Di-μ-methano­lato-κ4O:O-bis­[bis­(3-methyl-5-phenyl-1H-pyrazole-κN2)(nitrato-κO)copper(II)]

Li, X.-G.; Gao, M.-M.; Ng, S.W.

doi:10.1107/S160053681201241X

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m503

doi:10.1107/S160053681201241X

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Di-μ-methanolato-κ⁴O:O-bis[bis(3-methyl-5-phenyl-1H-pyrazole-κN²)(nitrato-κO)copper(II)]

Xu-Guang Li,^a Meng-Meng Gao ^b and Seik Weng Ng ^c ^*

^aFundamental Laboratory of Life Science, Medical School of Tibet University for Nationalities, Xianyang 712082, People's Republic of China, ^bSchool of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, People's Republic of China, and ^cDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and Chemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 16 March 2012; accepted 22 March 2012; online 31 March 2012)

Copper nitrate in methanol solution cleaves the N—C_methanol bond when reacted with 3-methyl-5-phenylpyrazole-1-methanol to yield the centrosymmetric dinuclear title compound, [Cu₂(CH₃O)₂(NO₃)₂(C₁₀H₁₀N₂)₄], in which the Cu^II atom is linked to a nitrate ion, two methanolate ions and two pyrazole ligands in a distorted square-pyramidal environment. The O atom of the nitrate anion occupies the apical site. The crystal structure features intramolecular N—H⋯O hydrogen bonds.

Related literature

For a related structure, see: He & Sykes (2007 ). For the synthesis of 3-methyl-5-phenylpyrazole-1-methanol, see: Zhu et al. (2004 ).

Experimental

Crystal data

[Cu₂(CH₃O)₂(NO₃)₂(C₁₀H₁₀N₂)₄]
M_r = 945.97
Triclinic, $[P \overline 1]$
a = 8.3896 (8) Å
b = 11.2569 (11) Å
c = 12.7200 (12) Å
α = 106.120 (2)°
β = 103.025 (2)°
γ = 95.853 (2)°
V = 1106.85 (18) Å³
Z = 1
Mo Kα radiation
μ = 1.02 mm⁻¹
T = 293 K
0.12 × 0.11 × 0.10 mm

Data collection

Bruker SMART-1000 diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.887, T_max = 0.905
6768 measured reflections
4898 independent reflections
3461 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.116
S = 1.02
4898 reflections
290 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.87 (1)	2.26 (2)	3.012 (3)	144 (3)
N4—H4⋯O3	0.87 (1)	2.17 (2)	3.022 (4)	166 (3)
Symmetry code: (i) -x+1, -y+1, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681201241X/xu5488sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681201241X/xu5488Isup2.hkl

checkCIF report

Comment top

Copper nitrate in methanol solution cleaves the N–C_methanol bond when reacted with 3-methyl-5-phenylpyrazole-1-methanol to yield the dinuclear title compound (Scheme I, Fig. 1). The molecule lies on a center-of-inversion; the Cu_II atom is linked to a nitrate ion, two methanolate ions and two of the pyrazole ligands in a square-pyramidal environment. In the perchlorate analog, [Cu(OCH₃)(C₁₀H₁₀N₂)₂]₂(ClO₄)₂,the counterion is not connected to the copper atom, whose geometry is a square pyramid. The compound was synthesized by directly reacting 3-methyl-5-phenylpyrazole with copper perchlorate in methanol medium (He & Sykes, 2007).

Related literature top

For a related structure, see: He & Sykes (2007). For the synthesis of 3-methyl-5-phenylpyrazole-1-methanol, see: Zhu et al. (2004).

Experimental top

3-Methyl-5-phenylpyrazole-1-methanol was synthesized by using a literature procedure (Zhu et al., 2004). The ligand (0.065 g, 0.4 mmol) was dissolved in dichloromethane (10 mol) and this was mixed with a methanol solution (10 ml) of copper nitrate trihydrate (0.024 g, 0.1 mmol). The clear blue solution was filtered and then set aside for the growth of deep blue crystals. CH&N elemental analysis. Calc. for C₄₂H₄₆Cu₂N₁₀O₈: C 53.33, H 4.90; N 14.81%. Found: C 56.36, H 5.18, N 15.02%.

Structure description top

For a related structure, see: He & Sykes (2007). For the synthesis of 3-methyl-5-phenylpyrazole-1-methanol, see: Zhu et al. (2004).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of centrosymmetric [Cu(OCH₃)(NO₃)(C₁₀H₁₀N₂)₂]₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. Inversion-related atoms are not labeled.

