Tetra-μ-acetato-κ8O:O′-bis­[(3,5-di­methyl-1H-pyrazole-κN2)­copper(II)]

Wyk, J. van; Omondi, B.; Darkwa, J.

doi:10.1107/S1600536811032600

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page m1299

doi:10.1107/S1600536811032600

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Tetra-μ-acetato-κ⁸O:O′-bis[(3,5-dimethyl-1H-pyrazole-κN²)copper(II)]

Juanita van Wyk,^a Bernard Omondi ^b ^* and James Darkwa ^a

^aDepartment of Chemistry, University of Johannesburg, PO Box 524 Auckland Park, Johannesburg, 2006, South Africa, and ^bSchool of Chemistry, University of KwaZulu-Natal, Westville Campus, Private Bag X54001, Durban 4000, South Africa
^*Correspondence e-mail: owaga@ukzn.ac.za

(Received 5 August 2011; accepted 11 August 2011; online 27 August 2011)

The dinuclear centrosymmetric title compound, [Cu₂(CH₃CO₂)₄(C₅H₈N₂)₂], has a distorted square-pyramidal coordination geometry around each Cu^II atom in which four O atoms from the bridging acetate ligands form the basal plane while two N atoms from the pyrazole ligands occupy the apical positions. The crystal has two half molecules in the asymmetric unit with a Cu⋯Cu distance of 2.6762 (4) Å. Disorder was found for two O atoms and two C atoms of one acetate ligand and refined with occupancies of 0.265 (7) and 0.735 (7). The crystal also features molecules linked through two N—H⋯O hydrogen bonds resulting in one-dimensional chains extending along the crystallographic b axis.

Related literature

For the properties and applications of 1H-pyrazolyl-3,5-substituted ligands, see: Deka et al. (2006 ); Guzei et al. (2003 ); Mohlala et al. (2005 ); Nelana et al. (2008 ); Ojwach et al. (2005 ).

Experimental

Crystal data

[Cu₂(C₂H₃O₂)₄(C₅H₈N₂)₂]
M_r = 555.52
Triclinic, $[P \overline 1]$
a = 8.1125 (4) Å
b = 13.6429 (7) Å
c = 13.7755 (7) Å
α = 61.571 (1)°
β = 87.449 (1)°
γ = 82.354 (1)°
V = 1328.55 (12) Å³
Z = 2
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 100 K
0.39 × 0.16 × 0.10 mm

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.566, T_max = 0.853
17190 measured reflections
6578 independent reflections
5934 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.089
S = 1.06
6578 reflections
310 parameters
17 restraints
H-atom parameters constrained
Δρ_max = 1.28 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O5	0.88	1.93	2.785 (2)	163
N3—H3⋯O3	0.88	2	2.847 (2)	163

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus and XPREP (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ), ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811032600/hg5077sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811032600/hg5077Isup2.hkl

checkCIF report

Comment top

Pyrazolyl ligands containing a carbonyl linker has been utilized to prepare a number of coordination compounds with palladium salts (Guzei et al., 2003; Mohlala et al., 2005, Ojwach et al., 2005). In these compounds the pyrazolyl carbonyl moiety appear to be robust enough to avoid hydrolysis. However in a few instances the presence of metal ions like Cu(II) (Deka et al., 2006) and Pd(II) (Nelana et al., 2008) appear to catalyze the hydrolysis of the benzoyl fragments. We have observed similar hydrolysis when reacting copper(II) acetate with (3,5-dimethyl-pyrazol-1-yl)-o-benzoyl-methane. The title compound formed from this reaction is the subject of this report. The half "solvent" molecule excluded from the structure had a total number of 30.7 electrons which is approximately half the total number of electrons that acetophenone has.

Compound (I) crystallizes with two half molecules in the assymetric unit. The compound is dinuclear with each of the Cu atoms coordinated to four O atoms and a N atom from the pyrazole ligand. The O atoms are from acetate ions, all in the equatorial positions of a slightly distorted octahedral geometry around the Cu atoms. The N atom is bound trans to the Cu—Cu vector completing a the distorted octahedral geometry as axial ligands.

The crystal structure of (I) is composed of two N—H···O hydrogen bonded chains (Table 1) that extend in the crystallographic b axis (Fig. 2).

Related literature top

For related literature [on what subject?], see: Deka et al. (2006); Guzei et al. (2003); Mohlala et al. (2005); Nelana et al. (2008); Ojwach et al. (2005).

