Tetra­kis(μ-4-ethyl­benzoato-κ2O:O′)­bis­[(4-ethyl­benzoic acid-κO)copper(II)]

Sunil, A.C.; Bezuidenhoudt, B.C.B.; Janse van Rensburg, J.M.

doi:10.1107/S1600536808015924

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page m939

doi:10.1107/S1600536808015924

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Tetrakis(μ-4-ethylbenzoato-κ²O:O′)bis[(4-ethylbenzoic acid-κO)copper(II)]

Abraham C. Sunil,^a Barend C. B. Bezuidenhoudt ^a ^* and J. Marthinus Janse van Rensburg ^a

^aDepartment of Chemistry, University of the Free State, PO Box 339, Bloemfontein 9300, South Africa
^*Correspondence e-mail: bezuidbc.sci@ufs.ac.za

(Received 20 May 2008; accepted 27 May 2008; online 19 June 2008)

The molecule of the title compound, [Cu₂(C₉H₉O₂)₄(C₉H₁₀O₂)₂], lies on a center of inversion. It consists of four bridging ethylbenzoate ligands, forming a cage around two Cu atoms in a syn–syn configuration, and two monodentate ethylbenzoic acid ligands bonded apically to the square-planar Cu atoms. The Cu⋯Cu distance is 2.6047 (5) Å.

Related literature

For the synthesis of aromatic carboxylic acids, see: Kaeding (1967 ). For tetrakis(μ₂-2-methylbenzoato)bis(2-methylbenzoic acid)dicopper(II), see: Sunil et al. (2008 ). For tetrakis(μ₂-2-fluorobenzoato)bis(2-fluorobenzoic acid)dicopper(II), see: Valach et al. (2000 ). For tetrakis(μ₂benzoato) bis(2-fluorobenzoic acid)dicopper(II), see: Kawata et al. (1992 ). For tetrakis-[μ-(2-phenoxybenzoato-O,O′)]bis[(2-phenoxybenzoic acid)copper(II)], see: Mak & Yip (1990 ).

Experimental

Crystal data

[Cu₂(C₉H₉O₂)₄(C₉H₁₀O₂)₂]
M_r = 1024.07
Triclinic, $[P \overline 1]$
a = 10.6167 (5) Å
b = 10.7394 (7) Å
c = 10.8096 (7) Å
α = 81.848 (3)°
β = 88.594 (3)°
γ = 79.468 (2)°
V = 1199.47 (12) Å³
Z = 1
Mo Kα radiation
μ = 0.95 mm⁻¹
T = 100 (2) K
0.54 × 0.4 × 0.39 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ) T_min = 0.628, T_max = 0.708
15971 measured reflections
5683 independent reflections
4721 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.103
S = 1.03
5683 reflections
311 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O3	1.9498 (15)
Cu1—O4	1.9501 (16)
Cu1—O2	1.9593 (16)
Cu1—O1	2.0040 (16)
Cu1—O5	2.1761 (15)
Cu1—Cu1ⁱ	2.6047 (5)
Symmetry code: (i) -x+1, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015924/fi2063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808015924/fi2063Isup2.hkl

checkCIF report

Comment top

The title compound forms part of the copper(II) complexes of the type [Cu₂(RCO₂)₄L₂] (R=aryl, L=monodentate ligand). This type of complex forms tetra-(carboxylato-O,O') bridges and four of the carboxylate groups hold together two Cu atoms (Fig. 1). The Cu···Cu distance in the title compound is 2.6047 (5) Å, probably displaying weak orbital interaction considering that the van der Waals radius of copper is 2.32 Å. The axial sites of each copper atom are bonded to a monodentate p-ethylbenzoic acid ligand. In turn the acid protons are hydrogen bonded to the cage carboxylate O atoms, O—H···O = 166.79° and O···O = 2.645 Å.

