. The propane-1,3-diyl group is disordered over two conformations, with refined occupancies of 0.755 (8) and 0.245 (8).

Related literature

For complexes based on substituted 4,5-imidazoledicarboxylic acids, see: Zhu et al. (2010 ▶, 2011 ▶); Lu et al. (2010 ▶); Song et al. (2010 ▶); Zhang et al. (2010 ▶); Wang et al. (2008 ▶); Feng et al. (2010 ▶); Liu et al. (2010 ▶); Zheng et al. (2011 ▶); Li et al. (2009 ▶, 2010 ▶).

Experimental

Crystal data

[Co(C₁₃H₁₀N₄O₈)(C₅H₅N)(H₂O)]·C₁₀H₈N₂
M _r = 661.47
Monoclinic,
a = 7.9733 (10) Å
b = 20.738 (3) Å
c = 8.2987 (11) Å
β = 91.350 (2)°
V = 1371.8 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 296 K
0.22 × 0.18 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T _min = 0.862, T _max = 0.927
11480 measured reflections
3443 independent reflections
2633 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.105
S = 1.05
3443 reflections
219 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.34 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 datablock(s) I, global. DOI: 10.1107/S1600536812029856/pk2422sup1.cif

e-68-m1109-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029856/pk2422Isup2.hkl

e-68-m1109-Isup2.hkl^{(168.9KB, 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—H3⋯O2	0.82	1.65	2.473 (2)	177
O5—H1W⋯N4ⁱ	0.82	1.95	2.727 (3)	157
N2—H2⋯O4ⁱⁱ	0.86	1.93	2.763 (3)	162

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

Acknowledgments

We gratefully acknowledge financial support by the Foundation of Henan Key Science and Technology Research (grant Nos. 122102210414 and 122102210415), the Foundation of Henan Educational Committee (grant Nos. 2010A150003 and 2011B150001), and the Foundation of Henan University of Urban Construction (grant Nos. 2010JYB007 and 2010JYB008).

supplementary crystallographic information

Comment

It is well known that aromatic polycarboxylates, especially the N-heterocyclic carboxylates, are excellent candidates for preparing novel MOFs, because of their versatile coordination modes and potential hydrogen-bonding donors and acceptors. Recently, 4,5-imidazoledicarboxylic acid (Zhu et al., 2010; Lu et al., 2010) and its 2-position substituent derivatives, such as 2-methyl-1H-imidazole-4,5-dicarboxylic acid (Song et al., 2010), 2-ethyl-1H-imidazole-4,5-dicarboxylic acid (Zhang et al., 2010; Wang et al., 2008), 2-propyl-1H-imidazole-4,5-dicarboxylic acid (Feng et al., 2010; Liu et al., 2010), 2-(hydroxymethyl)-1H-imidazole-4,5-dicarboxylic acid (Zheng et al., 2011), 2-phenyl-1H-imidazole-4,5-dicarboxylic acid (Zhu et al., 2011) and 2-pyridyl-1H-imidazole-4,5-dicarboxylic acid (Li et al., 2009; Li et al., 2010) have attracted great attention in the field of coordination chemistry. Now, our group has strong interest in adopting another imidazole dicarboxylate ligand, 1,3-bis-(1H-imidazole-4,5-dicarboxylate acid) propane to prepare various coordination compounds.

As shown in Fig. 1, the molecule is a discrete neutral monomer, in which the asymmetric unit comprises half a CoII complex located on a mirror plane and half a co-crystallized molecule of 4,4'-bipyridine located on an inversion center. The Co^II ion is six coordinate and has a distorted octahedral geometry. It is ligated by two nitrogen atoms and two oxygen atoms from a 1,3-bis-(1H-imidazole-4,5-dicarboxylate) propane dianion, one nitrogen atom from a pyridine molecule and one oxygen atom from a coordinated water molecule. The Co—O distances range from 2.076 (2) to 2.1441 (15) Å, while Co—N distances are 2.138 (3) and 2.1515 (17) Å, respectively. A two-dimensional network of N—H···O and O—H···N hydrogen bonds help to stabilize the crystal packing. Aromatic π-π interactions between bipyridine rings and imidazole rings [centroid—centroid distance = 3.7694 (4) Å] are also observed.

Experimental

A mixture of cobalt chloride hexahydrate (0.0238 g, 0.1 mmol), 1,3-bis-(1H-imidazole-4,5-dicarboxylate acid) propane (0.0352 g, 0.1 mmol), 4,4'-bipyridine (0.0198 g, 0.1 mmol), pyridine (0.8 ml) and H₂O (10 ml) was sealed in a Teflon-lined stainless autoclave and heated at 413 K for 3 days. The bomb was allowed to cool to room temperature gradually and red prismatic crystals were obtained.