Experimental top

A mixture of copper(II) acetate monohydrate (0.20 g, 1 mmol) and (3,5-dimethy-pyrazol-1-yl)-o-benzyl-methane (0.20 g, 1 mmol) was refluxed in methanol (20 ml) for 4 h. The bluish-green mixture turned deep green during the course of the reaction and upon removal of the solvent a green solid residue was obtained. Recrystallization from a methanol:ethylacetate (1:2) mixture produced X-ray quality crystals after several days. Yield = 0.36 g, 59%

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus and XPREP (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009); molecular graphics: DIAMOND (Brandenburg & Putz, 2005), ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. View of (I) (50% probability displacement ellipsoids) with H atoms presented as small spheres of arbitrary radii.
	Fig. 2. N—H···O hydrogen bond interactions in the crystal structure of (I). [Symmetry operators: (i) = 1 - x, 1 - y, 1 - z and (ii) = 1 - x, -y, 1 - z]

Tetra-µ-acetato-κ⁸O:O'-bis[(3,5- dimethyl-1H-pyrazole-κN²)copper(II) top

Crystal data top

[Cu₂(C₂H₃O₂)₄(C₅H₈N₂)₂]	Z = 2
M_r = 555.52	F(000) = 572
Triclinic, P1	D_x = 1.389 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1125 (4) Å	Cell parameters from 17682 reflections
b = 13.6429 (7) Å	θ = 2.5–28.4°
c = 13.7755 (7) Å	µ = 1.64 mm⁻¹
α = 61.571 (1)°	T = 100 K
β = 87.449 (1)°	Block, green
γ = 82.354 (1)°	0.39 × 0.16 × 0.1 mm
V = 1328.55 (12) Å³

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	5934 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −10→10
T_min = 0.566, T_max = 0.853	k = −18→17
17190 measured reflections	l = −18→18
6578 independent 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.089	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0503P)² + 0.7634P] where P = (F_o² + 2F_c²)/3
6578 reflections	(Δ/σ)_max = 0.012
310 parameters	Δρ_max = 1.28 e Å⁻³
17 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Cu₂(C₂H₃O₂)₄(C₅H₈N₂)₂]	γ = 82.354 (1)°
M_r = 555.52	V = 1328.55 (12) Å³
Triclinic, P1	Z = 2
a = 8.1125 (4) Å	Mo Kα radiation
b = 13.6429 (7) Å	µ = 1.64 mm⁻¹
c = 13.7755 (7) Å	T = 100 K
α = 61.571 (1)°	0.39 × 0.16 × 0.1 mm
β = 87.449 (1)°

Data collection top

Bruker X8 APEXII 4K Kappa CCD diffractometer	6578 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	5934 reflections with I > 2σ(I)
T_min = 0.566, T_max = 0.853	R_int = 0.022
17190 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	17 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.06	Δρ_max = 1.28 e Å⁻³
6578 reflections	Δρ_min = −0.59 e Å⁻³
310 parameters

Special details top

Experimental. Diorder: Disorder was found for two O atoms and two C atoms of one acetate ligand in which is not an uncommon situation. The disorder was modelled for two O–, two C– and H-atoms using distance restraints and PART instructions and the total occupancy at each atom site was kept as 1 during the refinement. DELU and SIMU constraints and restraints were used on the disordered atoms. All carbon atoms involved in disorder were modelled with anisotropic thermal parameters and refined with occupancies of 0.265 (7) and 0.735 (7). The "solvent" molecule resided in a special position and looked disordered as well. Modelling the disorder only distabillized the refinement. As a result, the moleculed was removed using the SQUEEZE subroutine in PLATON giving an R factor of 3.0%. H-atom Placement: All H-atoms were placed in idealized locations and refined as riding with appropriate thermal displacement coefficients U_iso(H) = 1.2 or 1.5 times U_eq(bearing atom).

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.

The following ALERTS were generated. Each ALERT has the format test-name_ALERT_alert-type_alert-level.

PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ···. 2.18

The solvent molecule was excluded. The remaining electron density peaks are very close to other atoms and make no chemical sense. PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) ···.. 3 PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L= 0.600 33 PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L= 0.600 39 PLAT913_ALERT_3_C Missing # of Very Strong Reflections in FCF ···. 1 PLAT002_ALERT_2_G Number of Distance or Angle Restraints on AtSite 10 PLAT003_ALERT_2_G Number of U_iso or U^ij Restrained Atom Sites ···. 4 PLAT154_ALERT_1_G The su's on the Cell Angles are Equal ·········. 0.00100 Deg.

These are noted PLAT301_ALERT_3_G Note: Main Residue Disorder ··················. 13 Perc.

