Bis(methanol-κO)bis­(1,2-diamino-2-hy­droxy­imino­ethanone oximato-κ2N,N′)copper(II) bis­(oxamide dioxime) methanol disolvate

Liu, D.; Zhang, R.; Hu, H.; Qi, J.; Yang, G.

doi:10.1107/S1600536812036811

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages m1235-m1236

https://doi.org/10.1107/S1600536812036811

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Bis(methanol-κO)bis(1,2-diamino-2-hydroxyiminoethanone oximato-κ²N,N′)copper(II) bis(oxamide dioxime) methanol disolvate

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

^aDepartment of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
^*Correspondence e-mail: yanggm@nankai.edu.cn

(Received 1 July 2012; accepted 25 August 2012; online 1 September 2012)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.033
wR(F²) = 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

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
Symmetry codes: (i) -x+1, -y, -z+2; (ii) -x+2, -y+1, -z+1; (iii) x, y+1, z-1; (iv) x, y, z-1; (v) x, y, z+1; (vi) -x+1, -y+1, -z+2; (vii) x-1, y, z; (viii) -x, -y+1, -z+1; (ix) -x+1, -y+1, -z+1; (x) x, y-1, z.

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812036811/hy2572sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812036811/hy2572Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812036811/hy2572Isup4.cdx

checkCIF report

Comment top

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.

Related literature top

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 top

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%.

Structure description top

Computing details top

Data collection: CrystalClear (Rigaku, 2009); cell refinement: CrystalClear (Rigaku, 2009); data reduction: CrystalClear (Rigaku, 2009); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i) 1-x, -y, 2-z; (ii) -x, 2-y, 1-z; (iii) 1-x, 1-y, 1-z.]

Bis(methanol-κO)bis(oxamide oxime oximato-κ²N,N')copper(II) bis(oxamide dioxime) methanol disolvate top

Crystal data top

[Cu(C₂H₅N₄O₂)₂(CH₄O)₂]·2C₂H₆N₄O₂·2CH₄O	Z = 1
M_r = 662.13	F(000) = 347
Triclinic, P1	D_x = 1.611 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.567 (3) Å	Cell parameters from 2266 reflections
b = 8.874 (4) Å	θ = 1.9–27.9°
c = 10.867 (5) Å	µ = 0.89 mm⁻¹
α = 92.046 (4)°	T = 113 K
β = 103.327 (9)°	Block, green
γ = 104.957 (5)°	0.28 × 0.24 × 0.22 mm
V = 682.5 (5) Å³

Data collection top

Rigaku Saturn724 CCD diffractometer	3212 independent reflections
Radiation source: rotating anode	2252 reflections with I > 2σ(I)
Multilayer monochromator	R_int = 0.044
Detector resolution: 14.22 pixels mm^-1	θ_max = 27.9°, θ_min = 1.9°
ω scans	h = −9→9
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	k = −11→11
T_min = 0.790, T_max = 0.829	l = −11→14
7216 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	w = 1/[σ²(F_o²) + (0.0231P)²] where P = (F_o² + 2F_c²)/3
3212 reflections	(Δ/σ)_max = 0.001
198 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu(C₂H₅N₄O₂)₂(CH₄O)₂]·2C₂H₆N₄O₂·2CH₄O	γ = 104.957 (5)°
M_r = 662.13	V = 682.5 (5) Å³
Triclinic, P1	Z = 1
a = 7.567 (3) Å	Mo Kα radiation
b = 8.874 (4) Å	µ = 0.89 mm⁻¹
c = 10.867 (5) Å	T = 113 K
α = 92.046 (4)°	0.28 × 0.24 × 0.22 mm
β = 103.327 (9)°

