Bis(methanol-κO)bis­(1,2-diamino-2-hy­droxy­imino­ethanone oximato-κ2 N,N′)copper(II) bis­(oxamide dioxime) methanol disolvate

Daying Liu; Ruihong Zhang; Hui Hu; Jing Qi; Guangming Yang

doi:10.1107/S1600536812036811

. 2012 Sep 1;68(Pt 10):m1235–m1236. doi: 10.1107/S1600536812036811

Bis(methanol-κO)bis(1,2-diamino-2-hydroxyiminoethanone oximato-κ² N,N′)copper(II) bis(oxamide dioxime) methanol disolvate

Daying Liu ^a, Ruihong Zhang ^a, Hui Hu ^a, Jing Qi ^a, Guangming Yang ^a,^*

PMCID: PMC3470128 PMID: 23125572

Abstract

In the title compound, [Cu(C₂H₅N₄O₂)₂(CH₃OH)₂]·2C₂H₆N₄O₂·2CH₃OH, the Cu^II atom, lying on an inversion center, is coordinated by four N atoms from two 1,2-diamino-2-hydroxyiminoethanone oximate anion and two O atoms from two methanol molecules in a distorted octahedral geometry. The two uncoordinating oxamide dioxime molecules, each lying on an inversion center, adopt a trans conformation. In the crystal, O—H⋯O, N—H⋯O and N—H⋯N hydrogen bonds link the complex molecules and the oxamide dioxime and methanol molecules.

Related literature

For related structures, see: Bélombé et al. (2006 ▶); Belombe et al. (2007) ▶; Egharevba et al. (1982 ▶); Endres (1980 ▶); Endres & Schlicksupp (1980 ▶); Endres et al. (1983 ▶); Gunasekaran et al. (1995 ▶).

Experimental

Crystal data

[Cu(C₂H₅N₄O₂)₂(CH₄O)₂]·2C₂H₆N₄O₂·2CH₄O
M _r = 662.13
Triclinic,
a = 7.567 (3) Å
b = 8.874 (4) Å
c = 10.867 (5) Å
α = 92.046 (4)°
β = 103.327 (9)°
γ = 104.957 (5)°
V = 682.5 (5) Å³
Z = 1
Mo Kα radiation
μ = 0.89 mm⁻¹
T = 113 K
0.28 × 0.24 × 0.22 mm

Data collection

Rigaku Saturn724 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009 ▶) T _min = 0.790, T _max = 0.829
7216 measured reflections
3212 independent reflections
2252 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.086
S = 0.99
3212 reflections
198 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: CrystalClear (Rigaku, 2009 ▶); 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: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812036811/hy2572sup1.cif

e-68-m1235-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036811/hy2572Isup2.hkl

e-68-m1235-Isup2.hkl^{(157.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812036811/hy2572Isup4.cdx

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
O2—H2⋯O1ⁱ	0.84	1.96	2.737 (3)	154
O3—H3⋯O5ⁱⁱ	0.84	1.92	2.744 (3)	166
O4—H4⋯O1ⁱⁱⁱ	0.84	1.79	2.621 (3)	169
O5—H5⋯O1^iv	0.81 (2)	1.87 (3)	2.657 (3)	164 (2)
O6—H6⋯O5^v	0.79 (3)	1.94 (3)	2.721 (3)	173 (3)
N3—H3A⋯N7^vi	0.88	2.50	3.195 (3)	136
N3—H3B⋯O6^vii	0.88	2.32	3.167 (3)	162
N4—H4A⋯O4^viii	0.88	2.35	3.112 (3)	145
N4—H4B⋯O6^vii	0.88	2.00	2.878 (3)	172
N6—H6A⋯O3^ix	0.88	2.26	3.097 (3)	159
N6—H6B⋯N7^vii	0.88	2.19	3.007 (3)	155
N8—H8A⋯O4^ix	0.88	2.20	3.043 (3)	159
N8—H8B⋯N5^x	0.88	2.21	3.031 (3)	154

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) .

Acknowledgments

This work was supported by the National Natural Science Foundation of China (Nos. 20941004, 21071084 and 90922032) and the MOE (IRT-0927), Tianjin Key Laboratory of Metal and Molecule Based Material Chemistry.

supplementary crystallographic information

Comment

Owing to the variety of structures and unique properties, transition metal complexes of oxamide oxime (diaminoglyoxime, oaoH₂) are of great interest. So far, most of the published work concerns 4-coordinated transition metal oxamide oximate complexs (Endres, 1980; Endres & Schlicksupp, 1980; Endres et al., 1983). The 6-coordinated transition metal oxamide oximate complexes have not been reported hitherto (Bélombé et al., 2006; Belombe et al., 2007; Egharevba et al., 1982). We used oxamide oxime as ligands (Gunasekaran et al., 1995) and obtained green crystals of the title compound from a methanol solution.

In the title compound, the Cu^II atom, lying on an inversion center, is surrounded in an octahedral environment defined by four N atoms from two oaoH ligands and two O atoms from two methanol molecules (Fig. 1). The methanol molecules are weakly coordinated to the Cu atom with a Cu—O distance of 2.797 (2) Å. In the crystal, O—H···O, N—H···O and N—H···N hydrogen bonds (Table 1) link the complex molecules and the oxamide oxime and methanol molecules.

Experimental

A methanol solution (10 ml) of copper acetate (0.1 mmol) was added dropwise to a methanol solution (10 ml) of oxamide oxime (0.1 mmol). The title compound was obtained as green crystals by slow evaporation of the filtrate in air at room temperature 5 days later. Analysis, calculated for C₁₂H₃₈CuN₁₆O₁₂: C 21.77, H 5.78, N 33.85, O 29.00%; found: C 21.79, H 5.76, N 33.88, O 29.02%.