See disorder explanation above. PLAT380_ALERT_4_G Check Incorrectly? Oriented X(sp2)-Methyl Moiety C18 PLAT605_ALERT_4_G Structure Contains Solvent Accessible VOIDS of. 199 A**3 PLAT869_ALERT_4_G ALERTS Related to the use of SQUEEZE Suppressed ! Solvent molecule was excluded as it was grossly disordered. PLAT764_ALERT_4_G Overcomplete CIF Bond List Detected (Rep/Expd). 1.17 Ratio PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ······. 17 PLAT961_ALERT_5_G Dataset Contains no Negative Intensities ······. ! Noted.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.53478 (2)	0.494657 (16)	0.406632 (17)	0.01851 (7)
O1	0.40264 (18)	0.64415 (11)	0.33807 (11)	0.0291 (3)
O2	0.34793 (16)	0.65464 (11)	0.49368 (11)	0.0270 (3)
C1	0.3431 (2)	0.69462 (15)	0.39072 (16)	0.0237 (3)
C2	0.2597 (3)	0.81398 (16)	0.32348 (18)	0.0329 (4)
H2A	0.1426	0.8186	0.3437	0.049*
H2B	0.2666	0.8358	0.2447	0.049*
H2C	0.3159	0.8648	0.3385	0.049*
O3	0.32633 (15)	0.42403 (12)	0.43652 (12)	0.0264 (3)
O4	0.26852 (16)	0.43494 (12)	0.59184 (11)	0.0272 (3)
N1	0.59519 (19)	0.48564 (13)	0.25736 (13)	0.0227 (3)
N2	0.61058 (18)	0.38656 (13)	0.25468 (13)	0.0225 (3)
H2	0.602	0.3213	0.3131	0.027*
C3	0.2366 (2)	0.40998 (14)	0.51864 (16)	0.0226 (3)
C4	0.0775 (2)	0.35986 (17)	0.52824 (19)	0.0308 (4)
H4A	0.0222	0.3494	0.5966	0.046*
H4B	0.1034	0.2871	0.5294	0.046*
H4C	0.0036	0.4106	0.4649	0.046*
C5	0.6131 (3)	0.68424 (17)	0.12252 (19)	0.0398 (5)
H5A	0.5011	0.7136	0.134	0.06*
H5B	0.6415	0.7267	0.0447	0.06*
H5C	0.6935	0.692	0.1687	0.06*
C6	0.6178 (2)	0.56309 (16)	0.15334 (16)	0.0269 (4)
C7	0.6457 (3)	0.51248 (17)	0.08502 (16)	0.0303 (4)
H7	0.6644	0.5488	0.0079	0.036*
C8	0.6403 (2)	0.39916 (17)	0.15302 (16)	0.0272 (4)
C9	0.6625 (3)	0.30197 (19)	0.12979 (19)	0.0363 (5)
H9A	0.7677	0.2549	0.1634	0.055*
H9B	0.6644	0.3298	0.0498	0.055*
H9C	0.5701	0.2574	0.1609	0.055*
Cu2	0.40853 (2)	0.091442 (18)	0.42346 (2)	0.02307 (7)
O7A	0.338 (2)	0.1009 (10)	0.5625 (7)	0.0308 (6)	0.265 (7)
O8A	0.500 (3)	−0.0504 (12)	0.6844 (12)	0.0307 (7)	0.265 (7)
C12A	0.390 (2)	0.0326 (10)	0.6618 (7)	0.0265 (7)	0.265 (7)
C13A	0.3283 (13)	0.0421 (10)	0.7642 (8)	0.0357 (8)	0.265 (7)
H13A	0.4128	0.0705	0.7894	0.054*	0.265 (7)
H13B	0.308	−0.0321	0.8231	0.054*	0.265 (7)
H13C	0.2247	0.094	0.7457	0.054*	0.265 (7)
O7	0.3327 (7)	0.1281 (3)	0.5399 (3)	0.0308 (6)	0.735 (7)
O8	0.4827 (8)	−0.0262 (4)	0.6696 (4)	0.0307 (7)	0.735 (7)
C12	0.3826 (6)	0.0633 (3)	0.6357 (3)	0.0265 (7)	0.735 (7)
C13	0.3140 (4)	0.0927 (3)	0.7245 (3)	0.0357 (8)	0.735 (7)
H13D	0.3479	0.1646	0.7103	0.054*	0.735 (7)
H13E	0.3576	0.0338	0.797	0.054*	0.735 (7)
H13F	0.1923	0.0988	0.7234	0.054*	0.735 (7)
O5	0.61101 (16)	0.16201 (11)	0.41197 (12)	0.0290 (3)
O6	0.76410 (15)	0.00869 (11)	0.53847 (12)	0.0264 (3)
N3	0.23162 (18)	0.33734 (13)	0.29863 (14)	0.0241 (3)
H3	0.2743	0.3505	0.3483	0.029*
N4	0.26197 (18)	0.23761 (13)	0.29750 (14)	0.0248 (3)
C10	0.7459 (2)	0.10916 (14)	0.46471 (16)	0.0217 (3)
C11	0.8953 (2)	0.17237 (16)	0.43519 (18)	0.0283 (4)
H11A	0.9293	0.1893	0.3602	0.042*
H11B	0.9871	0.1262	0.4874	0.042*
H11C	0.8665	0.2427	0.4387	0.042*
C14	0.0769 (3)	0.52926 (18)	0.2005 (2)	0.0438 (5)
