Bis(acetato-κ2O,O′)bis­(3,5-dimethyl-1H-pyrazole-κN2)copper(II)

Davydenko, Y.M.; Fritsky, I.O.; Pavlenko, V.O.; Meyer, F.; Dechert, S.

doi:10.1107/S1600536809019400

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m691-m692

doi:10.1107/S1600536809019400

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Bis(acetato-κ²O,O′)bis(3,5-dimethyl-1H-pyrazole-κN²)copper(II)

Yuliya M. Davydenko,^a Igor O. Fritsky,^a ^* Vadim O. Pavlenko,^a Franc Meyer ^b and Sebastian Dechert ^b

^aNational Taras Shevchenko University, Department of Chemistry, Volodymyrska Street 64, 01601 Kiev, Ukraine, and ^bInstitut für Anorganische Chemie, Universität Göttingen, Tammannstrasse 4, 37077 Göttingen, Germany
^*Correspondence e-mail: ifritsky@univ.kiev.ua

(Received 22 April 2009; accepted 21 May 2009; online 29 May 2009)

In the title compound, [Cu(C₂H₃O₂)₂(C₅H₈N₂)₂], the Cu^II atom has a distorted tetragonal–bipyramidal geometry, with the equatorial plane formed by two N atoms belonging to two 3,5-dimethyl-1H-pyrazole ligands and two O atoms from two acetate anions. The second O atoms of the acetate groups provide elongated Cu—O axial contacts, so that the acetates appear to be coordinated in a pseudo-chelate fashion. The pyrazole ligands are situated in cis positions with respect to each other. In the crystal structure, molecules are linked through intermolecular N—H⋯O hydrogen bonds, forming a one-dimensional chain.

Related literature

For properties and applications of 1H-pyrazole and its 3,5-substituted derivatives, see: Fritsky et al. (1993 , 1994a ,b ); Halcrow (2001 ); Jain et al. (2004 ); Krämer (1999 ); Krämer et al. (2002 ); Raptis et al. (1999 ); Seredyuk et al. (2007 ); Skopenko et al. (1990 ). For related compounds, see: Barooah et al. (2006 ); Deka et al. (2006 ); Karmakar et al. (2007 ); Porai-Koshits (1980 ); Pradeep et al. (2006 ).

Experimental

Crystal data

[Cu(C₂H₃O₂)₂(C₅H₈N₂)₂]
M_r = 373.90
Triclinic, $[P \overline 1]$
a = 9.2861 (11) Å
b = 10.1684 (12) Å
c = 10.3139 (13) Å
α = 110.755 (9)°
β = 100.901 (10)°
γ = 99.383 (9)°
V = 865.7 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 133 K
0.50 × 0.08 × 0.07 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: numerical (X-RED; Stoe & Cie, 2002 ) T_min = 0.790, T_max = 0.935
7882 measured reflections
3713 independent reflections
3129 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.071
S = 1.02
3713 reflections
222 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	1.9851 (18)
Cu1—N3	1.9925 (16)
Cu1—O1	1.9909 (15)
Cu1—O2	2.4774 (18)
Cu1—O3	2.0045 (14)
Cu1—O4	2.4603 (16)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4ⁱ	0.82 (3)	1.92 (3)	2.726 (3)	166 (3)
N4—H4⋯O2ⁱⁱ	0.87 (3)	1.91 (3)	2.732 (2)	157 (2)
Symmetry codes: (i) -x+1, -y, -z; (ii) -x+1, -y+1, -z+1.

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: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809019400/hy2196sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809019400/hy2196Isup2.hkl