Data collection top

Rigaku Saturn724 CCD diffractometer	3212 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2009)	2252 reflections with I > 2σ(I)
T_min = 0.790, T_max = 0.829	R_int = 0.044
7216 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 0.99	Δρ_max = 0.30 e Å⁻³
3212 reflections	Δρ_min = −0.39 e Å⁻³
198 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.2733 (3)	0.1538 (3)	1.0896 (2)	0.0102 (5)
C2	0.2003 (3)	0.1293 (3)	0.9482 (2)	0.0102 (5)
C3	0.0546 (3)	0.9542 (3)	0.47271 (19)	0.0089 (5)
C4	0.5721 (3)	0.4615 (3)	0.53280 (19)	0.0092 (5)
C5	0.6807 (3)	0.4989 (3)	0.2349 (2)	0.0207 (6)
H5A	0.7195	0.5685	0.3141	0.031*
H5B	0.5433	0.4548	0.2126	0.031*
H5C	0.7183	0.5586	0.1666	0.031*
C6	0.7357 (4)	0.3711 (3)	0.9294 (2)	0.0317 (7)
H6C	0.7999	0.4807	0.9621	0.048*
H6D	0.5989	0.3535	0.9151	0.048*
H6E	0.7658	0.3478	0.8490	0.048*
Cu1	0.5000	0.0000	1.0000	0.01296 (13)
N1	0.3058 (2)	0.0743 (2)	0.89207 (16)	0.0131 (4)
N2	0.4170 (2)	0.0981 (2)	1.12976 (16)	0.0105 (4)
N3	0.1956 (2)	0.2296 (2)	1.16254 (18)	0.0165 (5)
H3A	0.2423	0.2452	1.2454	0.020*
H3B	0.0982	0.2636	1.1274	0.020*
N4	0.0410 (2)	0.1635 (2)	0.89006 (17)	0.0163 (5)
H4A	0.0011	0.1485	0.8067	0.020*
H4B	−0.0236	0.2010	0.9353	0.020*
N5	0.1797 (2)	1.0348 (2)	0.41876 (16)	0.0100 (4)
N6	0.0166 (3)	0.7998 (2)	0.48310 (18)	0.0168 (5)
H6A	0.0792	0.7436	0.4517	0.020*
H6B	−0.0710	0.7546	0.5214	0.020*
N7	0.7401 (2)	0.5552 (2)	0.58021 (17)	0.0118 (4)
N8	0.5201 (2)	0.3067 (2)	0.53953 (18)	0.0172 (5)
H8A	0.6030	0.2596	0.5788	0.021*
H8B	0.4030	0.2519	0.5047	0.021*
O1	0.50028 (19)	0.11732 (19)	1.25853 (13)	0.0127 (4)
O2	0.2404 (2)	0.0421 (2)	0.76012 (14)	0.0200 (4)
H2	0.3155	0.0041	0.7315	0.030*
O3	0.86131 (19)	0.46482 (19)	0.63897 (15)	0.0158 (4)
H3	0.9731	0.5217	0.6610	0.024*
O4	0.2651 (2)	0.93020 (19)	0.36628 (14)	0.0130 (4)
H4	0.3493	0.9817	0.3336	0.019*
O5	0.7699 (2)	0.3745 (2)	0.25156 (15)	0.0168 (4)
H5	0.688 (3)	0.305 (3)	0.267 (2)	0.025*
O6	0.7980 (2)	0.2702 (2)	1.02027 (16)	0.0238 (5)
H6	0.791 (4)	0.308 (3)	1.085 (3)	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0102 (11)	0.0089 (13)	0.0107 (12)	−0.0007 (10)	0.0048 (9)	0.0005 (9)
C2	0.0085 (11)	0.0089 (13)	0.0121 (12)	−0.0014 (10)	0.0041 (9)	0.0038 (9)
C3	0.0072 (11)	0.0099 (13)	0.0082 (11)	0.0025 (10)	−0.0006 (9)	0.0002 (9)
C4	0.0116 (11)	0.0100 (13)	0.0073 (11)	0.0026 (10)	0.0054 (9)	0.0003 (9)
C5	0.0196 (13)	0.0204 (16)	0.0233 (14)	0.0076 (12)	0.0047 (11)	0.0038 (11)
C6	0.0400 (17)	0.0313 (19)	0.0320 (17)	0.0188 (15)	0.0132 (13)	0.0151 (14)
Cu1	0.0131 (2)	0.0178 (3)	0.0095 (2)	0.00752 (19)	0.00211 (16)	0.00014 (17)
N1	0.0129 (10)	0.0201 (13)	0.0062 (10)	0.0060 (9)	0.0005 (8)	0.0006 (8)
N2	0.0082 (9)	0.0146 (11)	0.0079 (10)	0.0026 (8)	0.0010 (7)	0.0004 (8)
N3	0.0149 (10)	0.0232 (13)	0.0136 (11)	0.0109 (10)	0.0019 (8)	−0.0016 (9)
N4	0.0150 (10)	0.0236 (13)	0.0110 (10)	0.0086 (10)	0.0013 (8)	−0.0006 (9)
N5	0.0102 (9)	0.0090 (11)	0.0126 (10)	0.0047 (8)	0.0038 (8)	0.0002 (8)
N6	0.0185 (11)	0.0108 (12)	0.0279 (12)	0.0046 (9)	0.0177 (9)	0.0049 (9)
N7	0.0083 (9)	0.0109 (11)	0.0171 (10)	0.0055 (8)	0.0017 (8)	0.0025 (8)
N8	0.0085 (9)	0.0082 (11)	0.0307 (12)	0.0021 (9)	−0.0032 (8)	0.0016 (9)
O1	0.0122 (8)	0.0186 (10)	0.0067 (8)	0.0030 (7)	0.0025 (6)	0.0010 (7)
O2	0.0206 (9)	0.0349 (12)	0.0080 (8)	0.0158 (9)	0.0013 (7)	−0.0009 (8)
O3	0.0085 (8)	0.0121 (10)	0.0238 (9)	0.0039 (7)	−0.0030 (7)	0.0029 (7)
O4	0.0143 (8)	0.0118 (9)	0.0185 (9)	0.0053 (7)	0.0131 (7)	0.0032 (7)
O5	0.0125 (9)	0.0142 (11)	0.0210 (10)	−0.0002 (8)	0.0031 (7)	0.0030 (8)
O6	0.0330 (10)	0.0288 (12)	0.0191 (10)	0.0202 (9)	0.0114 (8)	0.0069 (8)