H14A	−0.0194	0.5283	0.2464	0.066*
H14B	0.0469	0.5806	0.1228	0.066*
H14C	0.1688	0.5548	0.2226	0.066*
C15	0.1293 (2)	0.41377 (17)	0.21551 (17)	0.0295 (4)
C16	0.0898 (3)	0.36072 (18)	0.15710 (17)	0.0325 (4)
H16	0.0191	0.3919	0.0935	0.039*
C17	0.1746 (2)	0.25240 (17)	0.21025 (17)	0.0291 (4)
C18	0.1723 (3)	0.1581 (2)	0.1831 (2)	0.0442 (5)
H18A	0.2449	0.0919	0.2356	0.066*
H18B	0.2121	0.1813	0.108	0.066*
H18C	0.0585	0.1397	0.1881	0.066*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01382 (10)	0.01959 (11)	0.02424 (11)	−0.00497 (7)	−0.00013 (7)	−0.01135 (9)
O1	0.0309 (7)	0.0250 (6)	0.0293 (7)	0.0015 (5)	−0.0050 (5)	−0.0119 (6)
O2	0.0234 (6)	0.0237 (6)	0.0323 (7)	0.0002 (5)	0.0000 (5)	−0.0127 (5)
C1	0.0167 (7)	0.0199 (8)	0.0342 (9)	−0.0051 (6)	−0.0024 (7)	−0.0115 (7)
C2	0.0340 (10)	0.0204 (8)	0.0389 (11)	0.0002 (7)	−0.0056 (8)	−0.0102 (8)
O3	0.0175 (6)	0.0336 (7)	0.0382 (7)	−0.0098 (5)	0.0029 (5)	−0.0238 (6)
O4	0.0212 (6)	0.0345 (7)	0.0314 (7)	−0.0143 (5)	0.0032 (5)	−0.0176 (6)
N1	0.0203 (7)	0.0227 (7)	0.0261 (7)	−0.0055 (5)	0.0016 (5)	−0.0118 (6)
N2	0.0194 (7)	0.0231 (7)	0.0270 (7)	−0.0055 (5)	0.0019 (6)	−0.0129 (6)
C3	0.0142 (7)	0.0206 (8)	0.0342 (9)	−0.0043 (6)	−0.0016 (6)	−0.0132 (7)
C4	0.0189 (8)	0.0351 (10)	0.0491 (12)	−0.0132 (7)	0.0053 (8)	−0.0267 (9)
C5	0.0529 (13)	0.0254 (10)	0.0361 (11)	−0.0120 (9)	0.0088 (10)	−0.0095 (8)
C6	0.0270 (9)	0.0265 (9)	0.0261 (9)	−0.0064 (7)	0.0011 (7)	−0.0108 (7)
C7	0.0313 (10)	0.0348 (10)	0.0241 (9)	−0.0050 (8)	0.0017 (7)	−0.0133 (8)
C8	0.0221 (8)	0.0339 (10)	0.0296 (9)	−0.0051 (7)	0.0004 (7)	−0.0178 (8)
C9	0.0376 (11)	0.0404 (11)	0.0410 (11)	−0.0042 (9)	0.0013 (9)	−0.0276 (10)
Cu2	0.01346 (11)	0.02278 (12)	0.03971 (14)	−0.00579 (8)	0.00376 (9)	−0.01966 (10)
O7A	0.0260 (8)	0.0252 (19)	0.0478 (14)	0.0024 (16)	0.0025 (14)	−0.0243 (13)
O8A	0.0267 (17)	0.029 (2)	0.0418 (16)	−0.0021 (15)	0.0072 (12)	−0.0219 (16)
C12A	0.0203 (10)	0.028 (2)	0.0427 (16)	−0.0108 (16)	0.0121 (15)	−0.0251 (15)
C13A	0.0362 (13)	0.040 (2)	0.0327 (19)	0.0104 (15)	0.0002 (13)	−0.0219 (17)
O7	0.0260 (8)	0.0252 (19)	0.0478 (14)	0.0024 (16)	0.0025 (14)	−0.0243 (13)
O8	0.0267 (17)	0.029 (2)	0.0418 (16)	−0.0021 (15)	0.0072 (12)	−0.0219 (16)
C12	0.0203 (10)	0.028 (2)	0.0427 (16)	−0.0108 (16)	0.0121 (15)	−0.0251 (15)
C13	0.0362 (13)	0.040 (2)	0.0327 (19)	0.0104 (15)	0.0002 (13)	−0.0219 (17)
O5	0.0178 (6)	0.0226 (6)	0.0441 (8)	−0.0066 (5)	−0.0034 (5)	−0.0127 (6)
O6	0.0147 (5)	0.0223 (6)	0.0437 (8)	−0.0053 (5)	0.0016 (5)	−0.0162 (6)
N3	0.0181 (7)	0.0247 (7)	0.0330 (8)	−0.0053 (5)	−0.0005 (6)	−0.0157 (6)
N4	0.0186 (7)	0.0278 (8)	0.0349 (8)	−0.0079 (6)	0.0034 (6)	−0.0194 (7)
C10	0.0153 (7)	0.0212 (8)	0.0353 (9)	−0.0058 (6)	0.0042 (6)	−0.0183 (7)
C11	0.0166 (8)	0.0245 (8)	0.0461 (11)	−0.0078 (6)	0.0045 (7)	−0.0175 (8)
C14	0.0451 (13)	0.0270 (10)	0.0538 (14)	0.0009 (9)	−0.0147 (11)	−0.0148 (10)
C15	0.0233 (9)	0.0293 (9)	0.0334 (10)	−0.0073 (7)	0.0005 (7)	−0.0120 (8)
C16	0.0305 (10)	0.0382 (11)	0.0282 (9)	−0.0103 (8)	−0.0002 (8)	−0.0138 (8)
C17	0.0258 (9)	0.0365 (10)	0.0313 (9)	−0.0118 (7)	0.0051 (7)	−0.0197 (8)
C18	0.0488 (13)	0.0505 (14)	0.0502 (13)	−0.0092 (11)	−0.0038 (11)	−0.0363 (12)