Di-µ-methanolato-κ⁴O:O-bis[bis(3-methyl-5-phenyl-1H- pyrazole-κN²)(nitrato-κO)copper(II)] top

Crystal data top

[Cu₂(CH₃O)₂(NO₃)₂(C₁₀H₁₀N₂)₄]	Z = 1
M_r = 945.97	F(000) = 490
Triclinic, P1	D_x = 1.419 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3896 (8) Å	Cell parameters from 2170 reflections
b = 11.2569 (11) Å	θ = 2.5–24.5°
c = 12.7200 (12) Å	µ = 1.02 mm⁻¹
α = 106.120 (2)°	T = 293 K
β = 103.025 (2)°	Prism, blue
γ = 95.853 (2)°	0.12 × 0.11 × 0.10 mm
V = 1106.85 (18) Å³

Data collection top

Bruker SMART-1000 diffractometer	4898 independent reflections
Radiation source: fine-focus sealed tube	3461 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.887, T_max = 0.905	k = −12→14
6768 measured reflections	l = −16→10

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0516P)² + 0.4958P] where P = (F_o² + 2F_c²)/3
4898 reflections	(Δ/σ)_max = 0.001
290 parameters	Δρ_max = 0.38 e Å⁻³
2 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Cu₂(CH₃O)₂(NO₃)₂(C₁₀H₁₀N₂)₄]	γ = 95.853 (2)°
M_r = 945.97	V = 1106.85 (18) Å³
Triclinic, P1	Z = 1
a = 8.3896 (8) Å	Mo Kα radiation
b = 11.2569 (11) Å	µ = 1.02 mm⁻¹
c = 12.7200 (12) Å	T = 293 K
α = 106.120 (2)°	0.12 × 0.11 × 0.10 mm
β = 103.025 (2)°

