Bis(μ-2-phenyl­acetato-κ2 O:O)bis­[(2,2′-bipyridyl-κ2 N,N′)(2-phenyl­acetato-κO)copper(II)] dihydrate

Wei Xu; Ling Jin; Bin-Bin Liu

doi:10.1107/S1600536811035483

. 2011 Sep 14;67(Pt 10):m1334. doi: 10.1107/S1600536811035483

Bis(μ-2-phenylacetato-κ² O:O)bis[(2,2′-bipyridyl-κ² N,N′)(2-phenylacetato-κO)copper(II)] dihydrate

Wei Xu ^a,^*, Ling Jin ^a, Bin-Bin Liu ^a

PMCID: PMC3201355 PMID: 22058686

Abstract

The molecule of the binuclear title complex, [Cu₂(C₈H₇O₂)₄(C₁₀H₈N₂)₂]·2H₂O, is located on an inversion centre. The Cu atoms are bridged by two O atoms of the monodentate phenylacetate groups [Cu—O = 1.9808 (14) and 2.3668 (14) Å]. The longer of the two bridging Cu—O bonds takes the apical position of the distorted square-pyramidal environment of the Cu atom, which is completed by two N atoms of the chelate 2,2′-bipyridine ligand [Cu—N = 2.0107 (17) and 2.0234 (16) Å]. The molecules are assembled into stacks along [100] through π–π interactions with interplanar distances of 3.630 (4) and 3.407 (3) Å; the resulting stacks are further connected into a three-dimensional supramolecular architecture by O—H⋯O and C—H⋯O hydrogen-bonding interactions.

Related literature

For applications of inorganic–organic hybrid materials, see: Pan et al. (2003 ▶); Shibasaki & Yoshikawa (2002 ▶). For related structures, see: Addison & Rao (1984 ▶); Antolini et al. (1985 ▶); Zhang et al. (2006 ▶).

Experimental

Crystal data

[Cu₂(C₈H₇O₂)₄(C₁₀H₈N₂)₂]·2H₂O
M _r = 1016.02
Monoclinic,
a = 10.213 (2) Å
b = 16.058 (3) Å
c = 14.633 (3) Å
β = 100.75 (3)°
V = 2357.7 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.97 mm⁻¹
T = 295 K
0.17 × 0.14 × 0.11 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.678, T _max = 0.784
22348 measured reflections
5356 independent reflections
4268 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.090
S = 1.10
5356 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.56 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ▶); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811035483/ya2144sup1.cif

e-67-m1334-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035483/ya2144Isup2.hkl

e-67-m1334-Isup2.hkl^{(262.3KB, 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
O5—H51⋯O4	0.85	2.05	2.781 (3)	143
O5—H52⋯O2ⁱ	0.86	2.08	2.931 (3)	174
C20—H20A⋯O4ⁱⁱ	0.93	2.38	3.245 (3)	156
C24—H24A⋯O2ⁱⁱⁱ	0.93	2.48	3.172 (3)	131
C25—H25A⋯O5^iv	0.93	2.50	3.201 (3)	132

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

Acknowledgments

This project was supported by the K. C. Wong Magna Fund in Ningbo University.

supplementary crystallographic information

Comment

The use of metal centers for organizing of molecular building blocks into inorganic–organic hybrid materials have been studied for potential applications in catalysis, gas storage, and in molecular–based magnetic materials (Pan et al., 2003; Shibasaki & Yoshikawa, 2002). As part of our investigations of self-assemblies of Cu²⁺ ions and bipy with phenylacetic acid, we prepared the title complex, [Cu₂(C₈H₇O₂)₄(C₁₀H₈N₂)₂].2H₂O.

The molecule of the complex occupies a special position in the inversion centre (Fig. 1). The square pyramidal coordination environment of the Cu atom is formed by the N atoms of 2,2'-bipyridine ligands (Cu—N1 2.0108 (17) Å and Cu—N2 2.0234 (16) Å), the O atom of terminal phenylacetato ligand (Cu—O3 1.9557 (16) Å), and two O atoms of bridging phenylacetato groups, the O1ⁱ atom [symmetry code (i): 1 - x, -y, -z] takes one of the equatorial positions, whereas the O1 atom occupies the apical site. As one would expect (Antolini et al., 1985; Zhang et al., 2006), the apical bond Cu—O1 2.3669 (14) Å is substantially longer than the equatorial Cu—O1ⁱ distance of 1.9807 (14) Å. The Cu atom is displaced by 0.078 (1) Å towards the apical vertex from the mean plane of the equatorial ligands [τ = 0.04 according to Addison & Rao (1984)].

The molecules are assembled into stacks along [100] through π···π stacking interactions with the mean interplanar distance of 3.407 (3) Å between adjacent bipy ligands and 3.630 (4) Å between bipy ligands and phenylacetato groups, and the stacks are further stabilized by the weak C—H···O hydrogen bonding interactions from the phenyl CH groups to the uncoordinating carboxylate O2 and O4 atoms (Table 1), as well O—H···O bonds involving water molecule (Fig. 2). As a result, three-dimensional network is formed.

Experimental

Phenylacetic acid(0.2726 g, 2.000 mmol) was completely dissolved in a mixture of 10 ml of ethanol, 10 ml of water, and bipy (0.1561 g, 1.000 mmol). 0.2602 g (1.084 mmol) of Cu(NO₃)₂.3H₂O were then added, and after dropwise addition of 2.0 ml (1M) NaOH to the resulting solution under continuous stirring for 1 h, the blue suspension was produced. The suspension was filtered and the filtrate (pH = 6.51) was allowed to stand at room temperature for several weeks; the precipitation of blue block crystals was observed.