Geometric parameters (Å, º) top

Cu1—O2ⁱ	1.9691 (13)	Cu2—O7A	2.032 (9)
Cu1—O1	1.9685 (13)	Cu2—N4	2.1585 (17)
Cu1—O4ⁱ	1.9747 (12)	Cu2—Cu2ⁱⁱ	2.6755 (5)
Cu1—O3	1.9879 (12)	O7A—C12A	1.283 (8)
Cu1—N1	2.1492 (16)	O8A—C12A	1.265 (9)
Cu1—Cu1ⁱ	2.6763 (4)	O8A—Cu2ⁱⁱ	1.912 (15)
O1—C1	1.261 (2)	C12A—C13A	1.534 (9)
O2—C1	1.254 (2)	C13A—H13A	0.98
O2—Cu1ⁱ	1.9691 (13)	C13A—H13B	0.98
C1—C2	1.515 (2)	C13A—H13C	0.98
C2—H2A	0.98	O7—C12	1.236 (4)
C2—H2B	0.98	O8—C12	1.263 (4)
C2—H2C	0.98	O8—Cu2ⁱⁱ	1.997 (5)
O3—C3	1.266 (2)	C12—C13	1.522 (4)
O4—C3	1.254 (2)	C13—H13D	0.98
O4—Cu1ⁱ	1.9747 (12)	C13—H13E	0.98
N1—C6	1.338 (2)	C13—H13F	0.98
N1—N2	1.359 (2)	O5—C10	1.268 (2)
N2—C8	1.342 (2)	O6—C10	1.252 (2)
N2—H2	0.88	O6—Cu2ⁱⁱ	1.9657 (12)
C3—C4	1.512 (2)	N3—C15	1.344 (2)
C4—H4A	0.98	N3—N4	1.357 (2)
C4—H4B	0.98	N3—H3	0.88
C4—H4C	0.98	N4—C17	1.340 (3)
C5—C6	1.493 (3)	C10—C11	1.509 (2)
C5—H5A	0.98	C11—H11A	0.98
C5—H5B	0.98	C11—H11B	0.98
C5—H5C	0.98	C11—H11C	0.98
C6—C7	1.404 (3)	C14—C15	1.492 (3)
C7—C8	1.380 (3)	C14—H14A	0.98
C7—H7	0.95	C14—H14B	0.98
C8—C9	1.493 (3)	C14—H14C	0.98
C9—H9A	0.98	C15—C16	1.383 (3)
C9—H9B	0.98	C16—C17	1.392 (3)
C9—H9C	0.98	C16—H16	0.95
Cu2—O8Aⁱⁱ	1.912 (15)	C17—C18	1.503 (3)
Cu2—O7	1.949 (3)	C18—H18A	0.98
Cu2—O6ⁱⁱ	1.9657 (12)	C18—H18B	0.98
Cu2—O5	1.9756 (13)	C18—H18C	0.98
Cu2—O8ⁱⁱ	1.997 (5)