Neighbouring molecules stack with overlap between the axially bonded phenyl rings displaying a centroid to centroid distance of 4.2918 (3) Å and an interplanar distance of 3.6277 Å (Fig. 2 A). This inter-molecular interaction influence the dihedral angle displayed between the phenyl rings from the axially bonded monodentate ligands and the carboxylic oxygen plane, O1, O2, O1ⁱ and O2ⁱ (i = 1 - x, 1 - y, 2 - z). Molecular packing in the (0 0 h) plane is in a puckered pseudo-hexagonal close packing fashion. This close packing is stabilized by soft inter-molecular C···H contacts ranging from 2.720–2.813 Å (Fig. 2B).

Related literature top

For the synthesis of aromatic carboxylic acids, see: Kaeding (1967). For tetrakis(µ₂-2-methylbenzoato)bis(2-methylbenzoic acid)dicopper(II), see: Sunil et al. (2008). For tetrakis(µ₂-2-fluorobenzoato)bis(2-fluorobenzoic acid)dicopper(II), see: Valach et al. (2000). For tetrakis(µ₂benzoato) bis(2-fluorobenzoic acid)dicopper(II), see: Kawata et al. (1992). For tetrakis-[µ-(2-phenoxybenzoato-O,O')]bis[(2-phenoxybenzoic acid)copper(II)], see Mak & Yip (1990).

Experimental top

The complex [Cu₂(C₉H₁₀O₂)₄(C₉H₁₁O₂)₂] was prepared by heating 4-ethylbenzoic acid (1.77 g, 11.81 mmol), copper carbonate (0.74 g, 3.34 mmol) and magnesium oxide (0.20 g, 4.98 mmol) under reflux, in toluene (15 ml) for 60 h. The product was extacted and crystallized from diethyl ether to yield a blue crystalline solid. (Yield: 80%)

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A view of (I) showing the atom-numbering scheme with displacement ellipsoids at the 30% probability level, non labelled atoms are symmetric equivalents. For the phenyl C-atoms, the first digit indicates ring number and the second digit the position of the atom in the ring. Symmetry code: 1 - x, 1 - y, 2 - z.
	Fig. 2. (A) Hacked lines indicate overlap between ethylbenzoic groups of neighbouring molecules. (B) Indication of pseudo-hexagonal close packing along the c axis.

Tetrakis(µ-4-ethylbenzoato-κ²O:O')bis[(4-ethylbenzoic acid-κO)copper(II)] top

Crystal data top

[Cu₂(C₉H₉O₂)₄(C₉H₁₀O₂)₂]	Z = 1
M_r = 1024.07	F(000) = 534
Triclinic, P1	D_x = 1.418 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71069 Å
a = 10.6167 (5) Å	Cell parameters from 4441 reflections
b = 10.7394 (7) Å	θ = 2.5–28.2°
c = 10.8096 (7) Å	µ = 0.95 mm⁻¹
α = 81.848 (3)°	T = 100 K
β = 88.594 (3)°	Cuboid, blue
γ = 79.468 (2)°	0.54 × 0.4 × 0.39 mm
V = 1199.47 (12) Å³

Data collection top

Bruker Kappa APEXII diffractometer	5683 independent reflections
Radiation source: fine-focus sealed tube	4721 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω and ϕ scans	θ_max = 28°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −7→14
T_min = 0.628, T_max = 0.708	k = −14→14
15971 measured reflections	l = −14→14

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.040	w = 1/[σ²(F_o²) + (0.0447P)² + 0.9309P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.103	(Δ/σ)_max = 0.001
S = 1.04	Δρ_max = 0.50 e Å⁻³
5683 reflections	Δρ_min = −0.37 e Å⁻³
311 parameters

