Aqua­bis­(3-fluoro­benzoato-κO)(1,10-phenanthroline-κ2 N,N′)copper(II)

Xin Yin

doi:10.1107/S1600536811012220

. 2011 Apr 13;67(Pt 5):m564–m565. doi: 10.1107/S1600536811012220

Aquabis(3-fluorobenzoato-κO)(1,10-phenanthroline-κ² N,N′)copper(II)

Xin Yin ^a,^*

PMCID: PMC3089262 PMID: 21754295

Abstract

In the title compound, [Cu(C₇H₄FO₂)₂(C₁₂H₈N₂)(H₂O)], the coordination around the Cu^II atom is square-pyramidal. The equatorial positions are occupied by two N atoms from a 1,10-phenanthroline ligand [Cu—N = 2.008 (3) and 2.019 (3) Å] and two O atoms from 3-fluorobenzoate ligands and a water molecule [Cu—O = 1.950 (2) and 1.978 (2) Å]. One O atom from another 3-fluorobenzoate ligand occupies the apical positon [Cu—O = 2.210 (2) Å]. Hydrogen bonds occur between coordinated water molecules and benzoate ligands, while O—H⋯O, C—H⋯O, C—H⋯F and π–π stacking [centroid–centroid distance = 3.731 (2) Å] interactions consolidate the crystal packing.

Related literature

A number of copper SOD mimetics (SOD = superoxide dismutase) have been shown to possess antitumor activity and have been proposed as a new class of potential anticancer agents, see: Devereux et al. (2007 ▶). Phenoxyalkanoic acids interact with Cu(II) ions to form complexes which have been shown to have diverse stereochemistries, see: Smith et al. (1981 ▶, 1982 ▶). For the structures of similar coordination compounds, see: Liu et al. (2009 ▶); Zhu & Xiao (2006 ▶).

Experimental

Crystal data

[Cu(C₇H₄FO₂)₂(C₁₂H₈N₂)(H₂O)]
M _r = 539.96
Triclinic,
a = 9.9914 (8) Å
b = 10.7258 (9) Å
c = 11.6166 (10) Å
α = 73.208 (1)°
β = 70.082 (1)°
γ = 86.293 (1)°
V = 1119.74 (16) Å³
Z = 2
Mo Kα radiation
μ = 1.04 mm⁻¹
T = 295 K
0.25 × 0.20 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.782, T _max = 0.860
5876 measured reflections
3972 independent reflections
2924 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.132
S = 1.03
3972 reflections
325 parameters
H-atom parameters constrained
Δρ_max = 0.99 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 2003 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012220/hg5016sup1.cif

e-67-0m564-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012220/hg5016Isup2.hkl

e-67-0m564-Isup2.hkl^{(194.7KB, 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—H1W⋯O1	0.85	1.75	2.585 (4)	163
O1W—H2W⋯O4	0.85	1.80	2.612 (4)	161
C10—H10⋯O3	0.93	2.53	3.005 (4)	112
C1—H1⋯F1ⁱ	0.93	2.33	3.213 (6)	158
C8—H8⋯O4ⁱⁱ	0.93	2.39	3.309 (4)	171

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

Acknowledgments

This work was supported by the College of Chemistry and Molecular Engineering, East China University of Science and Technology.

supplementary crystallographic information

Comment

A number of copper SOD mimetics have been shown to possess antitumor activity and have been proposed as a new class of potential anticancer agents (Devereux et al. 2007). Morever, phenoxyalkanoic acids interact with Cu(II) ions to form complexes which have been shown to have diverse stereochemistries (Smith et al. 1981,1982). Studying structure of such copper complexes is important to the understanding of copper biochemistry. Therefore, we have synthesized the title compound, (I), and report its crystal structure here.

In the title monomer complex, the copper atom adopts a square pyramidal environment defined by two nitrogen donors from the 1,10-phenanthroline ligand, two carboxyl oxygen atoms from two 3-fluorobenzoate ligands and one oxygen atom from the coordinated water molecule O atom (Fig. 1). Atoms N1, N2, O3, and O1w are sitting on the basal plane, while atom O2 occupies the apical position. Each 3-fluorobenzoate ligand is mono-coordinated to the metal atom. The coordinated water molecule acts as double donor to the carbonyl groups of the 3-fluorobenzoate ligands, forming two intramolecular O-H···O hydrogen bonds (Table 1), which consolidates the solid structure. The crystal packing exhibits also weak intermolecularC—H···O hydrogen bonds, π–π interactions and short intermolecular C—H···F Contacts. Similar coordination is observed in other Cu structures (Liu et al.,2009; Zhu et al., 2006).

Experimental

All reagents were obtained from commercial sources and used without further purification. CuCl₂.2H₂O (0.017 g, 0.10 mmol) was successively added to 20 ml CH₃OH, H₂O (1:1, v/v)solution. Then 3-fluorobenzoic acid (0.028 g, 0.20 mmol) and 1,10-phenanthroline (0.017 g, 0.10 mmol) were subsequently added. The pH value of the mixture was adjusted to about 5.5 with NaOH solution and stirred continuously for 1 h to give a blue clear solution. After filtration, the blue filtrate was allowed to stand at room temperature for one week to give blue block-shaped crystals suitable for X-ray analysis.Analysis required for C₂₆H₁₈CuF₂N₂O₅: C 57.83, H 3.36, N 5.19%; found: C 57.64, H 3.58, N 5.09%. m.p. 463.5-464 K.