catena-Poly[[[aqua­bis(1H-imidazole-κN 3)copper(II)]-μ-naphthalene-1,4-dicarboxyl­ato-κ2 O 1:O 4] dihydrate]

Jun-Hua Li; Jing-Jing Nie; Duan-Jun Xu

doi:10.1107/S1600536808018515

. 2008 Jun 21;64(Pt 7):m948–m949. doi: 10.1107/S1600536808018515

catena-Poly[[[aquabis(1H-imidazole-κN ³)copper(II)]-μ-naphthalene-1,4-dicarboxylato-κ² O ¹:O ⁴] dihydrate]

Jun-Hua Li ^a, Jing-Jing Nie ^a, Duan-Jun Xu ^a,^*

PMCID: PMC2961746 PMID: 21202799

Abstract

In the title compound, {[Cu(C₁₂H₆O₄)(C₃H₄N₂)₂(H₂O)]·2H₂O}_n, the Cu^II cation is coordinated by two naphthalene-1,4-dicarboxylate (naph) dianions, two imidazole molecules and one water molecule in a distorted square-pyramidal geometry. The Cu—O bond distance in the apical direction is 0.509 (3) Å longer than the mean Cu—O bond distance in the basal plane. The naph dianion bridges two Cu^II cations, forming a one-dimensional polymeric chain. The coordinated water molecule is hydrogen-bonded to the carboxylate groups and imidazole ligands of adjacent polymeric chains, forming a three-dimensional supramolecular structure. No π–π stacking is observed in the crystal structure. One solvent water molecule is disordered equally over two positions.

Related literature

For general background, see: Su & Xu (2004 ▶); Li et al. (2005 ▶). For related structures, see: Derissen et al. (1979 ▶); Li et al. (2008 ▶).

Experimental

Crystal data

[Cu(C₁₂H₆O₄)(C₃H₄N₂)₂(H₂O)]·2H₂O
M _r = 467.92
Monoclinic,
a = 12.571 (2) Å
b = 14.698 (3) Å
c = 12.636 (2) Å
β = 119.011 (6)°
V = 2041.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 295 (2) K
0.33 × 0.30 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.660, T _max = 0.765
23205 measured reflections
3989 independent reflections
3251 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.097
S = 1.06
3989 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018515/sg2252sup1.cif

e-64-0m948-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018515/sg2252Isup2.hkl

e-64-0m948-Isup2.hkl^{(191.6KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Cu—N1	1.992 (2)
Cu—N3	1.990 (2)
Cu—O1	1.9819 (17)
Cu—O3ⁱ	2.0116 (17)
Cu—O5	2.506 (2)

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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
O1W—H1A⋯O3	0.87	1.99	2.846 (3)	170
O1W—H1B⋯O4ⁱⁱ	0.89	1.93	2.789 (3)	162
O2WA—H2A⋯O1W	0.91	1.97	2.828 (13)	155
O2WB—H2C⋯O2WA	0.85	1.55	2.156 (16)	126
N2—H2N⋯O1Wⁱⁱⁱ	0.86	1.96	2.798 (4)	165
N4—H4N⋯O5^iv	0.86	2.02	2.866 (3)	166
O5—H5A⋯O2ⁱⁱ	0.85	1.90	2.716 (3)	162
O5—H5B⋯O4^v	0.85	1.95	2.791 (3)	172
C17—H17⋯O2^vi	0.93	2.50	3.389 (4)	160

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

Acknowledgments

The work was supported by the ZIJIN project of Zhejiang University, China.

supplementary crystallographic information

Comment

As part of our investigation on the nature of π-π stacking between aromatic rings (Li et al., 2005), the title polymeric complex of Cu^II incorporating imidazole and naphthalenedicarboxylate (naph) ligands has been prepared and its crystal structure is reported here.

The Cu^II cation is coordinated by two naph dianions, two imidazole molecules and one water molecule in a distorted square pyramidal geometry. The Cu—O(water) bond distance in the apical direction is longer than mean Cu—O(carboxyl) bond distance in the basal plane by 0.509 (3) Å. The naph dianion bridges two Cu^II cations by two carboxyl groups to form the one dimensional polymeric chain (Fig. 1). Two carboxyl groups of the naph dianion are twisted with respect to the C1-benzene ring with the dihedral angles of 32.0 (2)° and 38.2 (2)°, which are close to that found in the free naphthalenedicarboxylic acid (ca 40°; Derissen et al., 1979) but are much smaller than those [52.5 (3)° and 48.7 (3)°] found in a Mn^II complex with the uncoordinated naph dianion (Li et al., 2008). The coordinated water molecule (O5) is hydrogen bonded to carboxyl groups and imidazole ligand of adjacent polymeric chains (Table 2) to form the three dimensional supra-molecular structure.

The parallel C8-benzene and C8ⁱⁱⁱ-benzene rings from the adjacent polymeric chains overlap as shown in Fig. 2 [symmetry code: (iii) 1 - x, 1 - y, 2 - z] with a face-to-face separation of 3.67 (2) Å indicating no π-π stacking existing between benzene rings, a similar situation to that found in the Mn^II complex with uncoordinated naph dianion (Li et al., 2008). The face-to-face distances between parallel N1-imidazole and N1^iv-imidazole rings and between parallel N3-imidazole and N3^v-imidazole rings are 3.310 (4) and 3.050 (17) Å, respectively [symmetry codes: (iv) 1 - x, -y, 1 - z; (v) 1 - x, 1 - y, 1 - z]. However the imidazole rings are not overlapping each other in the crystal structure (Fig. 3), therefore no π-p\ stacking exists between parallel imidazole rings too.

Experimental

A water-ethanol solution (12 ml, 1:1) containing naphthalene-1,4-dicarboxyllic acid (0.162 g, 0.75 mmol), sodium hydroxide (0.053 g, 1.3 mmol), sodium acetate trihydrate (0.204 g, 1.5 mmol), cupric chloride dihydrate (0.085 g, 0.5 mmol) and imidazole (0.034 g, 0.5 mmol) was refluxed for 3 h. After cooling to room temperature the solution was filtered. The single crystals of the title compound were obtained from the filtrate after 8 d.