Crystal data top

[Cu₂(C₉H₉O₂)₄(C₉H₁₀O₂)₂]	γ = 79.468 (2)°
M_r = 1024.07	V = 1199.47 (12) Å³
Triclinic, P1	Z = 1
a = 10.6167 (5) Å	Mo Kα radiation
b = 10.7394 (7) Å	µ = 0.95 mm⁻¹
c = 10.8096 (7) Å	T = 100 K
α = 81.848 (3)°	0.54 × 0.4 × 0.39 mm
β = 88.594 (3)°

Data collection top

Bruker Kappa APEXII diffractometer	5683 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2004)	4721 reflections with I > 2σ(I)
T_min = 0.628, T_max = 0.708	R_int = 0.040
15971 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.04	Δρ_max = 0.50 e Å⁻³
5683 reflections	Δρ_min = −0.37 e Å⁻³
311 parameters

Special details top

Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 2 s/frame. A total of 1507 frames were collected with a frame width of 0.5° covering up to θ = 28.0° with 98.3% completeness accomplished.

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.45033 (3)	0.46672 (2)	0.90347 (2)	0.01213 (9)
O6	0.58444 (17)	0.40202 (18)	0.62540 (16)	0.0239 (4)
H6	0.599	0.4445	0.679	0.036*
O1	0.60816 (15)	0.51776 (15)	0.82165 (14)	0.0152 (3)
O3	0.36215 (15)	0.64398 (14)	0.86973 (14)	0.0166 (3)
O4	0.54987 (16)	0.29874 (15)	0.96412 (14)	0.0181 (3)
O2	0.30749 (15)	0.42705 (15)	1.01089 (14)	0.0167 (3)
O5	0.40263 (15)	0.39621 (15)	0.73471 (14)	0.0168 (3)
C51	0.4404 (2)	0.2808 (2)	0.5616 (2)	0.0144 (4)
C11	0.8123 (2)	0.58002 (19)	0.80261 (19)	0.0124 (4)
C30	0.3784 (2)	0.7244 (2)	0.94028 (19)	0.0140 (4)
C53	0.3163 (2)	0.1251 (2)	0.5207 (2)	0.0192 (5)
H53	0.2542	0.0759	0.546	0.023*
C55	0.4715 (2)	0.1870 (2)	0.3717 (2)	0.0172 (5)
H55	0.5134	0.1806	0.2957	0.021*
C52	0.3464 (2)	0.2079 (2)	0.5971 (2)	0.0172 (5)
H52	0.3038	0.215	0.6727	0.021*
C54	0.3778 (2)	0.1138 (2)	0.4054 (2)	0.0169 (5)
C36	0.2111 (2)	0.8866 (2)	0.8178 (2)	0.0171 (5)
H36	0.1956	0.823	0.773	0.02*
C16	0.9223 (2)	0.5936 (2)	0.8637 (2)	0.0145 (4)
H16	0.9212	0.5918	0.95	0.017*
C10	0.6968 (2)	0.55566 (19)	0.87604 (19)	0.0133 (4)
C31	0.3059 (2)	0.8585 (2)	0.9087 (2)	0.0143 (4)
C34	0.1628 (2)	1.1064 (2)	0.8569 (2)	0.0184 (5)