Data collection top

Bruker SMART-1000 diffractometer	4898 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3461 reflections with I > 2σ(I)
T_min = 0.887, T_max = 0.905	R_int = 0.015
6768 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	2 restraints
wR(F²) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.38 e Å⁻³
4898 reflections	Δρ_min = −0.30 e Å⁻³
290 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.54841 (4)	0.37278 (3)	0.47584 (3)	0.04912 (14)
O1	0.7401 (3)	0.4733 (3)	0.3606 (2)	0.0769 (7)
O2	0.6684 (3)	0.6571 (2)	0.3847 (2)	0.0768 (7)
O3	0.5511 (3)	0.5059 (2)	0.23096 (17)	0.0703 (6)
O4	0.3871 (2)	0.46286 (18)	0.41469 (14)	0.0464 (5)
N1	0.7022 (3)	0.3017 (2)	0.57615 (18)	0.0508 (6)
N2	0.6938 (3)	0.3252 (2)	0.68576 (19)	0.0507 (6)
N3	0.4722 (3)	0.2251 (2)	0.3377 (2)	0.0576 (6)
N4	0.4708 (3)	0.2394 (3)	0.2345 (2)	0.0573 (6)
N5	0.6566 (3)	0.5464 (3)	0.3264 (2)	0.0535 (6)
C1	0.9035 (5)	0.2356 (4)	0.4677 (3)	0.0793 (11)
H1A	0.8149	0.2370	0.4056	0.119*
H1B	0.9330	0.1535	0.4525	0.119*
H1C	0.9983	0.2965	0.4764	0.119*
C2	0.8479 (4)	0.2663 (3)	0.5748 (2)	0.0519 (7)
C3	0.9314 (4)	0.2661 (3)	0.6822 (2)	0.0545 (7)
H3	1.0350	0.2440	0.7028	0.065*
C4	0.8307 (3)	0.3052 (3)	0.7523 (2)	0.0469 (6)
C5	0.8519 (3)	0.3269 (3)	0.8744 (2)	0.0493 (7)
C6	0.7739 (4)	0.4139 (3)	0.9353 (3)	0.0603 (8)
H6	0.7085	0.4603	0.8990	0.072*
C7	0.7932 (4)	0.4319 (4)	1.0499 (3)	0.0730 (10)
H7	0.7408	0.4906	1.0901	0.088*
C8	0.8892 (4)	0.3639 (4)	1.1049 (3)	0.0753 (11)
H8	0.8993	0.3748	1.1815	0.090*
C9	0.9694 (4)	0.2801 (4)	1.0461 (3)	0.0717 (10)
H9	1.0362	0.2353	1.0835	0.086*
C10	0.9524 (4)	0.2610 (3)	0.9315 (3)	0.0579 (8)
H10	1.0082	0.2040	0.8925	0.069*
C11	0.3473 (6)	0.0666 (4)	0.4104 (3)	0.0996 (15)
H11A	0.4399	0.1010	0.4763	0.149*
H11B	0.3330	−0.0234	0.3870	0.149*
H11C	0.2484	0.0925	0.4281	0.149*
C12	0.3794 (5)	0.1132 (3)	0.3157 (3)	0.0659 (9)
C13	0.3201 (5)	0.0571 (3)	0.1989 (3)	0.0731 (10)
H13	0.2534	−0.0214	0.1618	0.088*
C14	0.3786 (4)	0.1393 (3)	0.1488 (3)	0.0582 (8)
C15	0.3536 (4)	0.1299 (3)	0.0279 (3)	0.0616 (8)
C16	0.4062 (5)	0.2286 (4)	−0.0078 (3)	0.0764 (10)
H16	0.4597	0.3052	0.0456	0.092*
C17	0.3799 (5)	0.2146 (5)	−0.1229 (3)	0.0884 (12)
H17	0.4166	0.2815	−0.1461	0.106*
C18	0.3000 (6)	0.1023 (5)	−0.2022 (3)	0.0935 (14)
H18	0.2828	0.0925	−0.2792	0.112*
C19	0.2461 (7)	0.0050 (5)	−0.1673 (3)	0.1131 (18)
H19	0.1906	−0.0708	−0.2212	0.136*
C20	0.2722 (6)	0.0169 (4)	−0.0533 (3)	0.0944 (14)
H20	0.2353	−0.0507	−0.0310	0.113*
C21	0.2225 (4)	0.4090 (3)	0.3499 (3)	0.0620 (8)
H21A	0.1667	0.4727	0.3290	0.093*
H21B	0.1647	0.3730	0.3940	0.093*
H21C	0.2241	0.3446	0.2825	0.093*
H2	0.602 (2)	0.349 (3)	0.698 (3)	0.061 (10)*
H4	0.510 (4)	0.3130 (18)	0.231 (3)	0.079 (12)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0482 (2)	0.0578 (2)	0.03230 (18)	0.00578 (16)	−0.00269 (13)	0.01163 (15)
O1	0.0655 (15)	0.0950 (19)	0.0817 (17)	0.0317 (14)	0.0191 (13)	0.0398 (15)
O2	0.0714 (16)	0.0622 (15)	0.0842 (17)	0.0014 (13)	0.0201 (13)	0.0070 (14)
O3	0.0657 (14)	0.0978 (18)	0.0423 (12)	0.0083 (13)	0.0082 (10)	0.0205 (12)
O4	0.0393 (10)	0.0574 (12)	0.0334 (9)	0.0009 (9)	−0.0025 (8)	0.0123 (9)
N1	0.0506 (14)	0.0663 (16)	0.0343 (11)	0.0126 (12)	0.0056 (10)	0.0174 (11)
N2	0.0439 (14)	0.0703 (17)	0.0409 (12)	0.0157 (13)	0.0089 (11)	0.0217 (12)
N3	0.0634 (16)	0.0554 (16)	0.0418 (13)	0.0061 (13)	−0.0030 (11)	0.0109 (12)
N4	0.0658 (17)	0.0528 (16)	0.0400 (13)	0.0032 (13)	0.0029 (12)	0.0047 (12)
N5	0.0435 (14)	0.0709 (18)	0.0501 (14)	0.0076 (13)	0.0165 (11)	0.0225 (14)
C1	0.074 (2)	0.114 (3)	0.0451 (18)	0.029 (2)	0.0173 (17)	0.011 (2)
C2	0.0500 (17)	0.0613 (19)	0.0406 (15)	0.0102 (14)	0.0093 (13)	0.0118 (14)
C3	0.0439 (16)	0.068 (2)	0.0475 (16)	0.0148 (15)	0.0051 (13)	0.0148 (15)
C4	0.0457 (15)	0.0516 (17)	0.0411 (14)	0.0053 (13)	0.0041 (12)	0.0180 (13)
C5	0.0423 (15)	0.0620 (19)	0.0402 (14)	0.0003 (13)	0.0032 (12)	0.0199 (14)
C6	0.0504 (18)	0.081 (2)	0.0470 (16)	0.0099 (16)	0.0088 (14)	0.0196 (16)
C7	0.053 (2)	0.107 (3)	0.0500 (18)	0.0045 (19)	0.0137 (15)	0.0134 (19)
C8	0.056 (2)	0.119 (3)	0.0397 (16)	−0.012 (2)	0.0029 (15)	0.025 (2)
C9	0.060 (2)	0.095 (3)	0.0545 (19)	0.0006 (19)	−0.0066 (16)	0.037 (2)
C10	0.0499 (17)	0.073 (2)	0.0492 (16)	0.0066 (15)	0.0039 (13)	0.0259 (16)
C11	0.140 (4)	0.077 (3)	0.071 (2)	−0.007 (3)	0.002 (3)	0.035 (2)
C12	0.078 (2)	0.0510 (19)	0.0567 (19)	0.0079 (17)	−0.0037 (17)	0.0158 (16)
C13	0.085 (3)	0.0482 (19)	0.062 (2)	−0.0004 (18)	−0.0088 (18)	0.0060 (16)
C14	0.0610 (19)	0.0508 (18)	0.0482 (17)	0.0117 (15)	−0.0006 (14)	0.0035 (14)
C15	0.061 (2)	0.064 (2)	0.0430 (16)	0.0170 (16)	−0.0007 (14)	−0.0006 (15)
C16	0.073 (2)	0.088 (3)	0.0516 (19)	−0.003 (2)	0.0066 (17)	0.0086 (19)
C17	0.078 (3)	0.122 (4)	0.059 (2)	0.008 (3)	0.017 (2)	0.024 (2)
C18	0.098 (3)	0.125 (4)	0.045 (2)	0.033 (3)	0.015 (2)	0.006 (2)
C19	0.162 (5)	0.090 (3)	0.048 (2)	0.022 (3)	0.000 (3)	−0.017 (2)
C20	0.138 (4)	0.065 (2)	0.052 (2)	0.007 (2)	0.003 (2)	−0.0041 (18)
C21	0.0456 (17)	0.071 (2)	0.0514 (17)	−0.0038 (15)	−0.0093 (13)	0.0134 (16)