checkCIF report

Comment top

1H-Pyrazole and its 3,5-substituted derivatives have been widely used as bridging ligands in molecular magnetism and supramolecular chemistry because of their marked tendency to form high nuclearity species exhibiting specific magnetic properties (Krämer et al., 2002; Seredyuk et al., 2007). Copper complexes containing pyrazole-based ligands are of particular interest in bioinorganic chemistry, as they can be used as models for the active sites in copper proteins like hemocyanine and tyrosinase (Krämer, 1999; Raptis et al., 1999). In addition, copper carboxylates are important in biology and also in basic inorganic chemistry (Halcrow, 2001; Jain et al., 2004). The carboxylates show a large variety of coordination modes, which can lead to the formation of different assemblies, including supramolecular coordination polymers or metal–organic frameworks (Fritsky et al., 1993, 1994a,b; Skopenko et al., 1990). A large number of copper(II) carboxylates with flexible connection are reported (Barooah et al., 2006; Pradeep et al., 2006). Total use of 1H-pyrazole derivatives and carboxylates can lead to the formation of mononuclear complexes with vacant donor atoms, which can be use as building blocks for the preparation of polynuclear complexes or coordination polymers.

The title compound is a mononuclear complex (Fig. 1), which consists of a Cu^II ion as the central atom possessing a Jahn–Teller distorted tetragonal–bipyramidal environment. The four equatorial positions are occupied by two N atoms belonging to two monodentately coordinated 3,5-dimethyl-1H-pyrazole molecules [Cu—N = 1.9851 (18) and 1.9925 (16) Å] and two O atoms from the acetate anions [Cu—O = 1.9909 (15) and 2.0045 (14) Å]. The other two O atoms of the acetate anions occupy the axial positions [Cu—O = 2.4603 (16) and 2.4774 (18) Å] (Table 1). Each sort of ligands (3,5-dimethyl-1H-pyrazole and carboxylate) in the coordination sphere of central Cu^II is cis-oriented with respect to each other. According to the carboxylate coordination criteria (Poray-Coshits, 1980), the acetate anions of the title compound coordinate in a pseudo-chelate mode, forming a four-membered chelate ring. The specific chelation of the above mentioned acetate anions, when one of the two bonds always resides in the equatorial position and second bond occupies the axial position of tetragonal–bipyramidal environment, was found in many Cu^II compounds (Deka et al., 2006; Karmakar et al., 2007). The Cu—O equatorial distances varying in the range of 1.970 and 1.974 Å are somewhat shorter than those in the title compound. The axial Cu—O bond lengths in the title compound are less than 2.685 Å (Karmakar et al., 2007), but longer than 2.281 Å reported by Deka et al. (2006). In addition, asymmetric chelation of the acetate anions shows up in inequivalence of the two C—O bonds. Thus, C—O distances adjacent to the elongated axial Cu—O bonds [C13—O4 = 1.250 (3) and C11—O2 = 1.256 (2) Å] are a bit shorter than those in the equatorial plane [C13—O3 = 1.262 (3) and C11—O1 = 1.266 (3) Å]. The values of the angles around the central atom deviate from ideal tetragonal–bipyramidal geometry.

In the crystal packing (Fig. 2), the complex molecules are connected through intermolecular N—H···O hydrogen bonds into a one-dimensional linear chain. The hydrogen bonds in the structure are of two types, with distances N2···O4 = 2.726 (3) and N4···O2 = 2.732 (2)Å (Table 2). Each couple of hydrogen bonds of one type takes part in forming the different ten-membered cycles. Due to this crystal packing, the shortest intra-chain Cu···Cu separations are 6.018 and 6.123 Å.

Related literature top

For properties and applications of 1H-pyrazole and its 3,5-substituted derivatives, see: Fritsky et al. (1993, 1994a,b); Halcrow (2001); Jain et al. (2004); Krämer (1999); Krämer et al. (2002); Raptis et al. (1999); Seredyuk et al. (2007); Skopenko et al. (1990). For related compounds, see: Barooah et al. (2006); Deka et al. (2006); Karmakar et al. (2007); Poray-Coshits (1980); Pradeep et al. (2006).

Experimental top

The title complex was synthesized by a direct method at free access of air oxygen. The mixture of 3,5-dimethyl-1H-pyrazole (0.96 g, 0.01 mol), ammonium acetate (0.77 g, 0.01 mol) in dimethylsulfoxide solution (15 ml) was stirred with copper powder (0.64 g, 0.01 mol) at ambient temperature until dissolved. The resulting dark-green solution was filtered and the filtrate was left to stand at room temperature for crystallization in air. Slow evaporation yielded green crystals of the title complex suitable for X-ray analysis in 5 d.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); 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: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. The dashed grey lines represent the elongated axial Cu—O bonds.
	Fig. 2. A crystal packing diagram of the title compound, showing the intermolecular hydrogen bonds as underlined dotted and shaded grey lines, which link the molecules into a one-dimensional chain. The dashed black lines represent the axial Cu—O bonds. [Symmetry codes: (i) 1 - x, -y, -z; (ii) 1 - x, 1 - y, 1 - z.]