C32	0.3321 (2)	0.9558 (2)	0.9709 (2)	0.0191 (5)
H32	0.3968	0.9384	1.0306	0.023*
C56	0.5043 (2)	0.2694 (2)	0.4481 (2)	0.0162 (5)
H56	0.5682	0.3166	0.424	0.019*
C12	0.8152 (2)	0.5865 (2)	0.6725 (2)	0.0146 (4)
H12	0.743	0.5777	0.63	0.018*
C541	0.3421 (3)	0.0255 (2)	0.3213 (2)	0.0235 (5)
H54A	0.3627	−0.0618	0.3633	0.028*
H54B	0.3936	0.0313	0.2461	0.028*
C141	1.1539 (2)	0.6401 (2)	0.5944 (2)	0.0208 (5)
H14A	1.1803	0.571	0.5452	0.025*
H14B	1.2228	0.6391	0.6521	0.025*
C50	0.4725 (2)	0.3652 (2)	0.6484 (2)	0.0155 (5)
C13	0.9247 (2)	0.6059 (2)	0.6070 (2)	0.0158 (5)
H13	0.9246	0.6114	0.5203	0.019*
C15	1.0327 (2)	0.6096 (2)	0.7979 (2)	0.0164 (5)
H15	1.1059	0.6153	0.8408	0.02*
C14	1.0360 (2)	0.6173 (2)	0.6679 (2)	0.0152 (4)
C642	−0.0475 (3)	1.2359 (3)	0.9030 (3)	0.0385 (7)
H64A	−0.0923	1.1768	0.8717	0.058*
H64B	−0.0989	1.32	0.8901	0.058*
H64C	−0.0311	1.21	0.9907	0.058*
C641	0.0790 (3)	1.2371 (2)	0.8338 (2)	0.0254 (6)
H64D	0.0628	1.2612	0.7449	0.03*
H64E	0.1226	1.2997	0.8623	0.03*
C33	0.2619 (3)	1.0788 (2)	0.9443 (2)	0.0229 (5)
H33	0.2812	1.1435	0.9852	0.028*
C35	0.1394 (2)	1.0083 (2)	0.7935 (2)	0.0186 (5)
H35	0.0746	1.0253	0.7339	0.022*
C142	1.1323 (3)	0.7677 (3)	0.5072 (3)	0.0323 (6)
H14C	1.0651	0.7688	0.449	0.048*
H14D	1.2099	0.7775	0.4623	0.048*
H14E	1.1085	0.8367	0.5556	0.048*
C542	0.2016 (3)	0.0542 (2)	0.2846 (2)	0.0277 (6)
H54C	0.1498	0.0463	0.3583	0.042*
H54D	0.1855	−0.0053	0.231	0.042*
H54E	0.1807	0.1397	0.2412	0.042*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01076 (16)	0.01499 (14)	0.01135 (13)	−0.00383 (10)	0.00010 (10)	−0.00231 (9)
O6	0.0189 (10)	0.0369 (10)	0.0225 (9)	−0.0156 (8)	0.0057 (7)	−0.0139 (7)
O1	0.0110 (8)	0.0221 (8)	0.0148 (7)	−0.0076 (7)	0.0005 (6)	−0.0041 (6)
O3	0.0161 (9)	0.0154 (7)	0.0184 (8)	−0.0022 (6)	−0.0021 (7)	−0.0032 (6)
O4	0.0212 (9)	0.0164 (8)	0.0168 (8)	−0.0025 (7)	−0.0044 (7)	−0.0032 (6)
O2	0.0130 (8)	0.0256 (8)	0.0138 (7)	−0.0087 (7)	0.0014 (6)	−0.0036 (6)
O5	0.0144 (9)	0.0232 (8)	0.0142 (7)	−0.0042 (7)	0.0001 (6)	−0.0059 (6)
C51	0.0119 (12)	0.0176 (10)	0.0129 (10)	−0.0019 (9)	−0.0023 (8)	0.0001 (8)