Geometric parameters (Å, º) top

Cu1—O4ⁱ	1.9185 (19)	C7—C8	1.377 (5)
Cu1—O4	1.9256 (18)	C7—H7	0.9300
Cu1—N3	1.979 (2)	C8—C9	1.366 (5)
Cu1—N1	1.992 (2)	C8—H8	0.9300
Cu1—Cu1ⁱ	2.9939 (8)	C9—C10	1.385 (4)
O1—N5	1.239 (3)	C9—H9	0.9300
O2—N5	1.242 (3)	C10—H10	0.9300
O3—N5	1.261 (3)	C11—C12	1.505 (5)
O4—C21	1.412 (3)	C11—H11A	0.9600
O4—Cu1ⁱ	1.9185 (19)	C11—H11B	0.9600
N1—C2	1.326 (4)	C11—H11C	0.9600
N1—N2	1.364 (3)	C12—C13	1.391 (4)
N2—C4	1.344 (3)	C13—C14	1.370 (5)
N2—H2	0.873 (10)	C13—H13	0.9300
N3—C12	1.333 (4)	C14—C15	1.478 (4)
N3—N4	1.363 (3)	C15—C16	1.380 (5)
N4—C14	1.348 (4)	C15—C20	1.388 (5)
N4—H4	0.874 (10)	C16—C17	1.392 (5)
C1—C2	1.501 (4)	C16—H16	0.9300
C1—H1A	0.9600	C17—C18	1.370 (6)
C1—H1B	0.9600	C17—H17	0.9300
C1—H1C	0.9600	C18—C19	1.365 (6)
C2—C3	1.388 (4)	C18—H18	0.9300
C3—C4	1.379 (4)	C19—C20	1.383 (6)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.469 (4)	C20—H20	0.9300
C5—C6	1.387 (4)	C21—H21A	0.9600
C5—C10	1.393 (4)	C21—H21B	0.9600
C6—C7	1.383 (4)	C21—H21C	0.9600
C6—H6	0.9300

