(Benzoato-κO)(benzoic acid-κO)(4,4′-dimethyl-2,2′-bipyridine-κ2 N,N′)hydroxidocopper(II) monohydrate

Li Yao; Wen-Juan Li

doi:10.1107/S1600536809043189

. 2009 Nov 7;65(Pt 12):m1532. doi: 10.1107/S1600536809043189

(Benzoato-κO)(benzoic acid-κO)(4,4′-dimethyl-2,2′-bipyridine-κ² N,N′)hydroxidocopper(II) monohydrate

Li Yao ^a,^b,^*, Wen-Juan Li ^b

PMCID: PMC2972094 PMID: 21578575

Abstract

In the structure of the title complex, [Cu(C₇H₅O₂)(OH)(C₁₂H₁₂N₂)(C₇H₆O₂)]·H₂O, the Cu^II ion is pentacoordinated in a tetragonal-pyramidal geometry with one O atom of a hydroxide group, one O atom of a benzoate anion and two N atoms of a 4,4′-dimethyl-2,2′-bipyridine ligand occupying the basal plane, and one O atom of a benzoic acid molecule located at the apical site. The title complex was refined with a metal-coordinated OH group and a ‘free’ benzoic acid molecule, although it can be assumed that the proton is delocalized between the OH and the COOH group. The uncoordinated water molecule is equally disordered over two positions. The structure displays O—H⋯O hydrogen bonding.

Related literature

For selected 4,4′-dimethyl-2,2′-bipyridine copper complexes, see: Deschamps et al. (2002 ▶); Dong et al. (2006 ▶); Feng et al. (2007 ▶); Lin et al. (2008 ▶); Qian & Huang (2006 ▶); Willett et al. (2001 ▶). graphic file with name e-65-m1532-scheme1.jpg

Experimental

Crystal data

[Cu(C₇H₅O₂)(OH)(C₁₂H₁₂N₂)(C₇H₆O₂)]·H₂O
M _r = 526.03
Monoclinic,
a = 11.3325 (15) Å
b = 17.155 (2) Å
c = 13.4007 (18) Å
β = 98.049 (3)°
V = 2579.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 296 K
0.28 × 0.26 × 0.25 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.789, T _max = 0.808
13741 measured reflections
4538 independent reflections
3075 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.146
S = 0.95
4538 reflections
329 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); 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 datablocks I, global. DOI: 10.1107/S1600536809043189/zq2009sup1.cif

e-65-m1532-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043189/zq2009Isup2.hkl

e-65-m1532-Isup2.hkl^{(222.3KB, 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
O2W—H2WB⋯O2ⁱ	0.85	2.51	3.195 (8)	138
O2W—H2WA⋯O1W	0.85	2.24	2.821 (10)	125
O1W—H1WB⋯O4	0.85	2.26	2.932 (6)	136
O1W—H1WA⋯O2W ⁱⁱ	0.85	2.28	2.937 (10)	134
O5—H5A⋯O4	0.82	1.93	2.642 (4)	145
O2—H2⋯O5	0.82	1.86	2.636 (5)	158

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

supplementary crystallographic information

Comment

As a contribution to structural characterization of 4,4'-dimethyl-2,2'-bipyridine copper complexes (Deschamps et al., 2002; Dong et al., 2006; Feng et al., 2007; Lin et al. 2008; Qian & Huang, 2006; Willett et al., 2001), we present here the crystal structure of the title complex, [CuLL'L''(OH)].H₂O (L = benzoate, L' = benzoic acid, L'' = 4,4'-dimethyl-2,2'-bipyridine).

In the structure of the title complex, the short O2···O5 separation of 2.636 (5) Å clearly indicates a typical hydrogen bond. The corresponding hydrogen atom was located in the Fourier difference maps near O2 (hydroxido benzoic acid type complex A) although general chemical considerations would rather expect it on O5 (water benzoate type complex B). One can assume that the proton is delocalised somewhere in-between as presented in Scheme 1 but based on the X-ray data only, the title complex was finally refined with a metal-coordinated OH group and a "free" benzoic acid molecule.

In the complex, the Cu²⁺ ion is pentacoordinated, with two N atoms of 4,4'-dimethyl-2,2'-bipyridine, one O atom of a hydroxide group and one O atom of a benzoate anion in the basal plane and one O atom of a benzoic acid molecule completing the square-pyramidal geometry from the apical site (Fig. 1). The atoms N1, N2, O1 and O3 are nearly coplanar, and the Cu atom is displaced by 0.2309 (5) Å from this plane towards the apical O atom. The water solvent molecule is disordered over two positions in a 1:1 ratio.

With O—H···O hydrogen bonds (Table 1), an one-dimensional chain is formed as shown in Fig. 2.

Experimental

The title compound was synthesized hydrothermally in a Teflon-lined autoclave (25 ml) by heating a mixture of 4,4'-dimethyl-2,2'-bipyridine (0.2 mmol), benzoic acid (0.4 mmol) and CuSO₄.5H₂O (0.2 mmol) in water (10 ml) at 393 K for 3 d. Suitable crystals for an X-ray analysis were obtained.