C11	0.0097 (11)	0.0118 (9)	0.0152 (10)	−0.0021 (8)	−0.0009 (8)	−0.0005 (8)
C30	0.0114 (11)	0.0179 (10)	0.0130 (10)	−0.0047 (9)	0.0049 (8)	−0.0008 (8)
C53	0.0187 (13)	0.0212 (11)	0.0195 (11)	−0.0096 (10)	0.0022 (10)	−0.0010 (9)
C55	0.0149 (12)	0.0217 (11)	0.0139 (10)	0.0000 (9)	0.0025 (9)	−0.0030 (9)
C52	0.0159 (12)	0.0235 (11)	0.0126 (10)	−0.0057 (10)	0.0022 (9)	−0.0015 (9)
C54	0.0152 (12)	0.0178 (11)	0.0169 (11)	0.0007 (9)	−0.0032 (9)	−0.0041 (9)
C36	0.0165 (12)	0.0166 (10)	0.0184 (11)	−0.0035 (9)	0.0004 (9)	−0.0026 (8)
C16	0.0140 (12)	0.0171 (10)	0.0128 (10)	−0.0039 (9)	−0.0025 (9)	−0.0019 (8)
C10	0.0147 (12)	0.0124 (10)	0.0122 (9)	−0.0027 (9)	−0.0021 (8)	0.0009 (8)
C31	0.0111 (11)	0.0164 (10)	0.0155 (10)	−0.0038 (9)	0.0037 (9)	−0.0014 (8)
C34	0.0192 (13)	0.0159 (11)	0.0191 (11)	−0.0037 (9)	0.0064 (9)	0.0001 (9)
C32	0.0186 (13)	0.0215 (11)	0.0174 (11)	−0.0029 (10)	−0.0034 (9)	−0.0040 (9)
C56	0.0107 (12)	0.0200 (11)	0.0180 (11)	−0.0046 (9)	0.0013 (9)	−0.0015 (9)
C12	0.0112 (12)	0.0175 (10)	0.0161 (10)	−0.0041 (9)	−0.0022 (9)	−0.0029 (8)
C541	0.0256 (14)	0.0240 (12)	0.0239 (12)	−0.0073 (11)	0.0018 (11)	−0.0101 (10)
C141	0.0140 (12)	0.0277 (12)	0.0229 (12)	−0.0086 (10)	0.0037 (10)	−0.0059 (10)
C50	0.0142 (12)	0.0175 (10)	0.0145 (10)	−0.0032 (9)	−0.0027 (9)	−0.0008 (8)
C13	0.0145 (12)	0.0196 (11)	0.0133 (10)	−0.0033 (9)	0.0008 (9)	−0.0025 (8)
C15	0.0118 (12)	0.0185 (11)	0.0199 (11)	−0.0054 (9)	−0.0041 (9)	−0.0016 (9)
C14	0.0114 (12)	0.0131 (10)	0.0210 (11)	−0.0030 (9)	0.0021 (9)	−0.0019 (8)
C642	0.0278 (17)	0.0213 (13)	0.065 (2)	−0.0006 (12)	0.0111 (15)	−0.0078 (13)
C641	0.0290 (15)	0.0182 (11)	0.0273 (13)	−0.0024 (11)	0.0028 (11)	−0.0008 (10)
C33	0.0306 (15)	0.0184 (11)	0.0211 (12)	−0.0052 (11)	0.0008 (11)	−0.0067 (9)
C35	0.0147 (13)	0.0198 (11)	0.0202 (11)	−0.0022 (9)	−0.0024 (9)	−0.0003 (9)
C142	0.0232 (15)	0.0422 (16)	0.0296 (14)	−0.0106 (13)	−0.0002 (12)	0.0071 (12)
C542	0.0304 (16)	0.0261 (13)	0.0292 (13)	−0.0071 (11)	−0.0066 (11)	−0.0086 (10)