O4ⁱ—Cu1—O4	77.69 (8)	C8—C7—H7	119.6
O4ⁱ—Cu1—N3	166.83 (9)	C6—C7—H7	119.6
O4—Cu1—N3	91.96 (9)	C9—C8—C7	119.4 (3)
O4ⁱ—Cu1—N1	91.67 (9)	C9—C8—H8	120.3
O4—Cu1—N1	165.30 (9)	C7—C8—H8	120.3
N3—Cu1—N1	99.88 (10)	C8—C9—C10	120.8 (3)
O4ⁱ—Cu1—Cu1ⁱ	38.93 (5)	C8—C9—H9	119.6
O4—Cu1—Cu1ⁱ	38.76 (5)	C10—C9—H9	119.6
N3—Cu1—Cu1ⁱ	130.23 (7)	C5—C10—C9	120.1 (3)
N1—Cu1—Cu1ⁱ	129.86 (7)	C5—C10—H10	119.9
C21—O4—Cu1ⁱ	124.42 (19)	C9—C10—H10	119.9
C21—O4—Cu1	125.07 (19)	C12—C11—H11A	109.5
Cu1ⁱ—O4—Cu1	102.31 (8)	C12—C11—H11B	109.5
C2—N1—N2	105.4 (2)	H11A—C11—H11B	109.5
C2—N1—Cu1	133.5 (2)	C12—C11—H11C	109.5
N2—N1—Cu1	117.77 (18)	H11A—C11—H11C	109.5
C4—N2—N1	111.9 (2)	H11B—C11—H11C	109.5
C4—N2—H2	133 (2)	N3—C12—C13	109.7 (3)
N1—N2—H2	115 (2)	N3—C12—C11	120.9 (3)
C12—N3—N4	105.7 (2)	C13—C12—C11	129.3 (3)
C12—N3—Cu1	132.4 (2)	C14—C13—C12	107.1 (3)
N4—N3—Cu1	119.6 (2)	C14—C13—H13	126.5
C14—N4—N3	111.5 (3)	C12—C13—H13	126.5
C14—N4—H4	128 (2)	N4—C14—C13	106.0 (3)
N3—N4—H4	119 (2)	N4—C14—C15	123.3 (3)
O1—N5—O2	122.3 (3)	C13—C14—C15	130.7 (3)
O1—N5—O3	119.0 (3)	C16—C15—C20	118.7 (3)
O2—N5—O3	118.6 (3)	C16—C15—C14	123.0 (3)
C2—C1—H1A	109.5	C20—C15—C14	118.3 (3)
C2—C1—H1B	109.5	C15—C16—C17	120.6 (4)
H1A—C1—H1B	109.5	C15—C16—H16	119.7
C2—C1—H1C	109.5	C17—C16—H16	119.7
H1A—C1—H1C	109.5	C18—C17—C16	120.0 (4)
H1B—C1—H1C	109.5	C18—C17—H17	120.0
N1—C2—C3	110.3 (3)	C16—C17—H17	120.0
N1—C2—C1	120.8 (3)	C19—C18—C17	119.5 (4)
C3—C2—C1	128.8 (3)	C19—C18—H18	120.3
C4—C3—C2	106.6 (3)	C17—C18—H18	120.3
C4—C3—H3	126.7	C18—C19—C20	121.3 (4)
C2—C3—H3	126.7	C18—C19—H19	119.4
N2—C4—C3	105.7 (2)	C20—C19—H19	119.4
N2—C4—C5	121.9 (3)	C19—C20—C15	119.8 (4)
C3—C4—C5	132.4 (3)	C19—C20—H20	120.1
C6—C5—C10	118.7 (3)	C15—C20—H20	120.1
C6—C5—C4	120.9 (3)	O4—C21—H21A	109.5
C10—C5—C4	120.4 (3)	O4—C21—H21B	109.5
C7—C6—C5	120.2 (3)	H21A—C21—H21B	109.5
C7—C6—H6	119.9	O4—C21—H21C	109.5
C5—C6—H6	119.9	H21A—C21—H21C	109.5
C8—C7—C6	120.7 (4)	H21B—C21—H21C	109.5

