Tetra­kis(2,2′-bipyrid­ine)di-μ3-hydroxido-bis(μ-2-oxidobenzoato)tetra­copper(II) dinitrate tetra­hydrate

Miao Feng; Chao Gu; Huai-Feng Mi; Tong-Liang Hu

doi:10.1107/S1600536811011433

. 2011 Apr 7;67(Pt 5):m520. doi: 10.1107/S1600536811011433

Tetrakis(2,2′-bipyridine)di-μ₃-hydroxido-bis(μ-2-oxidobenzoato)tetracopper(II) dinitrate tetrahydrate

Miao Feng ^a, Chao Gu ^b, Huai-Feng Mi ^a,^*, Tong-Liang Hu ^b

PMCID: PMC3089088 PMID: 21754263

Abstract

The tetranuclear title complex, [Cu₄(C₇H₄O₃)₂(OH)₂(C₁₀H₈N₂)₄](NO₃)₂·4H₂O, has a crystallographically imposed centre of symmetry. The Cu^II atoms display a distorted square-pyramidal coordination geometry and are linked by two μ₂-phenolate O atoms from the salicylate ligands and two μ₃-hydroxo groups, forming a Cu₄O₄ core that adopts a ‘stepped-cubane’ geometry. In the crystal, the cations are linked by O—H⋯O hydrogen bonds to the nitrate anions, which are in turn connected via O—H⋯O interactions to centrosymmentric water tetramers.

Related literature

For the structures of related complexes, see: Albada et al. (2002 ▶); Chandrasekhar et al. (2000 ▶); Lu et al. (2007 ▶); Sletten et al. (1990 ▶); Zheng & Lin (2002 ▶); Fan et al. (2009 ▶); Li et al. (2008 ▶).

Experimental

Crystal data

[Cu₄(C₇H₄O₃)₂(OH)₂(C₁₀H₈N₂)₄](NO₃)₂·4H₂O
M _r = 1381.20
Triclinic,
a = 10.280 (2) Å
b = 11.777 (2) Å
c = 12.276 (3) Å
α = 113.66 (3)°
β = 95.19 (3)°
γ = 96.58 (3)°
V = 1337.0 (5) Å³
Z = 1
Mo Kα radiation
μ = 1.66 mm⁻¹
T = 113 K
0.22 × 0.06 × 0.02 mm

Data collection

Rigaku Saturn70 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.870, T _max = 1.000
17013 measured reflections
6339 independent reflections
4704 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.086
S = 1.04
6339 reflections
388 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.55 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011433/gk2359sup1.cif

e-67-0m520-sup1.cif^{(23.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011433/gk2359Isup2.hkl

e-67-0m520-Isup2.hkl^{(310.2KB, 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
O8—H1W⋯O6ⁱ	0.79	2.18	2.939 (3)	163
O8—H2W⋯O9ⁱⁱ	0.88	2.00	2.845 (3)	163
O9—H3W⋯O8ⁱⁱⁱ	0.74	2.04	2.745 (3)	160
O4—H4W⋯O7	0.73	2.13	2.838 (3)	164
O9—H5W⋯O2^iv	0.78	2.02	2.791 (3)	169

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (project approval No. 20974053).

supplementary crystallographic information

Comment

Recently, some tetranuclear hydroxo-bridged copper(II) complexes with cubane and the chair-like structure have been reported (Zheng & Lin, 2002; Sletten et al., 1990; Albada et al., 2002; Lu et al., 2007; Chandrasekhar et al., 2000; Fan et al. 2009; Li et al. 2008). In this paper, the crystal structure of a new copper(II) complex exhibiting a chair-like tetranuclear motif is presented.

The atom-numbering scheme of the title compound is shown in Fig. 1. The title complex has a crystallographically imposed centre of symmetry, and consists of a chair-like [Cu₄(C₇H₄O₃)₂(OH)₂(bpy)₄]2⁺ dication (bpy = 2,2'-bipyridine), two nitrate anions, and four lattice water molecules. The coordination geometry around each copper(II) ion can be described as a five-coordinate distorted square pyramid. In the crystal packing, the nitrate counter-anions stabilize the crystal structure through water O—H···O nitrate hydrogen bonds and the complex molecules are linked into one-dimensional chains by intermolecular O—H···O bonding interactions involving the solvent water molecules and the nitrate counter-anions (Fig. 2 and Table 1).

Experimental

A mixture of salicylic acid (0.05 mmol), copper nitrate trihydrate (0.05 mmol), 2,2'-bipyridine (0.05 mmol) and 10 ml H₂O were put into a 23-ml Teflon lined reactor and heated at 418 K in oven for 48 h. After the autoclave was cooled during 24 h to room temperature, the solid was filtered off. The resulting filtrate was allowed to stand at room temperature, and slow evaporation for 3 weeks afforded block single crystals.