Tetra­kis(2,2′-bipyrid­yl)dichlorido­di-μ3-hydroxido-di-μ2-hydroxido-tetra­copper(II) dinitrate hexa­hydrate

Ying Fan; Yong-Tao Cui; Hui-Fen Qian; Jian-Lan Liu; Wei Huang

doi:10.1107/S160053680804381X

. 2009 Jan 8;65(Pt 2):m131–m132. doi: 10.1107/S160053680804381X

Tetrakis(2,2′-bipyridyl)dichloridodi-μ₃-hydroxido-di-μ₂-hydroxido-tetracopper(II) dinitrate hexahydrate

Ying Fan ^a, Yong-Tao Cui ^a, Hui-Fen Qian ^a,^*, Jian-Lan Liu ^a, Wei Huang ^b,^*

PMCID: PMC2968164 PMID: 21581748

Abstract

The tetranuclear copper(II) title complex, [Cu₄Cl₂(OH)₄(C₁₀H₈N₂)₄](NO₃)₂·6H₂O, has a crystallographically imposed centre of symmetry. The metal atoms display a distorted tetragonal-pyramidal coordination geometry, and are linked by two μ ₂- and two μ₃-hydroxo groups, assuming a chair-like conformation for the Cu₄O₂ core. In the crystal, the complex molecules are linked into a three-dimensional network by intermolecular O—H⋯O, O—H⋯Cl, C—H⋯O and C—H⋯Cl hydrogen bonds and π–π stacking interactions with centroid–centroid separations of 3.724 (2) and 3.767 (3) Å.

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 ▶).

Experimental

Crystal data

[Cu₄Cl₂(OH)₄(C₁₀H₈N₂)₄](NO₃)₂·6H₂O
M _r = 1249.94
Triclinic,
a = 9.389 (3) Å
b = 10.622 (3) Å
c = 12.950 (4) Å
α = 86.909 (4)°
β = 77.263 (3)°
γ = 72.512 (4)°
V = 1201.4 (6) Å³
Z = 1
Mo Kα radiation
μ = 1.94 mm⁻¹
T = 291 (2) K
0.16 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.747, T _max = 0.830
6088 measured reflections
4181 independent reflections
3156 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.153
S = 1.08
4181 reflections
319 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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 global, I. DOI: 10.1107/S160053680804381X/rz2280sup1.cif

e-65-0m131-sup1.cif^{(21.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680804381X/rz2280Isup2.hkl

e-65-0m131-Isup2.hkl^{(204.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected bond lengths (Å).

Cu1—O2	1.927 (3)
Cu1—O1	1.980 (3)
Cu1—N1	2.016 (4)
Cu1—N2	2.029 (4)
Cu1—Cl1	2.5942 (17)
Cu2—O2	1.924 (3)
Cu2—O1	1.959 (3)
Cu2—N4	1.989 (4)
Cu2—N3	2.012 (4)
Cu2—O1ⁱ	2.323 (3)

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Symmetry code: (i) Inline graphic .

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O4	0.85	2.02	2.835 (7)	160
O2—H2A⋯O6	0.85	2.28	2.874 (6)	127
O7—H7A⋯O8ⁱⁱ	0.85	2.17	2.714 (9)	121
O8—H8A⋯Cl1	0.85	2.39	3.187 (7)	157
C2—H2⋯Cl1ⁱⁱⁱ	0.93	2.82	3.692 (5)	156
C5—H5⋯O4	0.93	2.55	3.394 (7)	152
C10—H10⋯O6	0.93	2.46	3.318 (7)	154
C12—H12⋯Cl1^iv	0.93	2.78	3.679 (5)	162
C15—H15⋯O4	0.93	2.58	3.185 (8)	123

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

Acknowledgments

WH acknowledges the National Natural Science Foundation of China (No. 20871065) and the Scientific Research Foundation for Returned Overseas Chinese Scholars, State Education Ministry, for financial aid.

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). 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, while selected bond distances are given in Table 1. The title complex has a crystallographically imposed centre of symmetry, and consists of a chair-like [Cu₄(bpy)₄(µ₂-OH)₂(µ₃-OH)₂Cl₂]²⁺ dication (bpy = 2,2'-bipyridine), two nitrate anions, and six lattice water molecules. The coordination geometry around each copper(II) ion can be described as a five-coordinate distorted pyramid. The basal sites are occupied by two N atoms from a bpy ligand and two O atoms from two µ₂-bridging hydroxo groups, with mean Cu–N and Cu–O bond distances of 2.011 (4) 1.948 (3) Å, respectively; the apical position is occupied by a chloride anion for atom Cu1 (Cu1–Cl1 = 2.594 (2) Å) and a µ₃-bridged OH anion for Cu2 (Cu2–O1ⁱ = 2.323 (3) Å; symmetry code: (i) = 1-x, 1-y, -z).

In the crystal packing, the complex molecules are linked into a three-dimensional network by intra- and intermolecular O—H···O, O—H···Cl, C—H···O and C—H···Cl hydrogen bonding interactions involving the solvent water molecules, the hydroxo groups and the chloride and nitrate anions (Table 2). The structure is further stabilized by π–π stacking interactions between adjacent bpy molecules with centroid-to-centroid separations of 3.724 (2) and 3.767 (3) Å (Fig. 2).

Experimental

The title compound was obtained as a by-product from the reaction between [Cu(bpy)](NO₃)₂ (0.398 g, 1 mmol) and D-(+)-1,2,2-trimethylcyclopentane-1,3-diamine dihydrogenchloride salt (0.284 g, 2 mmol) in the presence of NaOH (0.080 g, 2 mmol). Yield: 35 % based on the copper(II) amount. Single crystals suitable for X-ray diffraction were grown from a mixture of methanol/water (1:1 v/v) by slow evaporation in air at room temperature. Elemental Analysis: Calcd. for C₄₀H₄₈Cl₂Cu₄N₁₀O₁₆: C, 38.44; H, 3.87; N, 11.21 %; found: C,38.66; H,3.67; N, 11.03 %. Main FT-IR absorptions (KBr pellets, cm^-1): 3427 (vs), 2372 (m), 2341 (m), 1634 (s), 1383 (m), 1080 (s), 991 (m), 773 (m), and 549 (m).