Geometric parameters (Å, º) top

C1—N2	1.300 (3)	Cu1—N2ⁱⁱⁱ	1.9349 (18)
C1—N3	1.344 (3)	Cu1—N2	1.9349 (18)
C1—C2	1.496 (3)	Cu1—O6	2.797 (2)
C2—N1	1.285 (3)	N1—O2	1.397 (2)
C2—N4	1.340 (3)	N2—O1	1.380 (2)
C3—N5	1.299 (3)	N3—H3A	0.8800
C3—N6	1.340 (3)	N3—H3B	0.8800
C3—C3ⁱ	1.494 (4)	N4—H4A	0.8800
C4—N7	1.302 (3)	N4—H4B	0.8800
C4—N8	1.337 (3)	N5—O4	1.430 (2)
C4—C4ⁱⁱ	1.493 (4)	N6—H6A	0.8800
C5—O5	1.431 (3)	N6—H6B	0.8800
C5—H5A	0.9800	N7—O3	1.428 (2)
C5—H5B	0.9800	N8—H8A	0.8800
C5—H5C	0.9800	N8—H8B	0.8800
C6—O6	1.437 (3)	O2—H2	0.8400
C6—H6C	0.9800	O3—H3	0.8400
C6—H6D	0.9800	O4—H4	0.8400
C6—H6E	0.9800	O5—H5	0.81 (3)
Cu1—N1ⁱⁱⁱ	1.9314 (18)	O6—H6	0.79 (2)
Cu1—N1	1.9314 (18)

N2—C1—N3	125.9 (2)	N1—Cu1—O6	97.31 (8)
N2—C1—C2	112.90 (18)	N2ⁱⁱⁱ—Cu1—O6	90.37 (7)
N3—C1—C2	121.17 (19)	N2—Cu1—O6	89.63 (7)
N1—C2—N4	125.4 (2)	C2—N1—O2	115.67 (16)
N1—C2—C1	112.98 (18)	C2—N1—Cu1	116.25 (15)
N4—C2—C1	121.63 (19)	O2—N1—Cu1	126.33 (13)
N5—C3—N6	126.10 (19)	C1—N2—O1	118.35 (17)
N5—C3—C3ⁱ	115.4 (3)	C1—N2—Cu1	115.95 (15)
N6—C3—C3ⁱ	118.5 (3)	O1—N2—Cu1	125.67 (13)
N7—C4—N8	125.9 (2)	C1—N3—H3A	120.0
N7—C4—C4ⁱⁱ	115.2 (3)	C1—N3—H3B	120.0
N8—C4—C4ⁱⁱ	118.8 (2)	H3A—N3—H3B	120.0
O5—C5—H5A	109.5	C2—N4—H4A	120.0
O5—C5—H5B	109.5	C2—N4—H4B	120.0
H5A—C5—H5B	109.5	H4A—N4—H4B	120.0
O5—C5—H5C	109.5	C3—N5—O4	108.74 (18)
H5A—C5—H5C	109.5	C3—N6—H6A	120.0
H5B—C5—H5C	109.5	C3—N6—H6B	120.0
O6—C6—H6C	109.5	H6A—N6—H6B	120.0
O6—C6—H6D	109.5	C4—N7—O3	108.65 (19)
H6C—C6—H6D	109.5	C4—N8—H8A	120.0
O6—C6—H6E	109.5	C4—N8—H8B	120.0
H6C—C6—H6E	109.5	H8A—N8—H8B	120.0
H6D—C6—H6E	109.5	N1—O2—H2	109.5
N1ⁱⁱⁱ—Cu1—N1	179.999 (1)	N7—O3—H3	109.5
N1ⁱⁱⁱ—Cu1—N2ⁱⁱⁱ	80.90 (8)	N5—O4—H4	109.5
N1—Cu1—N2ⁱⁱⁱ	99.10 (8)	C5—O5—H5	101.6 (18)
N1ⁱⁱⁱ—Cu1—N2	99.10 (8)	C6—O6—Cu1	108.13 (15)
N1—Cu1—N2	80.90 (8)	C6—O6—H6	104 (2)
N2ⁱⁱⁱ—Cu1—N2	179.999 (1)	Cu1—O6—H6	97 (2)
N1ⁱⁱⁱ—Cu1—O6	82.69 (8)