O2ⁱ—Cu1—O1	167.13 (6)	O5—Cu2—O8ⁱⁱ	88.6 (2)
O2ⁱ—Cu1—O4ⁱ	90.21 (6)	O8Aⁱⁱ—Cu2—O7A	167.1 (4)
O1—Cu1—O4ⁱ	89.34 (6)	O7—Cu2—O7A	9.9 (3)
O2ⁱ—Cu1—O3	87.95 (6)	O6ⁱⁱ—Cu2—O7A	84.8 (5)
O1—Cu1—O3	89.68 (6)	O5—Cu2—O7A	92.1 (5)
O4ⁱ—Cu1—O3	167.33 (6)	O8ⁱⁱ—Cu2—O7A	158.3 (3)
O2ⁱ—Cu1—N1	95.41 (6)	O8Aⁱⁱ—Cu2—N4	90.8 (3)
O1—Cu1—N1	97.43 (6)	O7—Cu2—N4	93.06 (12)
O4ⁱ—Cu1—N1	95.81 (6)	O6ⁱⁱ—Cu2—N4	95.65 (6)
O3—Cu1—N1	96.84 (6)	O5—Cu2—N4	97.26 (6)
O2ⁱ—Cu1—Cu1ⁱ	84.06 (4)	O8ⁱⁱ—Cu2—N4	99.45 (13)
O1—Cu1—Cu1ⁱ	83.11 (4)	O7A—Cu2—N4	101.9 (3)
O4ⁱ—Cu1—Cu1ⁱ	83.34 (4)	O8Aⁱⁱ—Cu2—Cu2ⁱⁱ	88.0 (3)
O3—Cu1—Cu1ⁱ	83.99 (4)	O7—Cu2—Cu2ⁱⁱ	88.14 (11)
N1—Cu1—Cu1ⁱ	179.00 (4)	O6ⁱⁱ—Cu2—Cu2ⁱⁱ	84.11 (4)
C1—O1—Cu1	124.01 (12)	O5—Cu2—Cu2ⁱⁱ	82.99 (4)
C1—O2—Cu1ⁱ	123.04 (12)	O8ⁱⁱ—Cu2—Cu2ⁱⁱ	79.36 (12)
O2—C1—O1	125.59 (17)	O7A—Cu2—Cu2ⁱⁱ	79.3 (3)
O2—C1—C2	117.43 (17)	N4—Cu2—Cu2ⁱⁱ	178.78 (5)
O1—C1—C2	116.98 (17)	C12A—O7A—Cu2	127.1 (9)
C1—C2—H2A	109.5	C12A—O8A—Cu2ⁱⁱ	123.2 (10)
C1—C2—H2B	109.5	O8A—C12A—O7A	122.3 (10)
H2A—C2—H2B	109.5	O8A—C12A—C13A	112.9 (9)
C1—C2—H2C	109.5	O7A—C12A—C13A	124.8 (10)
H2A—C2—H2C	109.5	C12A—C13A—H13A	109.5
H2B—C2—H2C	109.5	C12A—C13A—H13B	109.5
C3—O3—Cu1	122.78 (11)	H13A—C13A—H13B	109.5
C3—O4—Cu1ⁱ	124.51 (12)	C12A—C13A—H13C	109.5
C6—N1—N2	105.07 (15)	H13A—C13A—H13C	109.5
C6—N1—Cu1	133.35 (13)	H13B—C13A—H13C	109.5
N2—N1—Cu1	121.51 (11)	C12—O7—Cu2	118.6 (3)
C8—N2—N1	112.54 (15)	C12—O8—Cu2ⁱⁱ	126.0 (3)
C8—N2—H2	123.7	O7—C12—O8	127.8 (4)
N1—N2—H2	123.7	O7—C12—C13	116.7 (3)
O4—C3—O3	125.35 (16)	O8—C12—C13	115.5 (4)
O4—C3—C4	117.62 (17)	C10—O5—Cu2	124.10 (12)
O3—C3—C4	117.03 (16)	C10—O6—Cu2ⁱⁱ	123.70 (11)
C3—C4—H4A	109.5	C15—N3—N4	112.53 (16)
C3—C4—H4B	109.5	C15—N3—H3	123.7
H4A—C4—H4B	109.5	N4—N3—H3	123.7
C3—C4—H4C	109.5	C17—N4—N3	104.94 (16)
H4A—C4—H4C	109.5	C17—N4—Cu2	131.64 (13)
H4B—C4—H4C	109.5	N3—N4—Cu2	123.27 (12)
C6—C5—H5A	109.5	O6—C10—O5	124.78 (16)
C6—C5—H5B	109.5	O6—C10—C11	117.99 (15)
H5A—C5—H5B	109.5	O5—C10—C11	117.23 (16)
C6—C5—H5C	109.5	C10—C11—H11A	109.5
H5A—C5—H5C	109.5	C10—C11—H11B	109.5
H5B—C5—H5C	109.5	H11A—C11—H11B	109.5
N1—C6—C7	110.27 (17)	C10—C11—H11C	109.5
N1—C6—C5	121.39 (18)	H11A—C11—H11C	109.5
C7—C6—C5	128.34 (18)	H11B—C11—H11C	109.5
C8—C7—C6	105.85 (17)	C15—C14—H14A	109.5
C8—C7—H7	127.1	C15—C14—H14B	109.5
C6—C7—H7	127.1	H14A—C14—H14B	109.5
N2—C8—C7	106.27 (17)	C15—C14—H14C	109.5
N2—C8—C9	122.23 (18)	H14A—C14—H14C	109.5
C7—C8—C9	131.49 (19)	H14B—C14—H14C	109.5
C8—C9—H9A	109.5	N3—C15—C16	105.90 (18)
C8—C9—H9B	109.5	N3—C15—C14	122.15 (19)
H9A—C9—H9B	109.5	C16—C15—C14	131.9 (2)
C8—C9—H9C	109.5	C15—C16—C17	106.16 (18)
H9A—C9—H9C	109.5	C15—C16—H16	126.9
H9B—C9—H9C	109.5	C17—C16—H16	126.9
O8Aⁱⁱ—Cu2—O7	175.4 (6)	N4—C17—C16	110.47 (18)
O8Aⁱⁱ—Cu2—O6ⁱⁱ	92.2 (7)	N4—C17—C18	120.98 (19)
O7—Cu2—O6ⁱⁱ	89.93 (17)	C16—C17—C18	128.53 (19)
O8Aⁱⁱ—Cu2—O5	88.0 (7)	C17—C18—H18A	109.5
O7—Cu2—O5	89.00 (18)	C17—C18—H18B	109.5
O6ⁱⁱ—Cu2—O5	167.08 (6)	H18A—C18—H18B	109.5
O8Aⁱⁱ—Cu2—O8ⁱⁱ	8.8 (4)	C17—C18—H18C	109.5
O7—Cu2—O8ⁱⁱ	167.47 (13)	H18A—C18—H18C	109.5
O6ⁱⁱ—Cu2—O8ⁱⁱ	89.6 (2)	H18B—C18—H18C	109.5