Bis(acetato-κ²O,O')bis(3,5-dimethyl-1H-pyrazole- κN²)copper(II) top

Crystal data top

[Cu(C₂H₃O₂)₂(C₅H₈N₂)₂]	Z = 2
M_r = 373.90	F(000) = 390
Triclinic, P1	D_x = 1.434 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.2861 (11) Å	Cell parameters from 7882 reflections
b = 10.1684 (12) Å	θ = 2.2–27.1°
c = 10.3139 (13) Å	µ = 1.29 mm⁻¹
α = 110.755 (9)°	T = 133 K
β = 100.901 (10)°	Needle, blue
γ = 99.383 (9)°	0.50 × 0.08 × 0.07 mm
V = 865.7 (2) Å³

Data collection top

Stoe IPDSII diffractometer	3713 independent reflections
Radiation source: fine-focus sealed tube	3129 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 27.1°, θ_min = 2.2°
Absorption correction: numerical (X-RED; Stoe & Cie, 2002)	h = −11→11
T_min = 0.790, T_max = 0.935	k = −12→12
7882 measured reflections	l = −13→13

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0405P)²] where P = (F_o² + 2F_c²)/3
3713 reflections	(Δ/σ)_max < 0.001
222 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Cu(C₂H₃O₂)₂(C₅H₈N₂)₂]	γ = 99.383 (9)°
M_r = 373.90	V = 865.7 (2) Å³
Triclinic, P1	Z = 2
a = 9.2861 (11) Å	Mo Kα radiation
b = 10.1684 (12) Å	µ = 1.29 mm⁻¹
c = 10.3139 (13) Å	T = 133 K
α = 110.755 (9)°	0.50 × 0.08 × 0.07 mm
β = 100.901 (10)°