Geometric parameters (Å, º) top

Cu1—O3	1.9498 (15)	C31—C32	1.392 (3)
Cu1—O4	1.9501 (16)	C34—C33	1.394 (3)
Cu1—O2	1.9593 (16)	C34—C35	1.397 (3)
Cu1—O1	2.0040 (16)	C34—C641	1.509 (3)
Cu1—O5	2.1761 (15)	C32—C33	1.387 (3)
Cu1—Cu1ⁱ	2.6047 (5)	C32—H32	0.93
O6—C50	1.326 (3)	C56—H56	0.93
O6—H6	0.82	C12—C13	1.380 (3)
O1—C10	1.277 (3)	C12—H12	0.93
O3—C30	1.267 (3)	C541—C542	1.517 (4)
O4—C30ⁱ	1.267 (3)	C541—H54A	0.97
O2—C10ⁱ	1.261 (2)	C541—H54B	0.97
O5—C50	1.223 (3)	C141—C14	1.505 (3)
C51—C52	1.392 (3)	C141—C142	1.532 (3)
C51—C56	1.397 (3)	C141—H14A	0.97
C51—C50	1.479 (3)	C141—H14B	0.97
C11—C16	1.396 (3)	C13—C14	1.400 (3)
C11—C12	1.398 (3)	C13—H13	0.93
C11—C10	1.488 (3)	C15—C14	1.396 (3)
C30—O4ⁱ	1.267 (3)	C15—H15	0.93
C30—C31	1.501 (3)	C642—C641	1.523 (4)
C53—C52	1.378 (3)	C642—H64A	0.96
C53—C54	1.403 (3)	C642—H64B	0.96
C53—H53	0.93	C642—H64C	0.96
C55—C56	1.386 (3)	C641—H64D	0.97
C55—C54	1.388 (3)	C641—H64E	0.97
C55—H55	0.93	C33—H33	0.93
C52—H52	0.93	C35—H35	0.93
C54—C541	1.505 (3)	C142—H14C	0.96
C36—C35	1.381 (3)	C142—H14D	0.96
C36—C31	1.387 (3)	C142—H14E	0.96
C36—H36	0.93	C542—H54C	0.96
C16—C15	1.382 (3)	C542—H54D	0.96
C16—H16	0.93	C542—H54E	0.96
C10—O2ⁱ	1.261 (2)

