(μ-4,4′-Bipyridine-κ2 N:N′)bis­[triaqua­(4,4′-bipyridine-κN)(3-nitro­phthalato-κO 2)cobalt(II)]

Hong-Xu Guo; Zhong-Liang Yao; Wen Weng; Xi-Zhong Li

doi:10.1107/S160053680902875X

. 2009 Jul 25;65(Pt 8):m992–m993. doi: 10.1107/S160053680902875X

(μ-4,4′-Bipyridine-κ² N:N′)bis[triaqua(4,4′-bipyridine-κN)(3-nitrophthalato-κO ²)cobalt(II)]

Hong-Xu Guo ^a,^*, Zhong-Liang Yao ^b, Wen Weng ^a, Xi-Zhong Li ^a

PMCID: PMC2977433 PMID: 21583433

Abstract

The title binuclear complex, [Co₂(C₈H₃NO₆)₂(C₁₀H₈N₂)₃(H₂O)₆], has been synthesized hydrothermally from 3-nitrophthalic acid (H₂NPA), Co(NO₃)₂·6H₂O and 4,4′-bipyridine (4,4′-bipy). The molecule of the complex occupies a special position on an inversion centre. The Co^II atom has a slightly distorted octahedral environment formed by two N atoms from two 4,4′-bipy ligands, one carboxylate O atom from NPA, and three O atoms of water molecules. An extensive O—H⋯O and N—H⋯O hydrogen-bonding system links molecules of the complex into a three-dimensional network.

Related literature

For background to metal-involved supramolecular compounds, see: Noro (2004 ▶); Yaghi et al. (2003 ▶); Rao et al. (2004 ▶); Huang et al. (2004 ▶); Zhang et al. (2004 ▶). For other 3-nitrophthalic derivatives, see: Deng et al. (2007 ▶); Guo (2004 ▶); Song et al. (2007 ▶); Xiong & Qi (2007 ▶).

Experimental

Crystal data

[Co₂(C₈H₃NO₆)₂(C₁₀H₈N₂)₃(H₂O)₆]
M _r = 1112.74
Monoclinic,
a = 15.672 (3) Å
b = 9.4283 (19) Å
c = 16.063 (3) Å
β = 103.92 (3)°
V = 2303.8 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.21 × 0.15 × 0.12 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.765, T _max = 0.872
21789 measured reflections
5252 independent reflections
3669 reflections with I > 2σ(I)
R _int = 0.079

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.134
S = 1.01
5252 reflections
352 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Data collection: SMART (Siemens, 1994 ▶); cell refinement: SAINT (Siemens, 1994 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680902875X/ya2101sup1.cif

e-65-0m992-sup1.cif^{(24.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680902875X/ya2101Isup2.hkl

e-65-0m992-Isup2.hkl^{(257.2KB, 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
O7—H7A⋯O3ⁱ	0.842 (10)	1.960 (11)	2.798 (3)	173 (3)
O7—H7B⋯O4ⁱⁱ	0.845 (10)	1.942 (12)	2.772 (3)	167 (3)
O8—H8A⋯O2	0.854 (10)	1.855 (13)	2.677 (3)	161 (3)
O8—H8B⋯N3ⁱⁱⁱ	0.847 (10)	2.021 (15)	2.830 (4)	159 (3)
O9—H9B⋯O4ⁱ	0.849 (10)	1.810 (13)	2.645 (3)	167 (3)
O9—H9C⋯O3	0.849 (10)	1.968 (13)	2.801 (3)	167 (3)

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

Acknowledgments

This work was supported by the Natural Science Foundation of Fujian Province (No. 2008 J0172) and the National Natural Science Foundation of China (20705031).

supplementary crystallographic information

Comment

Design and assembly of metal-involving supramolecular architectures are currently of great interest in the field of supramolecular chemistry and crystal engineering, because they can provide novel topology and functional materials (Noro, 2004; Yaghi et al., 2003; Rao et al., 2004). During the past decades, extensive efforts have been focused on the design and assembly of supramolecular architectures of this kind (Huang et al., 2004; Zhang et al., 2004). Although the multifunctional ligand, 3-nitrophthalic acid (H₂NPA), has been utilized to build many coordination complexes, such as dinuclear centrosymmetric complexes [LaL(HL)(H₂O)₃]₂.2H₂O (L = NPA) (Deng et al., 2007), [La₂(C₈H₃NO₆)₂(C₈H₄NO₆)₂(H₂O)₆].2H₂O (Xiong & Qi, 2007), and [Na(C₈H₄NO₆)(H₂O)₃].H₂O (Guo, 2004), only a few mixed ligand complexes involving NPA have been reported so far (Song et al., 2007). In this work, we employed NPA and 4,4'-bipy ligands to produce a novel binuclear complex, [Co₂(NPA)₂(bipy)₃(H₂O)₆](I).

Complex (I) occupies a special position in the inversion centre; the asymmetric unit consists of one cobalt(II) atom, one NPA ligand, one terminal and one-half of a bridging 4,4'-bipy groups, as well as three metal-coordinated water molecules.(Fig. 1 and Table 1). The Co1 atom has a a slightly distorted octahedral environment formed by two N atoms from two different bipy ligands, one carboyxlate O atom of the NPA ligand, and three water molecules. The µ₂-4,4'-bipyridine ligand bridges two [Co(NPA)(bipy)(H₂O)₃] units of the binuclear complex.

The extensive system of O—H···O hydrogen bonds links molecules of the complex into a three-dimensional network (Fig. 2; Table 1).

Experimental

A solution of Co(NO₃)₂.6H₂O (0.0291 g, 0.1 mmol) in 5 ml of water was added dropwise under continuous stirring to an aqueous solution (5 ml) of 3-nitrophthalic acid (0.0211 g, 0.1 mmol) and 4,4'-bipyridine (0.0156 g, 0.1 mmol). The resulting mixture was then transferred into a Teflon-lined stainless steel vessel, which was sealed and kept at 393 K for 72 h. The vessel was then cooled to room temperature, the reaction mixture was filtered, and single crystals were obtained from the filtrate after a few days of slow evaporation at room temperature.