Bis(ethyl­enediamine-κ2 N,N′)bis­(methanol-κO)copper(II) benzene-1,4-dicarboxyl­ate methanol disolvate

Abolfazl Abbaszadeh; Nasser Safari; Vahid Amani; Behrouz Notash

doi:10.1107/S1600536812028942

. 2012 Jun 30;68(Pt 7):m1012. doi: 10.1107/S1600536812028942

Bis(ethylenediamine-κ² N,N′)bis(methanol-κO)copper(II) benzene-1,4-dicarboxylate methanol disolvate

Abolfazl Abbaszadeh ^a, Nasser Safari ^a,^*, Vahid Amani ^a, Behrouz Notash ^a

PMCID: PMC3393248 PMID: 22807708

Abstract

In the cation of the title compound, [Cu(C₂H₈N₂)₂(CH₃OH)₂](C₈H₄O₄)·2CH₃OH, the Cu^II atom lies on an inversion centre. The four N atoms of two ethylenediamine ligands around the Cu^II atom form the equatorial plane, while two methanol O atoms in the axial positions complete a Jahn–Teller distorted octahedral coordination. The benzene-1,4-dicarboxylate anion is centrosymmetric. In the crystal, C—H⋯O, N—H⋯O and O—H⋯O hydrogen bonds link the cations, the anions and the methanol solvent molecules.

Related literature

For the role of copper compounds in biology, see: Kovala-Demertzi et al. (1997 ▶). For background to copper coordination polymers with carboxylate ligands, see: Eddaoudi et al. (2001 ▶); Wen et al. (2005 ▶). For related structures with copper(II) and carboxylate anions, see: Al-Hashemi et al. (2010a ▶,b ▶).

Experimental

Crystal data

[Cu(C₂H₈N₂)₂(CH₄O)₂](C₈H₄O₄)·2CH₄O
M _r = 476.04
Monoclinic,
a = 7.3075 (15) Å
b = 12.416 (3) Å
c = 12.551 (3) Å
β = 92.43 (3)°
V = 1137.7 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 120 K
0.30 × 0.25 × 0.20 mm

Data collection

Stoe IPDS-2T diffractometer
Absorption correction: numerical (X-SHAPE and X-RED; Stoe & Cie, 2002 ▶) T _min = 0.752, T _max = 0.824
7838 measured reflections
3038 independent reflections
2347 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.085
S = 1.03
3038 reflections
159 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812028942/hy2562sup1.cif

e-68-m1012-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028942/hy2562Isup2.hkl

e-68-m1012-Isup2.hkl^{(149.1KB, 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
N1—H1C⋯O2	0.82 (3)	2.27 (3)	3.075 (3)	167 (3)
N1—H1D⋯O3ⁱ	0.84 (3)	2.20 (3)	3.009 (2)	162 (3)
N2—H2C⋯O3	0.86 (2)	2.12 (3)	2.976 (2)	169 (3)
N2—H2D⋯O1ⁱ	0.92 (2)	2.18 (3)	3.065 (3)	160 (2)
O3—H3A⋯O2	0.79 (2)	1.89 (2)	2.675 (2)	172 (3)
O4—H4A⋯O1ⁱⁱ	0.78 (2)	1.85 (2)	2.628 (2)	171 (3)
C7—H7C⋯O4ⁱⁱⁱ	0.98	2.53	3.320 (3)	138

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

Acknowledgments

We are grateful to Shahid Beheshti University for financial support.

supplementary crystallographic information

Comment

Copper plays a role in a number of biological processes with therapeutically administered drugs (Kovala-Demertzi et al., 1997). Coordination chemistry of Cu(II) complexes is important as building-blocks to construct novel coordination architectures (Wen et al., 2005). Carboxylate anions are widely used in the synthesis of coordination polymers (Eddaoudi et al., 2001). In the recent years, we reported the synthesis and crystal structures of Cu(II) carboxylate complexes (Al-Hashemi et al., 2010a,b). In order to expand this field, the title compound has been synthesized and its crystal structure is reported herein.

The asymmetric unit of the title compound (Fig. 1) consists a half of Cu^II ion, one ethylenediamine (en), one coordinated methanol, one uncoordinated methanol and a half of benzene-1,4-dicarboxylate anion. The Cu^II atom in the [Cu(en)₂(CH₃OH)₂]²⁺ cation lies on an inversion centre. The four N atoms of the en ligands in the equatorial plane around the Cu^II atom form a slightly distorted square-planar arrangement, while the slightly distorted Jahn-Teller octahedral coordination is completed by two methanol O atoms in the axial positions. In the crystal, intermolecular C—H···O, N—H···O and O—H···O hydrogen bonds (Table 1) link the cations, the anions and the methanol solvent molecules (Fig. 2), which are effective in the stabilization of the structure.

Experimental

Benzene-1,4-dicarboxylic acid (0.10 g, 0.59 mmol) was dissolved in 6 ml methanol and 3.9 ml ethylenediamine (0.30 mol L^-1 in methanol). Then CuCl₂.2H₂O (0.10 g, 0.59 mmol) was added to the solution and the reaction mixture was stirred. After 10 min 2-methylimidazol (0.10 g, 1.18 mmol) was added to the stirred solution. The resulting violet solution stirred at 313 K for 25 min. This solution was left to evaporate slowly at room temperature. After one week, violet block crystals of the title compound were isolated (yield: 0.20 g, 70.2%).