O3—Cu1—O4	169.67 (6)	C55—C56—C51	119.3 (2)
O3—Cu1—O2	89.21 (7)	C55—C56—H56	120.3
O4—Cu1—O2	89.79 (7)	C51—C56—H56	120.3
O3—Cu1—O1	89.64 (7)	C13—C12—C11	120.3 (2)
O4—Cu1—O1	89.46 (7)	C13—C12—H12	119.8
O2—Cu1—O1	169.42 (6)	C11—C12—H12	119.8
O3—Cu1—O5	100.25 (6)	C54—C541—C542	113.8 (2)
O4—Cu1—O5	90.05 (6)	C54—C541—H54A	108.8
O2—Cu1—O5	99.99 (6)	C542—C541—H54A	108.8
O1—Cu1—O5	90.57 (6)	C54—C541—H54B	108.8
O3—Cu1—Cu1ⁱ	86.32 (5)	C542—C541—H54B	108.8
O4—Cu1—Cu1ⁱ	83.36 (5)	H54A—C541—H54B	107.7
O2—Cu1—Cu1ⁱ	87.95 (5)	C14—C141—C142	112.7 (2)
O1—Cu1—Cu1ⁱ	81.48 (4)	C14—C141—H14A	109.1
O5—Cu1—Cu1ⁱ	169.69 (5)	C142—C141—H14A	109.1
C50—O6—H6	109.5	C14—C141—H14B	109.1
C10—O1—Cu1	125.79 (14)	C142—C141—H14B	109.1
C30—O3—Cu1	120.62 (14)	H14A—C141—H14B	107.8
C30ⁱ—O4—Cu1	124.01 (14)	O5—C50—O6	123.3 (2)
C10ⁱ—O2—Cu1	120.97 (15)	O5—C50—C51	122.7 (2)
C50—O5—Cu1	128.90 (15)	O6—C50—C51	113.97 (19)
C52—C51—C56	119.6 (2)	C12—C13—C14	121.5 (2)
C52—C51—C50	118.4 (2)	C12—C13—H13	119.2
C56—C51—C50	122.0 (2)	C14—C13—H13	119.2
C16—C11—C12	118.5 (2)	C16—C15—C14	120.9 (2)
C16—C11—C10	120.04 (19)	C16—C15—H15	119.5
C12—C11—C10	121.5 (2)	C14—C15—H15	119.5
O3—C30—O4ⁱ	125.7 (2)	C15—C14—C13	117.8 (2)
O3—C30—C31	117.29 (19)	C15—C14—C141	121.5 (2)
O4ⁱ—C30—C31	117.03 (19)	C13—C14—C141	120.7 (2)
C52—C53—C54	121.0 (2)	C641—C642—H64A	109.5
C52—C53—H53	119.5	C641—C642—H64B	109.5
C54—C53—H53	119.5	H64A—C642—H64B	109.5
C56—C55—C54	121.9 (2)	C641—C642—H64C	109.5
C56—C55—H55	119.1	H64A—C642—H64C	109.5
C54—C55—H55	119.1	H64B—C642—H64C	109.5
C53—C52—C51	120.3 (2)	C34—C641—C642	110.1 (2)
C53—C52—H52	119.9	C34—C641—H64D	109.6
C51—C52—H52	119.9	C642—C641—H64D	109.6
C55—C54—C53	117.9 (2)	C34—C641—H64E	109.6
C55—C54—C541	121.5 (2)	C642—C641—H64E	109.6
C53—C54—C541	120.6 (2)	H64D—C641—H64E	108.2
C35—C36—C31	120.3 (2)	C32—C33—C34	120.8 (2)
C35—C36—H36	119.8	C32—C33—H33	119.6
C31—C36—H36	119.8	C34—C33—H33	119.6
C15—C16—C11	120.9 (2)	C36—C35—C34	121.1 (2)
C15—C16—H16	119.5	C36—C35—H35	119.5
C11—C16—H16	119.5	C34—C35—H35	119.5
O2ⁱ—C10—O1	123.7 (2)	C141—C142—H14C	109.5
O2ⁱ—C10—C11	117.84 (19)	C141—C142—H14D	109.5
O1—C10—C11	118.46 (18)	H14C—C142—H14D	109.5
C36—C31—C32	119.2 (2)	C141—C142—H14E	109.5
C36—C31—C30	120.3 (2)	H14C—C142—H14E	109.5
C32—C31—C30	120.5 (2)	H14D—C142—H14E	109.5
C33—C34—C35	118.2 (2)	C541—C542—H54C	109.5
C33—C34—C641	121.5 (2)	C541—C542—H54D	109.5
C35—C34—C641	120.2 (2)	H54C—C542—H54D	109.5
C33—C32—C31	120.3 (2)	C541—C542—H54E	109.5
C33—C32—H32	119.9	H54C—C542—H54E	109.5
C31—C32—H32	119.9	H54D—C542—H54E	109.5

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₉H₉O₂)₄(C₉H₁₀O₂)₂]
M_r	1024.07
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	10.6167 (5), 10.7394 (7), 10.8096 (7)
α, β, γ (°)	81.848 (3), 88.594 (3), 79.468 (2)
V (Å³)	1199.47 (12)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.95
Crystal size (mm)	0.54 × 0.4 × 0.39

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2004)
T_min, T_max	0.628, 0.708
No. of measured, independent and observed [I > 2σ(I)] reflections	15971, 5683, 4721
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.661

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.103, 1.04
No. of reflections	5683
No. of parameters	311
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.37

Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004) and XPREP (Bruker, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu1—O3	1.9498 (15)	Cu1—Cu1ⁱ	2.6047 (5)
Cu1—O4	1.9501 (16)	C51—C50	1.479 (3)
Cu1—O2	1.9593 (16)	C11—C10	1.488 (3)
Cu1—O1	2.0040 (16)	C30—C31	1.501 (3)
Cu1—O5	2.1761 (15)

Symmetry code: (i) −x+1, −y+1, −z+2.

Acknowledgements

Financial assistance from the University of the Free State and SASOL to ACS is gratefully acknowledged. Opinions, findings, conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of SASOL.

References

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