(2,2′-Bipyridine-κ2 N,N′)bis­(3-meth­oxy­benzoato-κ2 O 1,O 1′)copper(II) mono­hydrate

Ming-Hao Lin; Jing-Fan Zhou; Bin-Bin Liu; Jian-Li Lin

doi:10.1107/S1600536811005563

. 2011 Feb 19;67(Pt 3):m352. doi: 10.1107/S1600536811005563

(2,2′-Bipyridine-κ² N,N′)bis(3-methoxybenzoato-κ² O ¹,O ^1′)copper(II) monohydrate

Ming-Hao Lin ^a, Jing-Fan Zhou ^a, Bin-Bin Liu ^a, Jian-Li Lin ^a,^*

PMCID: PMC3052164 PMID: 21522281

Abstract

The title compound, [Cu(C₈H₇O₃)₂(C₁₀H₈N₂)]·H₂O, is comprised of a Cu^II ion, two 3-methoxybenzoate ligands, a 2,2′-bipyridine (bipy) ligand and one uncoordinated water molecule. The Cu^II ion and the water O atom lie on a twofold axis. The Cu^II ion exhibits a six-coordinate distorted octahedral geometry, with two N atoms from the bipy ligand [Cu—N = 1.9996 (16) Å] and four O atoms from two 3-methoxybenzoate ligands [Cu—O = 1.9551 (15) and 2.6016 (16) Å]. The molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For hydrogen bonds and crystal engineering, see: Aakeröy & Seddon (1993 ▶). For potential applications of transition metal complexes, see: Liu et al. (2007 ▶); Shibasaki & Yoshikawa (2002 ▶). For carboxylate compounds with six-coordinate metal atoms, see: Liu et al. (2010 ▶); Su et al. (2005 ▶).

Experimental

Crystal data

[Cu(C₈H₇O₃)₂(C₁₀H₈N₂)]·H₂O
M _r = 540.01
Monoclinic,
a = 19.888 (4) Å
b = 10.887 (2) Å
c = 11.612 (2) Å
β = 103.62 (3)°
V = 2443.5 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.94 mm⁻¹
T = 293 K
0.1 × 0.1 × 0.1 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.710, T _max = 0.780
12080 measured reflections
2796 independent reflections
2391 reflections with I > 2σ(I)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.113
S = 1.05
2796 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.39 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 datablocks global, I. DOI: 10.1107/S1600536811005563/rn2078sup1.cif

e-67-0m352-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811005563/rn2078Isup2.hkl

e-67-0m352-Isup2.hkl^{(137.4KB, 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
O4—H41⋯O1	0.88	2.24	3.023 (3)	147
C12—H12A⋯O4ⁱⁱ	0.93	2.41	3.339 (3)	178
C11—H11A⋯O3ⁱⁱ	0.93	2.57	3.483 (3)	166
C10—H10A⋯O2ⁱⁱⁱ	0.93	2.66	3.342 (3)	131

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

Acknowledgments

This project was supported by the Education Department of Zhejiang Province and the scientific research fund of Nibong University (grant No. XKL069). Thanks are also extended to the K. C. Wong Magna Fund, Ningbo University.

supplementary crystallographic information

Comment

In the past decade, a variety of supramolecular architectures based on hydrogen bonds, π···π interactions have been achieved by using transition metal centers and organic ligands (Aakeroy et al., 1993), they have potential application in catalysis, gas storage, and in molecular–based magnetic materials (Liu et al., 2007, Shibasaki et al., 2002). Herein, we are interested in self-assemblies of Cu²⁺ ions and bipy with 3–methoxybenzoic acid, which led to the preparation of [Cu(bipy)₂(C₈H₈O₃)₂].H₂O.

The title compound, [Cu(bipy)₂(C₈H₈O₃)₂].H₂O, is comprised of a Cu^II ion, two 3–methoxybenzoate ligands, a 2,2'–bipyridine(bipy) ligand and one lattice H₂O molecule. As illustrated in Fig.1, the Cu ion and water O atom lie on a two fold axis. The Cu^II ion has a six–coordinate distorted octahedral geometry with two N atoms from the bipy ligand [Cu–N = 1.9996 (16) Å] and four O atoms from two 3–methoxybenzoate ligands [Cu–O = 1.9551 (15) and 2.6016 (16) Å]. Owing to geometric constraints and the Jahn–Teller effect, the Cu–O bonds in the axial direction are longer than in the equatorial plane. Two O atoms and two N atoms occupy the equatorial plane position with the r.m.s. deviation from the ideal plane of 0.214 Å, while two O atoms lie in the apical positions with an axis angle of 140.53 (5)° showing a large deviation from the normal 180°,which is also seen in similar carboxylate complexes (Liu et al., 2010; Su et al., 2005). For 3–methoxybenzoate anions, the plane of benzene ring and carboxylate group are nearly co–planar where the dihedral angle between the benzene ring and carboxylate plane is 5.2 (3)°. The water molecules are not coordinated to Cu and the distance between copper and water oxygen atoms is 4.019 (2) Å.

The molecules are linked via hydrogen bonds (O4–H41···O1, C12–H12A···O4, C11–H11A···O3) into one-dimensional supramolecular chains extending along the [100] direction, which are linked by hydrogen bonds (C5–H5A···O2) into two dimensional layers parallel to (100) (Fig. 2). The layers are arranged alternately in an ···ABAB···sequence and further assembled into there–dimensional network by hydrogen bonds (C10–H10A···O2).

Experimental

CuCl₂.2H₂O (0.1705 g, 1.000 mmol) was successively added to 20 ml C₂H₅OH–H₂O(1:1, v/v), 3–methoxybenzoate (0.1520 g, 1.000 mmol) and bipy (0.1569 g, 1.004 mmol) were subsequently added, then 1.4 ml (1 M) NaOH was added dropwise and stirred continuously for 1 h to give a blue suspension. After filtration, the blue filtrate (pH = 5.80) was allowed to stand at room temperature for several weeks to give blue block–shaped crystals