N2—C1—C2—N1	−7.5 (3)	N3—C1—N2—Cu1	−178.33 (18)
N3—C1—C2—N1	171.1 (2)	C2—C1—N2—Cu1	0.2 (3)
N2—C1—C2—N4	172.8 (2)	N1ⁱⁱⁱ—Cu1—N2—C1	−175.60 (18)
N3—C1—C2—N4	−8.6 (4)	N1—Cu1—N2—C1	4.40 (18)
N4—C2—N1—O2	−3.1 (4)	O6—Cu1—N2—C1	101.86 (18)
C1—C2—N1—O2	177.20 (19)	N1ⁱⁱⁱ—Cu1—N2—O1	6.43 (18)
N4—C2—N1—Cu1	−168.98 (19)	N1—Cu1—N2—O1	−173.57 (18)
C1—C2—N1—Cu1	11.3 (3)	O6—Cu1—N2—O1	−76.10 (17)
N2ⁱⁱⁱ—Cu1—N1—C2	171.00 (17)	N6—C3—N5—O4	2.8 (3)
N2—Cu1—N1—C2	−9.00 (17)	C3ⁱ—C3—N5—O4	−177.3 (2)
O6—Cu1—N1—C2	−97.45 (18)	N8—C4—N7—O3	1.0 (3)
N2ⁱⁱⁱ—Cu1—N1—O2	6.80 (19)	C4ⁱⁱ—C4—N7—O3	−179.8 (2)
N2—Cu1—N1—O2	−173.20 (19)	N1ⁱⁱⁱ—Cu1—O6—C6	169.14 (15)
O6—Cu1—N1—O2	98.35 (17)	N1—Cu1—O6—C6	−10.87 (15)
N3—C1—N2—O1	−0.2 (4)	N2ⁱⁱⁱ—Cu1—O6—C6	88.36 (15)
C2—C1—N2—O1	178.31 (17)	N2—Cu1—O6—C6	−91.64 (15)

Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱⁱⁱ	0.84	1.96	2.737 (3)	154
O3—H3···O5^iv	0.84	1.92	2.744 (3)	166
O4—H4···O1^v	0.84	1.79	2.621 (3)	169
O5—H5···O1^vi	0.81 (2)	1.87 (3)	2.657 (3)	164 (2)
O6—H6···O5^vii	0.79 (3)	1.94 (3)	2.721 (3)	173 (3)
N3—H3A···N7^viii	0.88	2.50	3.195 (3)	136
N3—H3B···O6^ix	0.88	2.32	3.167 (3)	162
N4—H4A···O4^x	0.88	2.35	3.112 (3)	145
N4—H4B···O6^ix	0.88	2.00	2.878 (3)	172
N6—H6A···O3ⁱⁱ	0.88	2.26	3.097 (3)	159
N6—H6B···N7^ix	0.88	2.19	3.007 (3)	155
N8—H8A···O4ⁱⁱ	0.88	2.20	3.043 (3)	159
N8—H8B···N5^xi	0.88	2.21	3.031 (3)	154

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y, −z+2; (iv) −x+2, −y+1, −z+1; (v) x, y+1, z−1; (vi) x, y, z−1; (vii) x, y, z+1; (viii) −x+1, −y+1, −z+2; (ix) x−1, y, z; (x) −x, −y+1, −z+1; (xi) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₅N₄O₂)₂(CH₄O)₂]·2C₂H₆N₄O₂·2CH₄O
M_r	662.13
Crystal system, space group	Triclinic, P1
Temperature (K)	113
a, b, c (Å)	7.567 (3), 8.874 (4), 10.867 (5)
α, β, γ (°)	92.046 (4), 103.327 (9), 104.957 (5)
V (Å³)	682.5 (5)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.89
Crystal size (mm)	0.28 × 0.24 × 0.22

Data collection
Diffractometer	Rigaku Saturn724 CCD
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2009)
T_min, T_max	0.790, 0.829
No. of measured, independent and observed [I > 2σ(I)] reflections	7216, 3212, 2252
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.086, 0.99
No. of reflections	3212
No. of parameters	198
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.39

Computer programs: CrystalClear (Rigaku, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+1, −y, −z+2; (ii) −x+2, −y+1, −z+1; (iii) x, y+1, z−1; (iv) x, y, z−1; (v) x, y, z+1; (vi) −x+1, −y+1, −z+2; (vii) x−1, y, z; (viii) −x, −y+1, −z+1; (ix) −x+1, −y+1, −z+1; (x) x, y−1, z.

Acknowledgements

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.

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