O4ⁱ—Cu1—O4—C21	−149.3 (3)	C2—C3—C4—C5	−178.2 (3)
N3—Cu1—O4—C21	38.9 (2)	N2—C4—C5—C6	−27.0 (4)
N1—Cu1—O4—C21	−104.9 (4)	C3—C4—C5—C6	151.7 (3)
Cu1ⁱ—Cu1—O4—C21	−149.3 (3)	N2—C4—C5—C10	153.5 (3)
O4ⁱ—Cu1—O4—Cu1ⁱ	0.0	C3—C4—C5—C10	−27.7 (5)
N3—Cu1—O4—Cu1ⁱ	−171.78 (10)	C10—C5—C6—C7	−1.5 (5)
N1—Cu1—O4—Cu1ⁱ	44.5 (4)	C4—C5—C6—C7	179.0 (3)
O4ⁱ—Cu1—N1—C2	−104.9 (3)	C5—C6—C7—C8	−0.2 (5)
O4—Cu1—N1—C2	−148.1 (3)	C6—C7—C8—C9	1.7 (5)
N3—Cu1—N1—C2	68.7 (3)	C7—C8—C9—C10	−1.4 (5)
Cu1ⁱ—Cu1—N1—C2	−113.3 (3)	C6—C5—C10—C9	1.8 (5)
O4ⁱ—Cu1—N1—N2	50.9 (2)	C4—C5—C10—C9	−178.7 (3)
O4—Cu1—N1—N2	7.7 (5)	C8—C9—C10—C5	−0.4 (5)
N3—Cu1—N1—N2	−135.5 (2)	N4—N3—C12—C13	0.2 (4)
Cu1ⁱ—Cu1—N1—N2	42.5 (2)	Cu1—N3—C12—C13	162.2 (3)
C2—N1—N2—C4	−0.1 (3)	N4—N3—C12—C11	−177.8 (3)
Cu1—N1—N2—C4	−162.1 (2)	Cu1—N3—C12—C11	−15.7 (5)
O4ⁱ—Cu1—N3—C12	−141.7 (4)	N3—C12—C13—C14	−0.5 (4)
O4—Cu1—N3—C12	−103.9 (3)	C11—C12—C13—C14	177.2 (4)
N1—Cu1—N3—C12	67.3 (3)	N3—N4—C14—C13	−0.6 (4)
Cu1ⁱ—Cu1—N3—C12	−110.6 (3)	N3—N4—C14—C15	179.3 (3)
O4ⁱ—Cu1—N3—N4	18.4 (6)	C12—C13—C14—N4	0.7 (4)
O4—Cu1—N3—N4	56.2 (2)	C12—C13—C14—C15	−179.2 (3)
N1—Cu1—N3—N4	−132.6 (2)	N4—C14—C15—C16	−7.8 (5)
Cu1ⁱ—Cu1—N3—N4	49.4 (3)	C13—C14—C15—C16	172.1 (4)
C12—N3—N4—C14	0.3 (4)	N4—C14—C15—C20	172.8 (3)
Cu1—N3—N4—C14	−164.5 (2)	C13—C14—C15—C20	−7.3 (6)
N2—N1—C2—C3	0.5 (3)	C20—C15—C16—C17	−0.8 (6)
Cu1—N1—C2—C3	158.4 (2)	C14—C15—C16—C17	179.8 (3)
N2—N1—C2—C1	−178.3 (3)	C15—C16—C17—C18	0.5 (6)
Cu1—N1—C2—C1	−20.5 (5)	C16—C17—C18—C19	0.3 (7)
N1—C2—C3—C4	−0.8 (4)	C17—C18—C19—C20	−0.8 (8)
C1—C2—C3—C4	178.0 (3)	C18—C19—C20—C15	0.5 (8)
N1—N2—C4—C3	−0.4 (3)	C16—C15—C20—C19	0.3 (7)
N1—N2—C4—C5	178.6 (3)	C14—C15—C20—C19	179.7 (4)
C2—C3—C4—N2	0.7 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.87 (1)	2.26 (2)	3.012 (3)	144 (3)
N4—H4···O3	0.87 (1)	2.17 (2)	3.022 (4)	166 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu₂(CH₃O)₂(NO₃)₂(C₁₀H₁₀N₂)₄]
M_r	945.97
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.3896 (8), 11.2569 (11), 12.7200 (12)
α, β, γ (°)	106.120 (2), 103.025 (2), 95.853 (2)
V (Å³)	1106.85 (18)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.02
Crystal size (mm)	0.12 × 0.11 × 0.10

Data collection
Diffractometer	Bruker SMART1000
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.887, 0.905
No. of measured, independent and observed [I > 2σ(I)] reflections	6768, 4898, 3461
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.116, 1.02
No. of reflections	4898
No. of parameters	290
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.30

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.87 (1)	2.26 (2)	3.012 (3)	144 (3)
N4—H4···O3	0.87 (1)	2.17 (2)	3.022 (4)	166 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The authors acknowledge support from the Scientific Research Project of Higher Education of Inner Mongolia (grant No. NJ09204) and the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12).

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
He, H. & Sykes, A. G. (2007). Acta Cryst. E63, m2448. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhu, W.-R., Hu, P.-Z. & Li, M.-Y. (2004). Chin. J. Synth. Chem. 12, 28–30. CAS Google Scholar

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Volume 68| Part 4| April 2012| Page m503

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