(Acetato-κO)bis­(1,10-phenanthroline-κ2 N,N′)copper(II) acetate hepta­hydrate

Buqin Jing; Lianzhi Li; Jianfang Dong; Tao Xu

doi:10.1107/S1600536811009676

. 2011 Mar 19;67(Pt 4):m464. doi: 10.1107/S1600536811009676

(Acetato-κO)bis(1,10-phenanthroline-κ² N,N′)copper(II) acetate heptahydrate

Buqin Jing ^a,^b, Lianzhi Li ^b,^*, Jianfang Dong ^c, Tao Xu ^b

PMCID: PMC3099845 PMID: 21753980

Abstract

In the title complex, [Cu(CH₃CO₂)(C₁₂H₈N₂)₂](CH₃CO₂)·7H₂O, the central Cu^II ion is five coordinate, being bound to four N atoms from two 1,10-phenanthroline ligands and one O atom from an acetate anion in a strongly distorted square-pyramidal configuration. Hydrogen-bonded water molecules and an uncoordinated acetate anion form a two-dimensional polymeric structure parallel to (010). The cations are linked to this layer via O—H⋯O hydrogen bonds between one of the water molecules and the coordinated acetate anion.

Related literature

For the structures of similar five-coordinate copper(II) complexes with 1,10-phenanthroline and carboxylate anions, see: Tu et al. (2008 ▶); Xu et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₂H₃O₂)(C₁₂H₈N₂)₂](C₂H₃O₂)·7H₂O
M _r = 668.15
Triclinic,
a = 8.764 (4) Å
b = 12.307 (5) Å
c = 15.739 (7) Å
α = 103.257 (7)°
β = 102.243 (7)°
γ = 97.606 (7)°
V = 1585.2 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 298 K
0.42 × 0.38 × 0.32 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.728, T _max = 0.795
8364 measured reflections
5570 independent reflections
3220 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.057
wR(F ²) = 0.130
S = 0.95
5570 reflections
399 parameters
52 restraints
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 ▶) and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009676/gk2351sup1.cif

e-67-0m464-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009676/gk2351Isup2.hkl

e-67-0m464-Isup2.hkl^{(272.7KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu1—N3	1.988 (3)
Cu1—N1	1.989 (3)
Cu1—O1	2.001 (3)
Cu1—N4	2.051 (3)
Cu1—N2	2.191 (4)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H29⋯O3	0.85	1.90	2.738 (5)	170
O6—H31⋯O5	0.85	1.92	2.768 (5)	176
O7—H33⋯O4	0.85	1.96	2.797 (5)	167
O7—H34⋯O8	0.85	1.91	2.760 (5)	173
O8—H36⋯O2	0.85	1.86	2.710 (4)	173
O9—H37⋯O8	0.85	1.98	2.826 (5)	174
O10—H40⋯O11	0.85	2.23	3.070 (5)	168
O11—H42⋯O9	0.85	1.89	2.714 (5)	164
O5—H30⋯O10ⁱ	0.85	2.03	2.819 (5)	155
O6—H32⋯O4ⁱ	0.85	1.94	2.778 (5)	169
O9—H38⋯O6ⁱ	0.85	1.94	2.737 (6)	156
O10—H39⋯O4ⁱⁱ	0.85	1.87	2.702 (5)	164
O11—H41⋯O7ⁱⁱ	0.85	1.88	2.724 (5)	170
O8—H35⋯O11ⁱⁱⁱ	0.85	1.97	2.796 (5)	165

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

Acknowledgments

The authors thank the Natural Science Foundation of Shandong Province (No. Y2004B02) for a research grant.

supplementary crystallographic information

Comment

Construction of supramolecular architectures with intersting physical properties has grown rapidly owing to their potential use as new functional materials. Many intriguing supramolecular assemblies have been prepared by metal coordination or hydrogen bonding interactions. Here, we report a copper(II) complex formed in the reaction of Cu(CH₃COO)₂.H₂O with 1,10-phenanthroline.

Similar to the reported copper(II) complex (Xu et al., 2008), the asymmetric unit of the complex consists of one [Cu(phen)₂(CH₃COO)]⁺ complex cation, one acetate anion and seven water molecules. As shown in Fig 1, the central Cu^II ion is five coordinate, being bound to four N atoms from two bidentate chelating 1,10-phenanthroline ligands and one O atom from the acetate anion, forming a strongly distorted square-pyramidal geometry. The O1, N1, N4, and N3 atoms are in the equatorial plane, and N2 is in the axial position. The Cu^II ion lies 0.2243 (18) Å above the equatorial plane towards N2. The Cu1—N2 bond is significantly longer [2.191 (4) Å] (Table 1), as seen previously [2.1866 (19) Å] (Tu et al., 2008).

In the crystal, hydrogen-bonded water molecules and acetate anion form two-dimensional polymeric structure parallel to (0 1 0) (Fig. 2). The coordination cations are linked to this layer via O-H···O hydrogen bonds (Table 2) between one of the water molecules and coordinated acetate ligand (Fig. 3).

Experimental

2 ml of aqueous solution of potassium hydroxide (2 mmol, 112.2 mg) were added to a stirred aqueous solution (5 ml) of cupric acetate monohydrate (1 mmol, 199.7 mg) followe by a methanol solution (5 ml) of 1,10-phenanthroline (2 mmol, 396.4 mg). The reaction mixture was and stirred for 4 h. The resultant solution was held at room temperature for ten days, whereupon the blue block-shaped crystals suitable for X-ray diffraction were obtained.