Data collection top

Stoe IPDSII diffractometer	3713 independent reflections
Absorption correction: numerical (X-RED; Stoe & Cie, 2002)	3129 reflections with I > 2σ(I)
T_min = 0.790, T_max = 0.935	R_int = 0.029
7882 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.29 e Å⁻³
3713 reflections	Δρ_min = −0.66 e Å⁻³
222 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.59542 (3)	0.26364 (3)	0.28774 (3)	0.01892 (8)
N1	0.46111 (18)	0.31000 (19)	0.1448 (2)	0.0219 (4)
N2	0.35711 (19)	0.2059 (2)	0.0274 (2)	0.0236 (4)
N3	0.41420 (18)	0.17191 (19)	0.3311 (2)	0.0206 (4)
N4	0.30556 (18)	0.2416 (2)	0.3681 (2)	0.0208 (4)
O1	0.73397 (15)	0.25272 (16)	0.45427 (17)	0.0241 (3)
O2	0.69120 (17)	0.47040 (17)	0.52556 (18)	0.0290 (3)
O3	0.77354 (16)	0.32001 (17)	0.21787 (18)	0.0274 (3)
O4	0.67255 (17)	0.08587 (17)	0.09809 (18)	0.0313 (4)
C1	0.4435 (2)	0.4379 (2)	0.1444 (2)	0.0236 (4)
C2	0.3264 (2)	0.4129 (3)	0.0235 (3)	0.0281 (5)
H2A	0.2906	0.4827	−0.0025	0.080*
C3	0.2751 (2)	0.2644 (3)	−0.0486 (2)	0.0264 (5)
C4	0.5404 (3)	0.5761 (2)	0.2603 (3)	0.0295 (5)
H4A	0.4975	0.6013	0.3409	0.080*
H4B	0.5460	0.6519	0.2251	0.080*
H4C	0.6402	0.5645	0.2900	0.080*
C5	0.1575 (3)	0.1717 (3)	−0.1863 (3)	0.0361 (6)
H5A	0.2058	0.1261	−0.2587	0.080*
H5B	0.1002	0.2310	−0.2170	0.080*
H5C	0.0909	0.0986	−0.1719	0.080*
C6	0.3738 (2)	0.0426 (2)	0.3370 (2)	0.0223 (4)
C7	0.2394 (2)	0.0308 (2)	0.3797 (3)	0.0260 (5)
H7	0.1875	−0.0481	0.3924	0.080*
C8	0.1996 (2)	0.1597 (2)	0.3991 (2)	0.0226 (4)
C9	0.4646 (3)	−0.0668 (3)	0.2981 (3)	0.0331 (5)
H9A	0.4376	−0.1180	0.1954	0.080*
H9B	0.4442	−0.1345	0.3417	0.080*
H9C	0.5705	−0.0183	0.3320	0.080*
C10	0.0700 (2)	0.2149 (3)	0.4456 (3)	0.0317 (5)
H10A	0.1082	0.3080	0.5246	0.080*
H10B	0.0138	0.1479	0.4753	0.080*
H10C	0.0049	0.2240	0.3668	0.080*
C11	0.7570 (2)	0.3795 (2)	0.5494 (2)	0.0232 (4)
C12	0.8678 (3)	0.4198 (3)	0.6921 (3)	0.0344 (5)
H12A	0.9637	0.4742	0.6944	0.080*
H12B	0.8803	0.3331	0.7054	0.080*
H12C	0.8303	0.4777	0.7678	0.080*
C13	0.7706 (2)	0.1986 (3)	0.1243 (2)	0.0268 (5)
C14	0.8912 (3)	0.1923 (3)	0.0435 (3)	0.0450 (7)
H14A	0.9847	0.1944	0.1038	0.080*
H14B	0.9053	0.2743	0.0174	0.080*
H14C	0.8601	0.1042	−0.0418	0.080*
H4	0.319 (3)	0.334 (3)	0.384 (3)	0.023 (6)*
H2	0.351 (3)	0.118 (3)	0.003 (3)	0.027 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01590 (12)	0.01845 (13)	0.02150 (14)	0.00555 (9)	0.00670 (9)	0.00546 (10)
N1	0.0212 (8)	0.0212 (9)	0.0221 (10)	0.0048 (7)	0.0071 (7)	0.0068 (8)
N2	0.0227 (8)	0.0215 (10)	0.0224 (10)	0.0043 (7)	0.0060 (7)	0.0047 (8)
N3	0.0179 (7)	0.0201 (9)	0.0239 (10)	0.0087 (7)	0.0071 (7)	0.0064 (8)
N4	0.0182 (8)	0.0218 (9)	0.0241 (10)	0.0090 (7)	0.0086 (7)	0.0078 (8)
O1	0.0202 (7)	0.0217 (8)	0.0275 (9)	0.0083 (6)	0.0053 (6)	0.0057 (7)
O2	0.0331 (8)	0.0240 (8)	0.0318 (9)	0.0132 (7)	0.0121 (7)	0.0088 (7)
O3	0.0225 (7)	0.0264 (8)	0.0282 (9)	0.0029 (6)	0.0101 (6)	0.0046 (7)
O4	0.0274 (8)	0.0259 (8)	0.0331 (10)	0.0053 (7)	0.0110 (7)	0.0024 (7)
C1	0.0259 (10)	0.0257 (11)	0.0233 (12)	0.0093 (8)	0.0126 (9)	0.0102 (10)
C2	0.0303 (11)	0.0317 (12)	0.0293 (13)	0.0140 (9)	0.0125 (10)	0.0151 (11)
C3	0.0215 (9)	0.0365 (13)	0.0242 (12)	0.0094 (9)	0.0096 (9)	0.0126 (10)
C4	0.0364 (11)	0.0227 (11)	0.0294 (13)	0.0073 (9)	0.0106 (10)	0.0097 (10)
C5	0.0264 (11)	0.0475 (15)	0.0279 (13)	0.0065 (10)	0.0030 (10)	0.0109 (12)
C6	0.0225 (9)	0.0204 (10)	0.0233 (11)	0.0077 (8)	0.0063 (8)	0.0069 (9)
C7	0.0208 (9)	0.0273 (11)	0.0302 (12)	0.0035 (8)	0.0076 (9)	0.0123 (10)
C8	0.0175 (9)	0.0267 (11)	0.0214 (11)	0.0057 (8)	0.0054 (8)	0.0069 (9)
C9	0.0336 (11)	0.0251 (12)	0.0473 (16)	0.0153 (10)	0.0167 (11)	0.0155 (11)
C10	0.0225 (10)	0.0410 (14)	0.0336 (13)	0.0129 (10)	0.0137 (10)	0.0118 (12)
C11	0.0185 (9)	0.0244 (11)	0.0256 (12)	0.0059 (8)	0.0086 (8)	0.0073 (9)
C12	0.0298 (11)	0.0380 (14)	0.0276 (13)	0.0105 (10)	0.0049 (10)	0.0048 (11)
C13	0.0203 (9)	0.0308 (12)	0.0238 (12)	0.0061 (9)	0.0048 (9)	0.0053 (10)
C14	0.0316 (12)	0.0565 (18)	0.0360 (15)	0.0053 (12)	0.0197 (11)	0.0029 (14)