O2ⁱ—Cu1—O1—C1	8.2 (3)	Cu2—O7A—C12A—O8A	3 (3)
O4ⁱ—Cu1—O1—C1	−79.85 (15)	Cu2—O7A—C12A—C13A	−178.1 (12)
O3—Cu1—O1—C1	87.51 (15)	O6ⁱⁱ—Cu2—O7—C12	82.6 (4)
N1—Cu1—O1—C1	−175.63 (14)	O5—Cu2—O7—C12	−84.5 (4)
Cu1ⁱ—Cu1—O1—C1	3.53 (14)	O8ⁱⁱ—Cu2—O7—C12	−5.3 (15)
Cu1ⁱ—O2—C1—O1	4.2 (3)	O7A—Cu2—O7—C12	24 (4)
Cu1ⁱ—O2—C1—C2	−175.42 (12)	N4—Cu2—O7—C12	178.3 (4)
Cu1—O1—C1—O2	−5.7 (3)	Cu2ⁱⁱ—Cu2—O7—C12	−1.5 (4)
Cu1—O1—C1—C2	173.89 (12)	Cu2—O7—C12—O8	1.6 (9)
O2ⁱ—Cu1—O3—C3	85.70 (14)	Cu2—O7—C12—C13	−177.4 (3)
O1—Cu1—O3—C3	−81.65 (14)	Cu2ⁱⁱ—O8—C12—O7	−0.5 (10)
O4ⁱ—Cu1—O3—C3	3.9 (3)	Cu2ⁱⁱ—O8—C12—C13	178.5 (4)
N1—Cu1—O3—C3	−179.09 (14)	O8Aⁱⁱ—Cu2—O5—C10	−84.2 (4)
Cu1ⁱ—Cu1—O3—C3	1.46 (13)	O7—Cu2—O5—C10	92.26 (18)
O2ⁱ—Cu1—N1—C6	−150.52 (17)	O6ⁱⁱ—Cu2—O5—C10	7.0 (4)
O1—Cu1—N1—C6	30.33 (18)	O8ⁱⁱ—Cu2—O5—C10	−75.43 (19)
O4ⁱ—Cu1—N1—C6	−59.76 (18)	O7A—Cu2—O5—C10	82.9 (4)
O3—Cu1—N1—C6	120.91 (17)	N4—Cu2—O5—C10	−174.79 (15)
O2ⁱ—Cu1—N1—N2	32.91 (13)	Cu2ⁱⁱ—Cu2—O5—C10	4.01 (15)
O1—Cu1—N1—N2	−146.24 (12)	C15—N3—N4—C17	−0.2 (2)
O4ⁱ—Cu1—N1—N2	123.67 (13)	C15—N3—N4—Cu2	−176.20 (12)
O3—Cu1—N1—N2	−55.66 (13)	O8Aⁱⁱ—Cu2—N4—C17	41.6 (7)
C6—N1—N2—C8	−0.6 (2)	O7—Cu2—N4—C17	−140.9 (2)
Cu1—N1—N2—C8	176.81 (12)	O6ⁱⁱ—Cu2—N4—C17	−50.68 (17)
Cu1ⁱ—O4—C3—O3	1.4 (3)	O5—Cu2—N4—C17	129.72 (17)
Cu1ⁱ—O4—C3—C4	−178.07 (13)	O8ⁱⁱ—Cu2—N4—C17	39.9 (3)
Cu1—O3—C3—O4	−2.1 (3)	O7A—Cu2—N4—C17	−136.6 (6)
Cu1—O3—C3—C4	177.33 (12)	O8Aⁱⁱ—Cu2—N4—N3	−143.5 (7)
N2—N1—C6—C7	0.6 (2)	O7—Cu2—N4—N3	34.0 (2)
Cu1—N1—C6—C7	−176.34 (13)	O6ⁱⁱ—Cu2—N4—N3	124.19 (13)
N2—N1—C6—C5	−178.95 (18)	O5—Cu2—N4—N3	−55.42 (14)
Cu1—N1—C6—C5	4.1 (3)	O8ⁱⁱ—Cu2—N4—N3	−145.3 (3)
N1—C6—C7—C8	−0.5 (2)	O7A—Cu2—N4—N3	38.3 (6)
C5—C6—C7—C8	179.1 (2)	Cu2ⁱⁱ—O6—C10—O5	6.4 (3)
N1—N2—C8—C7	0.3 (2)	Cu2ⁱⁱ—O6—C10—C11	−173.03 (13)
N1—N2—C8—C9	179.72 (17)	Cu2—O5—C10—O6	−7.4 (3)
C6—C7—C8—N2	0.1 (2)	Cu2—O5—C10—C11	172.06 (13)
C6—C7—C8—C9	−179.2 (2)	N4—N3—C15—C16	0.3 (2)
O8Aⁱⁱ—Cu2—O7A—C12A	8 (5)	N4—N3—C15—C14	179.44 (19)
O7—Cu2—O7A—C12A	−154 (6)	N3—C15—C16—C17	−0.3 (2)
O6ⁱⁱ—Cu2—O7A—C12A	85.3 (17)	C14—C15—C16—C17	−179.3 (2)
O5—Cu2—O7A—C12A	−82.2 (17)	N3—N4—C17—C16	−0.1 (2)
O8ⁱⁱ—Cu2—O7A—C12A	10 (3)	Cu2—N4—C17—C16	175.49 (13)
N4—Cu2—O7A—C12A	180.0 (17)	N3—N4—C17—C18	−178.19 (18)
Cu2ⁱⁱ—Cu2—O7A—C12A	0.3 (17)	Cu2—N4—C17—C18	−2.6 (3)
Cu2ⁱⁱ—O8A—C12A—O7A	−5 (3)	C15—C16—C17—N4	0.3 (2)
Cu2ⁱⁱ—O8A—C12A—C13A	175.6 (13)	C15—C16—C17—C18	178.2 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.88	1.93	2.785 (2)	163
N3—H3···O3	0.88	2	2.847 (2)	163

