Bis(μ-3-chloro­benzene-1,2-dicarboxyl­ato-κ2 O 2:O 2)bis­[diaqua­(5,5′-dimethyl-2,2′-bipyridine-κ2 N,N′)copper(II)]

Fu-An Li; Fu Xu; Xiao-Ming Hu

doi:10.1107/S1600536811035112

. 2011 Sep 14;67(Pt 10):m1366. doi: 10.1107/S1600536811035112

Bis(μ-3-chlorobenzene-1,2-dicarboxylato-κ² O ²:O ²)bis[diaqua(5,5′-dimethyl-2,2′-bipyridine-κ² N,N′)copper(II)]

Fu-An Li ^a,^*, Fu Xu ^a, Xiao-Ming Hu ^a

PMCID: PMC3201524 PMID: 22058694

Abstract

In the centrosymmetric binuclear title compound, [Cu₂(C₈H₃ClO₄)₂(C₁₂H₁₂N₂)₂(H₂O)₄], the Cu^II ion is six-coordinated by two N atoms from a 5,5′-dimethyl-2,2′-bipyridine ligand, two bridging O atoms from two 3-chlorobenzene-1,2-dicarboxylate ligands and two water molecules in a distorted octahedral geometry. The binuclear complex molecules are linked together by intermolecular O—H⋯O hydrogen bonds into a layer parallel to (100). The layers are connected by C—H⋯Cl hydrogen bonds. Intramolecular O—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distance = 3.5958 (16) Å] are also present.

Related literature

For background to polynuclear coordination compounds containing benzenecarboxylate ligands, see: Baca et al. (2005 ▶); Ma et al. (2004 ▶); Thirumurugan & Rao (2005 ▶); Zang et al. (2010 ▶). For O—H⋯O and C—H⋯Cl hydrogen bonds, see: Desiraju (2004 ▶); Song & Iyoda (2009 ▶); Wang et al. (2011 ▶).

Experimental

Crystal data

[Cu₂(C₈H₃ClO₄)₂(C₁₂H₁₂N₂)₂(H₂O)₄]
M _r = 964.72
Monoclinic,
a = 11.6908 (7) Å
b = 11.8643 (6) Å
c = 17.2869 (13) Å
β = 124.806 (5)°
V = 1968.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.774, T _max = 0.792
7602 measured reflections
3450 independent reflections
2845 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.094
S = 1.07
3450 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811035112/hy2462sup1.cif

e-67-m1366-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035112/hy2462Isup2.hkl

e-67-m1366-Isup2.hkl^{(169.2KB, 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
O1W—H1WA⋯O3	0.85	1.79	2.622 (3)	164
O1W—H1WB⋯O4ⁱ	0.85	1.82	2.655 (3)	167
O2W—H2WA⋯O1	0.85	2.17	2.731 (3)	124
O2W—H2WB⋯O4ⁱ	0.85	2.06	2.786 (3)	143
C6—H6⋯Cl1ⁱⁱ	0.93	2.82	3.609 (4)	144

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

Acknowledgments

We thank the Science Research Foundation for High-level Talents of Pingdingshan University (No. 2006046) for support.

supplementary crystallographic information

Comment

It is common knowledge that the coordination geometry of metal ion and the shape and bonding mode of ligand are generally the primary considerations in metal-mediated self-assembly reactions. Relatively small changes in the bridging ligand can give rise to large variation in the overall structure of the assembly. Recently, some polynuclear coordination compounds containing benzenecarboxylate ligands and O—H···O and C—H···Cl hydrogen bonds (Desiraju, 2004; Song & Iyoda, 2009; Wang et al., 2011) have been reported (Baca et al., 2005; Ma et al., 2004; Thirumurugan & Rao, 2005; Zang et al., 2010). To better understand the influence of benzenecarboxylate ligands and hydrogen-bonding interactions on the resultant structures, we have begun working on the architectures of polynuclear structures from 3-chlorobenzene-1,2-dioic acid. As part of our ongoing investigation, the title compound has been prepared and its structure was determined.

The title compound is a binuclear complex (Fig. 1). The Cu^II atom is coordinated by two N atoms from a 5,5'-dimethyl-2,2'-bipyridine ligand, two O atoms from two 3-chlorobenzene-1,2-dicarboxylate ligands and two O atoms from two coordinated water molecules, forming a distorted octahedral geometry. As shown in Fig. 2, each complex molecule is connected to four neighboring molecules through O—H···O hydrogen bonds (Table 1), resulting in a two-dimensional supramolecular structure parallel to (1 0 0). Adjacent layers are associated together by C—H···Cl hydrogen bonds, forming a three-dimensional supramolecular structure (Fig. 3).

Experimental

A mixture of CuSO₄.5H₂O (7.5 mg, 0.03 mmol), 3-chlorobenzene-1,2-dioic acid (6 mg, 0.03 mmol), 5,5'-dimethyl-2,2'-bipyridine (5.5 mg, 0.03 mmol) and NaOH (2.4 mg, 0.06 mmol) in 10 ml of H₂O was sealed in a stainless-steel reactor with a Teflon liner and heated at 393 K for 72 h. A quantity of green single crystals was obtained after the solution was cooled to room temperature at a rate of 10 K h^-1.