Geometric parameters (Å, º) top

Cu1—N1	1.9851 (18)	C4—H4B	0.9600
Cu1—N3	1.9925 (16)	C4—H4C	0.9600
Cu1—O1	1.9909 (15)	C5—H5A	0.9600
Cu1—O2	2.4774 (18)	C5—H5B	0.9600
Cu1—O3	2.0045 (14)	C5—H5C	0.9600
Cu1—O4	2.4603 (16)	C6—C7	1.402 (3)
N1—C1	1.338 (3)	C6—C9	1.492 (3)
N1—N2	1.355 (3)	C7—C8	1.377 (3)
N2—C3	1.342 (3)	C7—H7	0.9300
N2—H2	0.82 (3)	C8—C10	1.497 (3)
N3—C6	1.333 (3)	C9—H9A	0.9600
N3—N4	1.361 (2)	C9—H9B	0.9600
N4—C8	1.343 (3)	C9—H9C	0.9600
N4—H4	0.87 (3)	C10—H10A	0.9600
O1—C11	1.266 (3)	C10—H10B	0.9600
O2—C11	1.256 (2)	C10—H10C	0.9600
O3—C13	1.262 (3)	C11—C12	1.502 (3)
O4—C13	1.250 (3)	C12—H12A	0.9600
C1—C2	1.405 (3)	C12—H12B	0.9600
C1—C4	1.485 (3)	C12—H12C	0.9600
C2—C3	1.377 (3)	C13—C14	1.513 (3)
C2—H2A	0.9300	C14—H14A	0.9600
C3—C5	1.492 (3)	C14—H14B	0.9600
C4—H4A	0.9600	C14—H14C	0.9600

N1—Cu1—O1	170.00 (7)	C3—C5—H5A	109.5
N1—Cu1—N3	89.80 (7)	C3—C5—H5B	109.5
O1—Cu1—N3	91.52 (7)	H5A—C5—H5B	109.5
N1—Cu1—O3	90.43 (7)	C3—C5—H5C	109.5
O1—Cu1—O3	90.04 (6)	H5A—C5—H5C	109.5
N3—Cu1—O3	169.70 (7)	H5B—C5—H5C	109.5
N1—Cu1—O4	91.91 (7)	N3—C6—C7	109.75 (17)
O1—Cu1—O4	96.79 (6)	N3—C6—C9	121.28 (18)
N3—Cu1—O4	111.84 (6)	C7—C6—C9	128.9 (2)
O3—Cu1—O4	57.86 (6)	C8—C7—C6	106.03 (18)
N1—Cu1—O2	112.23 (6)	C8—C7—H7	127.0
O1—Cu1—O2	57.78 (6)	C6—C7—H7	127.0
N3—Cu1—O2	95.42 (7)	N4—C8—C7	106.80 (17)
O3—Cu1—O2	94.03 (6)	N4—C8—C10	121.04 (19)
O4—Cu1—O2	143.81 (5)	C7—C8—C10	132.2 (2)
C1—N1—N2	106.62 (17)	C6—C9—H9A	109.5
C1—N1—Cu1	130.74 (16)	C6—C9—H9B	109.5
N2—N1—Cu1	122.49 (13)	H9A—C9—H9B	109.5
C3—N2—N1	111.34 (19)	C6—C9—H9C	109.5
C3—N2—H2	125.2 (19)	H9A—C9—H9C	109.5
N1—N2—H2	123.2 (18)	H9B—C9—H9C	109.5
C6—N3—N4	106.06 (15)	C8—C10—H10A	109.5
C6—N3—Cu1	131.10 (13)	C8—C10—H10B	109.5
N4—N3—Cu1	122.80 (13)	H10A—C10—H10B	109.5
C8—N4—N3	111.35 (17)	C8—C10—H10C	109.5
C8—N4—H4	127.8 (15)	H10A—C10—H10C	109.5
N3—N4—H4	119.9 (15)	H10B—C10—H10C	109.5
C11—O1—Cu1	101.34 (13)	O2—C11—O1	121.5 (2)
C11—O2—Cu1	79.30 (13)	O2—C11—C12	120.4 (2)
C13—O3—Cu1	100.41 (13)	O1—C11—C12	118.11 (19)
C13—O4—Cu1	79.78 (13)	C11—C12—H12A	109.5
N1—C1—C2	109.0 (2)	C11—C12—H12B	109.5
N1—C1—C4	120.58 (19)	H12A—C12—H12B	109.5
C2—C1—C4	130.46 (19)	C11—C12—H12C	109.5
C3—C2—C1	106.30 (19)	H12A—C12—H12C	109.5
C3—C2—H2A	126.8	H12B—C12—H12C	109.5
C1—C2—H2A	126.8	O4—C13—O3	121.95 (19)
N2—C3—C2	106.8 (2)	O4—C13—C14	120.2 (2)
N2—C3—C5	121.5 (2)	O3—C13—C14	117.8 (2)
C2—C3—C5	131.7 (2)	C13—C14—H14A	109.5
C1—C4—H4A	109.5	C13—C14—H14B	109.5
C1—C4—H4B	109.5	H14A—C14—H14B	109.5
H4A—C4—H4B	109.5	C13—C14—H14C	109.5
C1—C4—H4C	109.5	H14A—C14—H14C	109.5
H4A—C4—H4C	109.5	H14B—C14—H14C	109.5
H4B—C4—H4C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.82 (3)	1.92 (3)	2.726 (3)	166 (3)
N4—H4···O2ⁱⁱ	0.87 (3)	1.91 (3)	2.732 (2)	157 (2)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₂H₃O₂)₂(C₅H₈N₂)₂]
M_r	373.90
Crystal system, space group	Triclinic, P1
Temperature (K)	133
a, b, c (Å)	9.2861 (11), 10.1684 (12), 10.3139 (13)
α, β, γ (°)	110.755 (9), 100.901 (10), 99.383 (9)
V (Å³)	865.7 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.50 × 0.08 × 0.07

Data collection
Diffractometer	Stoe IPDSII diffractometer
Absorption correction	Numerical (X-RED; Stoe & Cie, 2002)
T_min, T_max	0.790, 0.935
No. of measured, independent and observed [I > 2σ(I)] reflections	7882, 3713, 3129
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.641

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.071, 1.02
No. of reflections	3713
No. of parameters	222
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.66

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Selected bond lengths (Å) top

Cu1—N1	1.9851 (18)	Cu1—O2	2.4774 (18)
Cu1—N3	1.9925 (16)	Cu1—O3	2.0045 (14)
Cu1—O1	1.9909 (15)	Cu1—O4	2.4603 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4ⁱ	0.82 (3)	1.92 (3)	2.726 (3)	166 (3)
N4—H4···O2ⁱⁱ	0.87 (3)	1.91 (3)	2.732 (2)	157 (2)

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

Acknowledgements

The authors thank the Ministry of Education and Science of Ukraine for financial support (grant No. M/42-2008).

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