Experimental details

Crystal data
Chemical formula	[Cu₂(C₂H₃O₂)₄(C₅H₈N₂)₂]
M_r	555.52
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.1125 (4), 13.6429 (7), 13.7755 (7)
α, β, γ (°)	61.571 (1), 87.449 (1), 82.354 (1)
V (Å³)	1328.55 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.64
Crystal size (mm)	0.39 × 0.16 × 0.1

Data collection
Diffractometer	Bruker X8 APEXII 4K Kappa CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.566, 0.853
No. of measured, independent and observed [I > 2σ(I)] reflections	17190, 6578, 5934
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.06
No. of reflections	6578
No. of parameters	310
No. of restraints	17
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.28, −0.59

Computer programs: APEX2 (Bruker, 2007), SAINT-Plus (Bruker, 2007), SAINT-Plus and XPREP (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009), DIAMOND (Brandenburg & Putz, 2005), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O5	0.88	1.93	2.785 (2)	162.9
N3—H3···O3	0.88	2	2.847 (2)	162.6

Acknowledgements

The authors gratefully acknowledge the University of Johannesburg for funding and Dr Ilia Guzei for help with the refinement of the structure.

References

Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2007). APEX2, SADABS, SAINT-Plus and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Deka, K., Laskar, M. & Baruah, J. B. (2006). Polyhedron, 25, 2525–2529. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Guzei, I. A., Li, K., Bikhazanova, G. A., Darkwa, J. & Mapolie, S. F. (2003). Dalton Trans. pp. 715–722. Web of Science CSD CrossRef Google Scholar
Mohlala, M. S., Guzei, I. A., Darkwa, J. & Mapolie, S. F. (2005). J. Mol. Catal. A Chem. 241, 93–100. CrossRef CAS Google Scholar
Nelana, S. M., Kruger, G. J. & Darkwa, J. (2008). Acta Cryst. E64, m206–m207. Google Scholar
Ojwach, S. O., Tshivhase, M. G., Guzei, I. A., Darkwa, J. & Mapolie, S. F. (2005). Can. J. Chem. 83, 843–853. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar