Bis­[μ-2-hydroxy-5-methyl-1,3-bis(3-oxido-κO-3-phenyl­prop-2-enonyl-κO)­benzene]­bis­[(N,N-di­methyl­form­amide-O)copper(II)] bis(N,N-di­methyl­form­amide) solvate

Kooijman, H.; Spek, A.L.; Aromí, G.; Gamez, P.; Carrero Berzal, P.; Driessen, W.L.; Reedijk, J.

doi:10.1107/S1600536802006918

Bis[μ-2-hydroxy-5-methyl-1,3-bis(3-oxido-κO-3-phenylprop-2-enonyl-κO)benzene]bis[(N,N-dimethylformamide-O)copper(II)] bis(N,N-dimethylformamide) solvate

H. Kooijman, A. L. Spek, G. Aromí, P. Gamez, P. Carrero Berzal, W. L. Driessen and J. Reedijk

The title compound, [Cu₂(C₂₅H₁₈O₅)₂(C₃H₇NO)₂]·2C₃H₇NO, is located on a crystallographic inversion centre. The bis(1,3-diketonato)phenol ligand displays a twisted conformation, with a larger planar section stabilized by an intramolecular hydrogen bond.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006918/na6156sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006918/na6156Isup2.hkl Contains datablock I

CCDC reference: 185756

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Key indicators

Single-crystal X-ray study
T = 150 K
Mean (C-C) = 0.005 Å
R factor = 0.057
wR factor = 0.157
Data-to-parameter ratio = 17.3

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No syntax errors found

ADDSYM reports no extra symmetry

Comment top

Initial investigations on the coordination properties of the ligand 1,3-bis(3-oxo-3-phenylpropionyl)-2-hydroxy-5-methylbenzene (abbreviated H₃L) have lead to a variety of coordination architectures (Aromí\ et al., 2001, Aromí, Gamez, Roubeau, Carrero Berzal, Driessen et al., 2002; Aromí, Gamez, Roubeau, Carrero Berzal, Kooijman et al., 2002; Aromí, Gamez, Roubeau, Driessen et al., 2002). From part of this work it was found that the preferred local stereochemistry at the metal centre in simple dinuclear complexes of formulation [M₂(HL)₂(py)₄] (where M = Ni^II, Mn^II) can lead to assemblies with completely different overall structures (Aromí\ et al., 2002a). This prompted us to determine analogous structures with differenct metal ions and coordinating solvents. We present here the crystal structure of [Cu^II₂(HL)₂(dmf)₂], (I).

Molecules of (I) are located on crystallographic inversion centres (see Fig. 1). The crystal contains two molecules of N,N-dimethylformamide cocrystallized as non-coordinating solvent for each dinuclear Cu complex. The copper ion displays a square-pyramid coordination sphere. The Cu atom is displaced 0.1177 (3) Å from the least-squares plane through the four coordinating O atoms in the direction of the coordinating N,N-dimethylformamide molecule (all least-squares planes mentioned in this Comment are calculated with unit weights). The maximum deviation of the constituent O atoms from the plane is 0.085 (3) Å. The angle between the two diketonate units coordinating to a single copper ion is 26.02 (16)°, with the diketonate moieties tilted towards the N,N-dimethylformamide molecule. The angles between the individual diketonate units and the basal Cu coordination plane are 14.62 (14) and 11.45 (14)° for the moieties containg O2 and O5, respectively. Due to the inversion symmetry of the complex, the angle between the two diketonate moieties within one ligand HL is also 26.02 (16)°. The core of the HL ligand, i.e. without the peripheral phenyl rings, consists of two roughly planar segments, hinged at the bond C41—C50. The overall conformation of the HL ligand can be described with the angles between phenyl rings A (C21/C22/C25–C28), B (C40–C45) and C (C61–C66) and the diketonate moieties 1 (O2, ···, O3) and 2 (O5, ···, O6). The angle (A,1) is 17.21 (16)°, (1,B) is 7.76 (16)°, (B,2) is 33.62 (16)° and (2,C) 17.24 (17)°.

The OH group at O4 in the centre of the ligand HL donates a hydrogen bond to O3, thereby stabilizing the larger planar fragment of HL. Geometric details of the hydrogen bond are given in Table 2. The distance O4···O5 is significantly larger [2.673 (4) Å] than O3···O4 due to the twist of the ligand. The aldehyde H atom of the coordinated N,N-dimethylformamide is in quite close contact with two O atoms of the organic ligand (see Fig. 1). Details of these relatively weak C—H···O interactions are included in Table 2. The non-coordinating N,N-dimethylformamide solvent molecule is not involved in any weak hydrogen bonds.

Experimental top

The complex [Cu^II₂(HL)₂(dmf)₂] was prepared in two different ways.

Method 1: H₃L (100 mg, 0.25 mmol) was dissolved in hot EtOH (8 ml). This solution was added to a solution of Cu(AcO)₂·3H₂O (50 mg, 0.25 mmol) in EtOH (8 ml) and the mixture was refluxed for 1 h. A green powder was obtained, which was dissolved in DMF to saturation and layered with Et₂O. After a few days, green needles of the title compound were obtained, which were suitable for X-ray crystallography.

Method 2: a solution of H₃L (50 mg, 0.13 mmol) in DMF (5 ml) was mixed with an equimolar amount of Cu(AcO)₂·3H₂O (25 mg, 0.125 mmol) in DMF (5 ml). The solution was stirred for a few minutes and was stored undisturbed at 278 K. After a few hours, a microcrystalline precipitate of the title compound had formed, which was collected by filtration. The yield was 47%.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO; program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2002); software used to prepare material for publication: PLATON.

Figures top

Fig. 1. View of the title compound with the atom-numbering scheme. The non-coordinating N,N-dimethylformamide solvent molecule and H atoms not involved in hydrogen bonds have been omitted for clarity. Displacement ellipsoids for non-H atoms are drawn at the 50% probability l evel. [Symmetry code: (i) -x, -y, 1 - z.]

(I) top

Crystal data top

[Cu₂(C₂₅H₁₈O₅)₂(C₃H₇NO)₂]·2C₃H₇NO	F(000) = 1268
M_r = 1216.27	Quoted _cell_measurement_* data items refer to the initial cell determination. The cell parameters as reported in _cell_* are based on the complete data set.
Monoclinic, P2₁/c	D_x = 1.430 Mg m⁻³
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 10.784 (1) Å	Cell parameters from 537 reflections
b = 29.701 (4) Å	θ = 2.0–25.0°
c = 8.8317 (10) Å	µ = 0.83 mm⁻¹
β = 93.015 (10)°	T = 150 K
V = 2824.8 (6) Å³	Needle, green
Z = 2	0.30 × 0.10 × 0.10 mm

Data collection top

Nonius KappaCCD area-detector diffractometer	4487 reflections with I > 2σ(I)
Radiation source: Rotating Anode	R_int = 0.095
Graphite monochromator	θ_max = 27.5°, θ_min = 1.9°
Detector resolution: 18.4 pixels mm^-1	h = −13→13
ϕ scans and ω scans with κ offset	k = −38→38
58094 measured reflections	l = −11→11
6483 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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.157	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0835P)² + 1.47P] where P = (F_o² + 2F_c²)/3
6483 reflections	(Δ/σ)_max = 0.001
375 parameters	Δρ_max = 0.98 e Å⁻³
0 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Cu₂(C₂₅H₁₈O₅)₂(C₃H₇NO)₂]·2C₃H₇NO	V = 2824.8 (6) Å³
M_r = 1216.27	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.784 (1) Å	µ = 0.83 mm⁻¹
b = 29.701 (4) Å	T = 150 K
c = 8.8317 (10) Å	0.30 × 0.10 × 0.10 mm
β = 93.015 (10)°

Data collection top

Nonius KappaCCD area-detector diffractometer	4487 reflections with I > 2σ(I)
58094 measured reflections	R_int = 0.095
6483 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.157	H-atom parameters constrained
S = 1.05	Δρ_max = 0.98 e Å⁻³
6483 reflections	Δρ_min = −0.58 e Å⁻³
375 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F^{2 for ALL reflections except those flagged by the user
for potential systematic errors. Weighted} ^R^-factors ^wR ^{and all goodnesses of fit} ^S ^{are based on} ^F2, conventional R-factors R are based on F, with F set to zero for negative F^{2. The observed criterion of} ^F2 > σ(F^{2) is used only for calculating -}^R^-factor-obs ^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
Cu1	0.24109 (3)	−0.06756 (1)	0.74281 (4)	0.0199 (1)
O2	0.40757 (19)	−0.05745 (7)	0.8235 (3)	0.0248 (7)
O3	0.22865 (18)	−0.00666 (7)	0.6712 (3)	0.0225 (7)
O4	0.06562 (19)	0.04292 (8)	0.5501 (3)	0.0274 (7)
O5	−0.06518 (19)	0.06995 (7)	0.3011 (3)	0.0218 (7)
O6	−0.24544 (19)	0.12804 (7)	0.1806 (3)	0.0230 (7)
O71	0.2977 (2)	−0.08998 (8)	0.4936 (3)	0.0280 (8)
N73	0.2177 (3)	−0.10909 (10)	0.2581 (3)	0.0279 (9)
C20	0.4788 (3)	−0.02554 (11)	0.7848 (4)	0.0207 (9)
C21	0.6104 (3)	−0.02848 (10)	0.8483 (4)	0.0214 (10)
C22	0.6379 (3)	−0.05693 (12)	0.9706 (4)	0.0261 (10)
C25	0.7588 (3)	−0.06111 (12)	1.0297 (4)	0.0321 (11)
C26	0.8531 (3)	−0.03731 (12)	0.9677 (4)	0.0325 (11)
C27	0.8273 (3)	−0.00927 (12)	0.8445 (4)	0.0316 (11)
C28	0.7062 (3)	−0.00441 (11)	0.7868 (4)	0.0243 (10)
C30	0.3200 (3)	0.01910 (10)	0.6380 (3)	0.0196 (9)
C31	0.4418 (3)	0.01042 (11)	0.6890 (4)	0.0225 (10)
C40	0.1598 (3)	0.06643 (10)	0.4943 (4)	0.0210 (9)
C41	0.1294 (3)	0.10034 (10)	0.3862 (4)	0.0210 (9)
C42	0.2856 (3)	0.05857 (10)	0.5409 (3)	0.0194 (9)
C43	0.3764 (3)	0.08682 (11)	0.4840 (4)	0.0221 (10)
C44	0.2239 (3)	0.12703 (11)	0.3353 (4)	0.0230 (10)
C45	0.3480 (3)	0.12125 (11)	0.3829 (4)	0.0225 (10)
C46	0.4477 (3)	0.15066 (12)	0.3209 (4)	0.0308 (11)
C50	−0.0004 (3)	0.10587 (11)	0.3196 (4)	0.0212 (9)
C51	−0.0432 (3)	0.14894 (11)	0.2757 (4)	0.0236 (10)
C60	−0.1596 (3)	0.15765 (11)	0.2052 (3)	0.0215 (10)
C61	−0.1923 (3)	0.20404 (11)	0.1501 (4)	0.0225 (9)
C62	−0.1035 (3)	0.23735 (12)	0.1321 (4)	0.0331 (11)
C63	−0.1393 (4)	0.27917 (13)	0.0761 (5)	0.0400 (14)
C64	−0.2616 (3)	0.28881 (12)	0.0406 (4)	0.0342 (11)
C65	−0.3506 (3)	0.25643 (12)	0.0597 (5)	0.0360 (11)
C66	−0.3157 (3)	0.21403 (12)	0.1134 (4)	0.0297 (11)
C72	0.2101 (3)	−0.09345 (11)	0.3987 (4)	0.0258 (10)
C74	0.3358 (3)	−0.12264 (15)	0.2005 (5)	0.0417 (14)
C75	0.1094 (3)	−0.11285 (15)	0.1556 (4)	0.0430 (14)
O81	0.2113 (4)	0.28237 (13)	0.5801 (4)	0.0804 (16)
N83	0.2531 (4)	0.30696 (12)	0.3422 (4)	0.0508 (12)
C82	0.1782 (6)	0.2959 (2)	0.4546 (8)	0.080 (3)
C84	0.3800 (6)	0.3059 (4)	0.3566 (11)	0.172 (6)
C85	0.1969 (6)	0.3226 (2)	0.1995 (6)	0.077 (2)
H4	0.09350	0.02430	0.61130	0.0410*
H22	0.57470	−0.07320	1.01290	0.0310*
H25	0.77630	−0.08010	1.11180	0.0380*
H26	0.93410	−0.04000	1.00830	0.0390*
H27	0.89120	0.00620	0.80080	0.0380*
H28	0.68870	0.01510	0.70620	0.0290*
H31	0.50320	0.02980	0.65750	0.0270*
H43	0.45900	0.08220	0.51560	0.0270*
H44	0.20360	0.14980	0.26620	0.0280*
H46A	0.50270	0.16090	0.40280	0.0460*
H46B	0.41000	0.17610	0.27000	0.0460*
H46C	0.49390	0.13360	0.25060	0.0460*
H51	0.00960	0.17320	0.29500	0.0280*
H62	−0.02030	0.23150	0.15770	0.0390*
H63	−0.07930	0.30110	0.06230	0.0480*
H64	−0.28430	0.31710	0.00380	0.0410*
H65	−0.43390	0.26290	0.03670	0.0430*
H66	−0.37600	0.19210	0.12480	0.0360*
H72	0.13230	−0.08440	0.42770	0.0310*
H74A	0.40020	−0.11950	0.27910	0.0630*
H74B	0.35430	−0.10390	0.11610	0.0630*
H74C	0.33100	−0.15350	0.16840	0.0630*
H75A	0.03810	−0.10160	0.20430	0.0640*
H75B	0.09630	−0.14390	0.12870	0.0640*
H75C	0.12170	−0.09560	0.06580	0.0640*
H82	0.09320	0.29900	0.43380	0.0950*
H84A	0.41180	0.33610	0.35190	0.2580*
H84B	0.41140	0.28840	0.27570	0.2580*
H84C	0.40580	0.29260	0.45210	0.2580*
H85A	0.23110	0.35130	0.17510	0.1160*
H85B	0.10880	0.32530	0.20760	0.1160*
H85C	0.21360	0.30140	0.12110	0.1160*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0166 (2)	0.0178 (2)	0.0248 (2)	−0.0008 (2)	−0.0035 (2)	0.0037 (2)
O2	0.0184 (11)	0.0221 (12)	0.0330 (13)	−0.0032 (9)	−0.0066 (9)	0.0064 (10)
O3	0.0160 (11)	0.0211 (12)	0.0299 (13)	−0.0016 (9)	−0.0035 (9)	0.0064 (10)
O4	0.0153 (11)	0.0293 (13)	0.0376 (14)	−0.0001 (9)	0.0009 (10)	0.0160 (11)
O5	0.0146 (10)	0.0167 (11)	0.0335 (13)	−0.0015 (9)	−0.0032 (9)	0.0036 (10)
O6	0.0193 (11)	0.0208 (12)	0.0285 (13)	−0.0011 (9)	−0.0036 (9)	0.0052 (10)
O71	0.0272 (13)	0.0311 (14)	0.0253 (13)	0.0011 (10)	−0.0038 (10)	−0.0007 (10)
N73	0.0246 (15)	0.0314 (17)	0.0272 (16)	0.0029 (12)	−0.0029 (12)	−0.0025 (13)
C20	0.0191 (16)	0.0211 (17)	0.0217 (16)	0.0023 (13)	−0.0020 (12)	−0.0025 (13)
C21	0.0205 (16)	0.0212 (17)	0.0221 (17)	0.0023 (13)	−0.0034 (13)	−0.0048 (13)
C22	0.0241 (17)	0.0296 (19)	0.0242 (18)	0.0000 (14)	−0.0016 (13)	−0.0011 (14)
C25	0.0294 (19)	0.040 (2)	0.0257 (19)	0.0054 (16)	−0.0088 (14)	0.0023 (16)
C26	0.0191 (17)	0.042 (2)	0.035 (2)	0.0047 (15)	−0.0107 (14)	−0.0027 (17)
C27	0.0205 (17)	0.035 (2)	0.039 (2)	−0.0034 (15)	−0.0018 (15)	−0.0026 (17)
C28	0.0204 (16)	0.0232 (18)	0.0288 (18)	0.0020 (14)	−0.0043 (13)	−0.0016 (14)
C30	0.0173 (15)	0.0211 (16)	0.0202 (16)	−0.0013 (13)	−0.0009 (12)	−0.0034 (13)
C31	0.0195 (16)	0.0217 (17)	0.0260 (17)	−0.0002 (13)	−0.0012 (13)	0.0018 (14)
C40	0.0177 (15)	0.0199 (16)	0.0256 (17)	−0.0009 (13)	0.0019 (12)	−0.0011 (14)
C41	0.0181 (15)	0.0184 (16)	0.0261 (17)	0.0006 (12)	−0.0025 (13)	−0.0012 (13)
C42	0.0198 (15)	0.0192 (16)	0.0189 (16)	−0.0013 (12)	−0.0012 (12)	−0.0038 (13)
C43	0.0149 (15)	0.0237 (17)	0.0271 (18)	0.0005 (13)	−0.0045 (12)	−0.0008 (14)
C44	0.0212 (16)	0.0212 (17)	0.0262 (18)	0.0004 (13)	−0.0012 (13)	0.0022 (14)
C45	0.0160 (15)	0.0242 (17)	0.0272 (18)	−0.0017 (13)	−0.0003 (13)	0.0007 (14)
C46	0.0198 (17)	0.0292 (19)	0.043 (2)	−0.0044 (14)	−0.0021 (15)	0.0083 (16)
C50	0.0178 (15)	0.0230 (17)	0.0228 (17)	−0.0007 (13)	0.0010 (12)	0.0030 (14)
C51	0.0176 (15)	0.0200 (17)	0.0329 (19)	−0.0006 (13)	−0.0019 (13)	0.0029 (14)
C60	0.0196 (16)	0.0242 (17)	0.0207 (17)	0.0024 (13)	0.0001 (12)	0.0020 (13)
C61	0.0237 (16)	0.0201 (16)	0.0235 (17)	0.0010 (13)	−0.0003 (13)	0.0003 (13)
C62	0.0236 (18)	0.031 (2)	0.044 (2)	−0.0016 (15)	−0.0043 (15)	0.0113 (17)
C63	0.038 (2)	0.026 (2)	0.055 (3)	−0.0068 (17)	−0.0062 (18)	0.0111 (18)
C64	0.043 (2)	0.0205 (18)	0.038 (2)	0.0007 (16)	−0.0076 (17)	0.0049 (16)
C65	0.0244 (18)	0.031 (2)	0.052 (2)	0.0054 (15)	−0.0051 (16)	0.0078 (18)
C66	0.0233 (17)	0.0253 (19)	0.040 (2)	−0.0015 (14)	−0.0042 (15)	0.0068 (16)
C72	0.0238 (17)	0.0239 (18)	0.0300 (19)	0.0025 (14)	0.0033 (14)	0.0016 (15)
C74	0.028 (2)	0.059 (3)	0.038 (2)	0.0082 (18)	−0.0002 (16)	−0.013 (2)
C75	0.034 (2)	0.061 (3)	0.033 (2)	0.0007 (19)	−0.0082 (17)	−0.0082 (19)
O81	0.100 (3)	0.081 (3)	0.059 (2)	0.001 (2)	−0.006 (2)	0.012 (2)
N83	0.055 (2)	0.047 (2)	0.050 (2)	−0.0101 (18)	−0.0017 (18)	0.0048 (18)
C82	0.069 (4)	0.083 (4)	0.086 (5)	−0.007 (3)	−0.002 (3)	0.014 (4)
C84	0.057 (5)	0.284 (13)	0.174 (9)	0.016 (6)	−0.011 (5)	0.043 (9)
C85	0.092 (4)	0.071 (4)	0.067 (4)	−0.009 (3)	−0.011 (3)	0.007 (3)

Geometric parameters (Å, º) top

Cu1—O2	1.920 (2)	C60—C61	1.497 (5)
Cu1—O3	1.918 (2)	C61—C66	1.385 (5)
Cu1—O71	2.409 (3)	C61—C62	1.392 (5)
Cu1—O5ⁱ	1.917 (2)	C62—C63	1.384 (5)
Cu1—O6ⁱ	1.919 (2)	C63—C64	1.370 (5)
O2—C20	1.278 (4)	C64—C65	1.375 (5)
O3—C30	1.293 (4)	C65—C66	1.391 (5)
O4—C40	1.347 (4)	C22—H22	0.9297
O5—C50	1.281 (4)	C25—H25	0.9301
O6—C60	1.287 (4)	C26—H26	0.9301
O71—C72	1.234 (4)	C27—H27	0.9289
O4—H4	0.8193	C28—H28	0.9295
O81—C82	1.215 (8)	C31—H31	0.9309
N73—C74	1.453 (5)	C43—H43	0.9295
N73—C75	1.444 (5)	C44—H44	0.9293
N73—C72	1.332 (4)	C46—H46A	0.9604
N83—C84	1.368 (8)	C46—H46B	0.9587
N83—C82	1.353 (8)	C46—H46C	0.9607
N83—C85	1.446 (7)	C51—H51	0.9286
C20—C21	1.501 (5)	C62—H62	0.9300
C20—C31	1.407 (5)	C63—H63	0.9306
C21—C28	1.390 (5)	C64—H64	0.9291
C21—C22	1.391 (5)	C65—H65	0.9306
C22—C25	1.384 (5)	C66—H66	0.9296
C25—C26	1.376 (5)	C72—H72	0.9297
C26—C27	1.387 (5)	C74—H74A	0.9603
C27—C28	1.384 (5)	C74—H74B	0.9596
C30—C42	1.488 (4)	C74—H74C	0.9600
C30—C31	1.390 (5)	C75—H75B	0.9609
C40—C42	1.416 (5)	C75—H75C	0.9592
C40—C41	1.414 (5)	C75—H75A	0.9605
C41—C50	1.499 (5)	C82—H82	0.9299
C41—C44	1.385 (5)	C84—H84A	0.9620
C42—C43	1.403 (5)	C84—H84B	0.9596
C43—C45	1.381 (5)	C84—H84C	0.9592
C44—C45	1.392 (5)	C85—H85A	0.9578
C45—C46	1.510 (5)	C85—H85B	0.9599
C50—C51	1.407 (5)	C85—H85C	0.9599
C51—C60	1.396 (5)

Cu1···C75ⁱⁱ	4.203 (4)	C60···H75C^v	3.0651
Cu1···C26ⁱⁱⁱ	4.188 (4)	C62···H82^ix	3.0204
Cu1···H74Bⁱⁱ	3.6195	C62···H51	2.6463
Cu1···H75Cⁱⁱ	3.2977	C66···H74C^v	3.0676
Cu1···H4	3.3363	C72···H64^viii	2.8927
Cu1···H46C^iv	3.4643	C72···H28^iv	2.7515
O3···C25ⁱⁱⁱ	3.318 (4)	C74···H84A^xiii	3.0425
O3···O4	2.491 (3)	C82···H62^vi	2.9776
O4···O4ⁱ	3.026 (3)	H4···Cu1	3.3363
O4···O5	2.673 (4)	H4···O3	1.7800
O4···C72ⁱ	3.382 (4)	H4···C30	2.4464
O4···O3	2.491 (3)	H22···O2	2.4389
O5···O4	2.673 (4)	H25···C30ⁱⁱⁱ	3.0798
O6···C75^v	3.410 (4)	H28···C72^iv	2.7515
O81···C85^vi	3.297 (7)	H28···O71^iv	2.8476
O2···H46C^iv	2.5973	H28···C31	2.6625
O2···H22	2.4389	H28···H31	2.0705
O3···H4	1.7800	H31···H28	2.0705
O4···H72ⁱ	2.4811	H31···C43	2.6202
O5···H72ⁱ	2.5743	H31···H43	2.0389
O6···H66	2.4026	H31···C28	2.6203
O6···H74B^v	2.9043	H43···H31	2.0389
O6···H75C^v	2.7839	H43···H46A	2.5938
O6···H46C^vii	2.9144	H43···C31	2.6372
O71···H74A	2.4082	H43···H74A^iv	2.5555
O71···H64^viii	2.7638	H43···O71^iv	2.6394
O71···H43^iv	2.6394	H44···C51	2.6673
O71···H28^iv	2.8476	H44···H46B	2.3575
O81···H62^vi	2.6566	H44···H51	2.2317
O81···H85C^vi	2.5142	H44···O81^ix	2.6041
O81···H44^vi	2.6041	H46A···H43	2.5938
O81···H84C	2.4534	H46A···H64^xiv	2.5066
C20···C43^iv	3.432 (5)	H46B···H44	2.3575
C20···C22ⁱⁱⁱ	3.541 (5)	H46C···O6^xii	2.9144
C21···C45^iv	3.473 (5)	H46C···Cu1^iv	3.4642
C21···C43^iv	3.418 (5)	H46C···O2^iv	2.5973
C22···C31ⁱⁱⁱ	3.458 (5)	H46C···H66^xii	2.5270
C22···C20ⁱⁱⁱ	3.541 (5)	H51···C44	2.6947
C25···O3ⁱⁱⁱ	3.318 (4)	H51···C62	2.6463
C25···C30ⁱⁱⁱ	3.340 (4)	H51···H62	2.1287
C26···Cu1ⁱⁱⁱ	4.188 (4)	H51···H44	2.2317
C27···C40^iv	3.449 (5)	H62···C51	2.6809
C27···C41^iv	3.433 (5)	H62···C82^ix	2.9776
C28···C42^iv	3.316 (4)	H62···H51	2.1287
C28···C43^iv	3.504 (5)	H62···O81^ix	2.6566
C28···C40^iv	3.467 (5)	H62···H82^ix	2.5463
C28···C72^iv	3.479 (5)	H63···C51^ix	2.9772
C30···C25ⁱⁱⁱ	3.340 (4)	H63···H85B	2.4503
C31···C22ⁱⁱⁱ	3.458 (5)	H64···H46A^xv	2.5066
C40···C27^iv	3.449 (5)	H64···O71^x	2.7638
C40···C28^iv	3.467 (5)	H64···C72^x	2.8927
C41···C27^iv	3.433 (5)	H65···H84C^xv	2.4755
C42···C28^iv	3.316 (4)	H66···C46^vii	2.9112
C43···C21^iv	3.418 (5)	H66···H46C^vii	2.5270
C43···C28^iv	3.504 (5)	H66···O6	2.4026
C43···C20^iv	3.432 (5)	H72···O4ⁱ	2.4811
C44···C85^vi	3.573 (6)	H72···O5ⁱ	2.5743
C45···C21^iv	3.473 (5)	H72···H75A	2.2304
C50···C72ⁱ	3.469 (5)	H72···C50ⁱ	2.7829
C60···C75^v	3.521 (5)	H74A···O71	2.4082
C60···C64^vi	3.585 (5)	H74A···H43^iv	2.5555
C61···C64^vi	3.573 (5)	H74B···Cu1^xi	3.6195
C64···C60^ix	3.585 (5)	H74B···H75C	2.5363
C64···C61^ix	3.573 (5)	H74B···O6^v	2.9043
C64···C72^x	3.577 (5)	H74C···H75B	2.5528
C72···C50ⁱ	3.469 (5)	H74C···C66^v	3.0676
C72···C28^iv	3.479 (5)	H75A···H72	2.2304
C72···O4ⁱ	3.382 (4)	H75B···C60^v	3.0888
C72···C64^viii	3.577 (5)	H75B···H74C	2.5528
C75···Cu1^xi	4.203 (4)	H75C···Cu1^xi	3.2977
C75···O6^v	3.410 (4)	H75C···O6^v	2.7839
C75···C60^v	3.521 (5)	H75C···C60^v	3.0651
C85···C44^ix	3.573 (6)	H75C···H74B	2.5363
C85···O81^ix	3.297 (7)	H82···H85B	2.1598
C28···H31	2.6203	H82···C62^vi	3.0204
C30···H4	2.4464	H82···H62^vi	2.5463
C30···H25ⁱⁱⁱ	3.0798	H84A···H85A	2.4737
C31···H43	2.6372	H84A···C74^xvi	3.0425
C31···H28	2.6625	H84B···H85C	2.5014
C40···H85A^vi	2.9971	H84C···O81	2.4534
C41···H85A^vi	3.0792	H84C···H65^xiv	2.4755
C42···H85A^vi	2.9982	H85A···H84A	2.4737
C43···H85A^vi	2.9933	H85A···C40^ix	2.9971
C43···H31	2.6202	H85A···C41^ix	3.0792
C44···H51	2.6947	H85A···C42^ix	2.9982
C44···H85A^vi	3.0662	H85A···C43^ix	2.9933
C45···H85A^vi	3.0423	H85A···C44^ix	3.0662
C46···H66^xii	2.9112	H85A···C45^ix	3.0423
C50···H72ⁱ	2.7829	H85B···H63	2.4503
C51···H63^vi	2.9772	H85B···H82	2.1598
C51···H62	2.6809	H85C···H84B	2.5014
C51···H44	2.6673	H85C···O81^ix	2.5142
C60···H75B^v	3.0888

O2—Cu1—O3	91.31 (9)	C61—C66—C65	120.9 (3)
O2—Cu1—O71	96.05 (9)	O71—C72—N73	125.4 (3)
O2—Cu1—O5ⁱ	167.60 (11)	C21—C22—H22	119.80
O2—Cu1—O6ⁱ	90.60 (9)	C25—C22—H22	119.85
O3—Cu1—O71	88.63 (10)	C26—C25—H25	119.87
O3—Cu1—O5ⁱ	85.24 (9)	C22—C25—H25	119.79
O3—Cu1—O6ⁱ	177.00 (9)	C25—C26—H26	120.09
O5ⁱ—Cu1—O71	95.77 (9)	C27—C26—H26	119.98
O6ⁱ—Cu1—O71	93.47 (10)	C26—C27—H27	120.03
O5ⁱ—Cu1—O6ⁱ	92.42 (9)	C28—C27—H27	120.11
Cu1—O2—C20	125.5 (2)	C21—C28—H28	119.65
Cu1—O3—C30	126.28 (19)	C27—C28—H28	119.77
Cu1ⁱ—O5—C50	125.7 (2)	C20—C31—H31	117.73
Cu1ⁱ—O6—C60	125.2 (2)	C30—C31—H31	117.60
Cu1—O71—C72	115.0 (2)	C45—C43—H43	118.67
C40—O4—H4	109.49	C42—C43—H43	118.70
C72—N73—C74	121.4 (3)	C41—C44—H44	118.54
C72—N73—C75	121.6 (3)	C45—C44—H44	118.52
C74—N73—C75	117.0 (3)	C45—C46—H46A	109.47
C82—N83—C85	118.6 (5)	H46A—C46—H46C	109.45
C84—N83—C85	117.4 (6)	H46B—C46—H46C	109.52
C82—N83—C84	124.0 (6)	H46A—C46—H46B	109.48
C21—C20—C31	120.1 (3)	C45—C46—H46B	109.48
O2—C20—C21	115.3 (3)	C45—C46—H46C	109.42
O2—C20—C31	124.6 (3)	C50—C51—H51	117.75
C22—C21—C28	118.9 (3)	C60—C51—H51	117.81
C20—C21—C22	119.0 (3)	C61—C62—H62	120.01
C20—C21—C28	122.1 (3)	C63—C62—H62	120.12
C21—C22—C25	120.4 (3)	C62—C63—H63	119.47
C22—C25—C26	120.3 (3)	C64—C63—H63	119.44
C25—C26—C27	119.9 (3)	C65—C64—H64	120.17
C26—C27—C28	119.9 (3)	C63—C64—H64	120.13
C21—C28—C27	120.6 (3)	C64—C65—H65	120.05
O3—C30—C42	115.3 (3)	C66—C65—H65	120.15
O3—C30—C31	122.3 (3)	C61—C66—H66	119.57
C31—C30—C42	122.4 (3)	C65—C66—H66	119.55
C20—C31—C30	124.7 (3)	N73—C72—H72	117.27
C41—C40—C42	119.9 (3)	O71—C72—H72	117.29
O4—C40—C41	117.6 (3)	N73—C74—H74B	109.46
O4—C40—C42	122.5 (3)	H74A—C74—H74C	109.38
C40—C41—C50	121.4 (3)	N73—C74—H74C	109.46
C44—C41—C50	119.9 (3)	H74A—C74—H74B	109.46
C40—C41—C44	118.6 (3)	N73—C74—H74A	109.51
C30—C42—C40	120.2 (3)	H74B—C74—H74C	109.55
C30—C42—C43	121.3 (3)	N73—C75—H75C	109.55
C40—C42—C43	118.3 (3)	H75A—C75—H75C	109.46
C42—C43—C45	122.6 (3)	H75B—C75—H75C	109.46
C41—C44—C45	122.9 (3)	H75A—C75—H75B	109.50
C43—C45—C46	121.6 (3)	N73—C75—H75A	109.42
C44—C45—C46	120.7 (3)	N73—C75—H75B	109.44
C43—C45—C44	117.6 (3)	O81—C82—N83	126.3 (6)
O5—C50—C41	116.8 (3)	O81—C82—H82	116.89
C41—C50—C51	119.6 (3)	N83—C82—H82	116.83
O5—C50—C51	123.6 (3)	N83—C84—H84A	109.37
C50—C51—C60	124.4 (3)	N83—C84—H84B	109.49
O6—C60—C51	124.8 (3)	N83—C84—H84C	109.49
O6—C60—C61	114.8 (3)	H84A—C84—H84B	109.41
C51—C60—C61	120.4 (3)	H84A—C84—H84C	109.53
C60—C61—C66	118.7 (3)	H84B—C84—H84C	109.53
C60—C61—C62	122.7 (3)	N83—C85—H85A	109.47
C62—C61—C66	118.6 (3)	N83—C85—H85B	109.45
C61—C62—C63	119.9 (3)	N83—C85—H85C	109.39
C62—C63—C64	121.1 (4)	H85A—C85—H85B	109.68
C63—C64—C65	119.7 (3)	H85A—C85—H85C	109.42
C64—C65—C66	119.8 (3)	H85B—C85—H85C	109.42

O3—Cu1—O2—C20	−19.4 (3)	O3—C30—C42—C43	−173.7 (3)
O71—Cu1—O2—C20	69.4 (3)	O3—C30—C42—C40	1.5 (4)
O6ⁱ—Cu1—O2—C20	162.9 (3)	O3—C30—C31—C20	−2.4 (5)
O2—Cu1—O3—C30	25.0 (3)	C31—C30—C42—C43	6.1 (4)
O71—Cu1—O3—C30	−71.0 (3)	C42—C30—C31—C20	177.9 (3)
O5ⁱ—Cu1—O3—C30	−166.9 (3)	C42—C40—C41—C50	172.3 (3)
O2—Cu1—O71—C72	−170.2 (2)	O4—C40—C42—C30	8.9 (5)
O3—Cu1—O71—C72	−79.0 (2)	C42—C40—C41—C44	−3.9 (5)
O5ⁱ—Cu1—O71—C72	6.1 (2)	C41—C40—C42—C43	3.7 (5)
O6ⁱ—Cu1—O71—C72	98.9 (2)	O4—C40—C41—C44	175.5 (3)
O3—Cu1—O5ⁱ—C50ⁱ	160.6 (3)	O4—C40—C41—C50	−8.3 (5)
O71—Cu1—O5ⁱ—C50ⁱ	72.5 (3)	C41—C40—C42—C30	−171.6 (3)
O2—Cu1—O6ⁱ—C60ⁱ	−174.5 (3)	O4—C40—C42—C43	−175.7 (3)
O71—Cu1—O6ⁱ—C60ⁱ	−78.4 (2)	C50—C41—C44—C45	−174.6 (3)
Cu1—O2—C20—C21	−171.9 (2)	C44—C41—C50—C51	−34.8 (5)
Cu1—O2—C20—C31	7.6 (5)	C44—C41—C50—O5	142.8 (3)
Cu1—O3—C30—C31	−18.3 (4)	C40—C41—C50—O5	−33.3 (5)
Cu1—O3—C30—C42	161.5 (2)	C40—C41—C50—C51	149.1 (3)
Cu1ⁱ—O5—C50—C41	166.9 (2)	C40—C41—C44—C45	1.7 (5)
Cu1ⁱ—O5—C50—C51	−15.6 (5)	C40—C42—C43—C45	−1.2 (5)
Cu1ⁱ—O6—C60—C51	8.3 (4)	C30—C42—C43—C45	174.1 (3)
Cu1ⁱ—O6—C60—C61	−172.3 (2)	C42—C43—C45—C44	−1.1 (5)
Cu1—O71—C72—N73	−173.8 (3)	C42—C43—C45—C46	−178.8 (3)
C75—N73—C72—O71	178.6 (3)	C41—C44—C45—C46	178.6 (3)
C74—N73—C72—O71	−2.1 (5)	C41—C44—C45—C43	0.8 (5)
C84—N83—C82—O81	−2.5 (10)	C41—C50—C51—C60	176.4 (3)
C85—N83—C82—O81	−179.9 (5)	O5—C50—C51—C60	−1.0 (6)
O2—C20—C31—C30	8.0 (6)	C50—C51—C60—O6	4.9 (5)
C31—C20—C21—C28	−17.5 (5)	C50—C51—C60—C61	−174.4 (3)
O2—C20—C21—C22	−16.6 (5)	O6—C60—C61—C66	15.4 (4)
O2—C20—C21—C28	162.0 (3)	C51—C60—C61—C66	−165.2 (3)
C31—C20—C21—C22	163.9 (3)	O6—C60—C61—C62	−163.6 (3)
C21—C20—C31—C30	−172.5 (3)	C51—C60—C61—C62	15.8 (5)
C22—C21—C28—C27	1.1 (5)	C66—C61—C62—C63	−1.1 (5)
C20—C21—C28—C27	−177.5 (3)	C60—C61—C66—C65	−179.1 (3)
C28—C21—C22—C25	0.0 (5)	C60—C61—C62—C63	178.0 (3)
C20—C21—C22—C25	178.6 (3)	C62—C61—C66—C65	0.0 (5)
C21—C22—C25—C26	−0.3 (5)	C61—C62—C63—C64	1.3 (6)
C22—C25—C26—C27	−0.6 (5)	C62—C63—C64—C65	−0.5 (6)
C25—C26—C27—C28	1.7 (5)	C63—C64—C65—C66	−0.7 (6)
C26—C27—C28—C21	−2.0 (5)	C64—C65—C66—C61	0.9 (6)
C31—C30—C42—C40	−178.8 (3)

Symmetry codes: (i) −x, −y, −z+1; (ii) x, y, z+1; (iii) −x+1, −y, −z+2; (iv) −x+1, −y, −z+1; (v) −x, −y, −z; (vi) x, −y+1/2, z+1/2; (vii) x−1, y, z; (viii) −x, y−1/2, −z+1/2; (ix) x, −y+1/2, z−1/2; (x) −x, y+1/2, −z+1/2; (xi) x, y, z−1; (xii) x+1, y, z; (xiii) −x+1, y−1/2, −z+1/2; (xiv) x+1, −y+1/2, z+1/2; (xv) x−1, −y+1/2, z−1/2; (xvi) −x+1, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3	0.82	1.78	2.491 (3)	144
C46—H46C···O2^iv	0.96	2.60	3.455 (4)	149
C72—H72···O4ⁱ	0.93	2.48	3.382 (4)	163
C72—H72···O5ⁱ	0.93	2.57	3.224 (4)	127
C74—H74A···O71	0.96	2.41	2.815 (5)	105
C84—H84C···O81	0.96	2.45	2.841 (9)	104
C85—H85C···O81^ix	0.96	2.51	3.297 (7)	139

Symmetry codes: (i) −x, −y, −z+1; (iv) −x+1, −y, −z+1; (ix) x, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₂₅H₁₈O₅)₂(C₃H₇NO)₂]·2C₃H₇NO
M_r	1216.27
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	150
a, b, c (Å)	10.784 (1), 29.701 (4), 8.8317 (10)
β (°)	93.015 (10)
V (Å³)	2824.8 (6)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.83
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	58094, 6483, 4487
R_int	0.095
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.157, 1.05
No. of reflections	6483
No. of parameters	375
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.98, −0.58

Computer programs: COLLECT (Nonius, 1998), DENZO (Otwinowski & Minor, 1997), DENZO, SHELXS86 (Sheldrick, 1985), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2002), PLATON.

Selected geometric parameters (Å, º) top

Cu1—O2	1.920 (2)	O4—C40	1.347 (4)
Cu1—O3	1.918 (2)	O5—C50	1.281 (4)
Cu1—O71	2.409 (3)	O6—C60	1.287 (4)
Cu1—O5ⁱ	1.917 (2)	C20—C31	1.407 (5)
Cu1—O6ⁱ	1.919 (2)	C50—C51	1.407 (5)
O2—C20	1.278 (4)	C51—C60	1.396 (5)
O3—C30	1.293 (4)

O2—Cu1—O3	91.31 (9)	O3—Cu1—O5ⁱ	85.24 (9)
O2—Cu1—O71	96.05 (9)	O3—Cu1—O6ⁱ	177.00 (9)
O2—Cu1—O5ⁱ	167.60 (11)	O5ⁱ—Cu1—O71	95.77 (9)
O2—Cu1—O6ⁱ	90.60 (9)	O6ⁱ—Cu1—O71	93.47 (10)
O3—Cu1—O71	88.63 (10)	O5ⁱ—Cu1—O6ⁱ	92.42 (9)

Symmetry code: (i) −x, −y, −z+1.