A dinuclear copper complex: bis­(μ-4-amino­benzoato)bis­[aqua(1,10-phenanthroline)copper(II)] dichloride bis(4-amino­benzoic acid) dihydrate

Miao-Ling Huang; Qing-Fan Xie; Jing-Chun Xian; Yan-Min Chen; Zi-Qiao Zhou

doi:10.1107/S1600536808023647

. 2008 Jul 31;64(Pt 8):m1086. doi: 10.1107/S1600536808023647

A dinuclear copper complex: bis(μ-4-aminobenzoato)bis[aqua(1,10-phenanthroline)copper(II)] dichloride bis(4-aminobenzoic acid) dihydrate

Miao-Ling Huang ^a,^*, Qing-Fan Xie ^a, Jing-Chun Xian ^a, Yan-Min Chen ^a, Zi-Qiao Zhou ^a

PMCID: PMC2961994 PMID: 21203064

Abstract

The title complex, [Cu₂(C₇H₆NO₂)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₇H₇NO₂·2H₂O, consists of a dinuclear [Cu₂(C₇H₆NO₂)₂(C₁₂H₈N₂)₂(H₂O)₂]²⁺ cation, two Cl⁻ anions, two 4-aminobenzoic acid molecules and two disordered water molecules (site occupancy factors 0.5). The Cu(II) ion adopts a distorted square-pyramidal geometry formed by two N atoms from the 1,10-phenanthroline ligand and two O atoms of the two 4-aminobenzoic acid ligands and one water O atom. The Cu⋯Cu separation is 3.109 (2) Å. A twofold axis passes through the mid-point of the Cu⋯Cu vector.

Related literature

For related literature, see: Lo et al. (2000 ▶); Zoroddu et al. (1996 ▶); Rao et al. (2004 ▶); Müller et al. (2003 ▶).

Experimental

Crystal data

[Cu₂(C₇H₆NO₂)₂(C₁₂H₈N₂)₂(H₂O)₂]·2C₇H₇NO₂·2H₂O
M _r = 1174.96
Monoclinic,
a = 25.748 (2) Å
b = 10.0988 (8) Å
c = 20.9156 (17) Å
β = 110.3070 (10)°
V = 5100.5 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 291 (2) K
0.49 × 0.40 × 0.37 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.638, T _max = 0.708
18514 measured reflections
4744 independent reflections
3886 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.091
S = 1.02
4744 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808023647/pv2085sup1.cif

e-64-m1086-sup1.cif^{(26.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808023647/pv2085Isup2.hkl

e-64-m1086-Isup2.hkl^{(232.5KB, 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
O1—H2W⋯Cl1ⁱ	0.85	2.71	3.549 (7)	170
O1—H1W⋯O1ⁱⁱ	0.88	2.32	2.938 (11)	127
O2—H4W⋯O1	0.82	1.80	2.477 (8)	138
O2—H3W⋯N4	0.83	2.30	3.081 (5)	157
O3—H5W⋯Cl1	0.83	2.32	3.1259 (17)	163
O3—H6W⋯O6	0.84	1.90	2.737 (2)	179
N3—H3A⋯Cl1ⁱⁱⁱ	0.86	2.68	3.475 (3)	154
N3—H3B⋯O2^iv	0.86	2.07	2.898 (5)	161
N4—H4A⋯Cl1^v	0.86	2.71	3.512 (3)	155
N4—H4B⋯Cl1ⁱ	0.86	2.59	3.433 (3)	167

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

Acknowledgments

This work was supported by the Natural Science Foundition of Fujian Province of China (Grant no. Z0513017).

supplementary crystallographic information

Comment

During the last three decades, copper complexes have received much attention because of their interesting interactions with biological ligands to generate stable mixed coordinated complexes, which play a key role in life processes such as enzymatic catalysis, storage and conveyance of the matter, transfer of copper ions (Müller, et al., 2003; Rao, et al., 2004; Lo, et al., 2000). 4-Aminobenzoic acid, an important part of folic acid, is a constituent of the vitamin B complex and is found in animal and plant tissues, and has been shown to be a growth factor in certain microorganisms, particularly Enterococci and Lactobacilli (Zoroddu et al., 1996). In order to extend further the study of 4-aminobenzoic acid ligand coordinated to copper ion, we have synthesized the title complex, (I) and determined its crystal structure by X-ray diffraction which is presented in this article.

The molecular structure and crystal packing diagram of the title compound are presented in Figs. 1 and 2, respectively. The structure is composed of a dimeric [Cu₂(C₇H₆NO₂)₂(C₁₂H₈N₂)₂(H₂O)₂]₂⁺ cation with two five-coordinated Cu(II) ions linked by two oxygen atoms of 4-aminobenzoic acid, two Cl^- anions, two 4-aminobenzoic acid molecules and two disordered water molecules lying over four sites with 0.5 occupancy factors each. The Cu(II) ion has a distorted square-pyramidal geometry with two N atoms of 1,10-phenanthroline ligand and two O atoms of two 4-aminobenzoic acid ligands occupying basal sites and the apical position being occupied by an O atom of H₂O. The benzoic acid molecules not coordinated to Cu are hydrogen bonded to Cl^- ions by amino H-atoms and to water of coordination by hydroxyl H-atoms (details are given in Table 1). As a matter of fact, the complex molecules, Cl^- anions, 4-aminobenzoic acid molecules and water molecules are linked by a network of O—H···O, N—H···O and O—H···Cl hydrogen bonds into a three-dimensional supramolecular structure. In the complex, the two 1,10-phenanthroline ligands are stacked with their centroids separated by 3.661 (2) Å indicating significant π-π interactions.

Experimental

An aqueous solution (5 ml) of CuCl₂.3H₂O (1 mmol) was added slowly to a mixed solution of 4-aminobenzoic acid (1.5 mmol) in H₂O (5 ml) and 1,10-phenanthroline (1 mmol) in ethanol (95%, 5 ml). After refluxing for 3 h, the mixture was filtered off while hot. The dark-green single crystals suitable for X-ray analysis were obtained by slow evaporation of the above filtrate at room temperature after a week.