Tetra­kis(μ-4-chloro­benzoato-κ2O:O′)bis­[(ethanol-κO)copper(II)](Cu—Cu)

Mollica Nardo, V.; Nicoló, F.; Saccà, A.; Bruno, G.; Ielo, I.

doi:10.1107/S1600536813006909

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 4| April 2013| Page m221

doi:10.1107/S1600536813006909

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Tetrakis(μ-4-chlorobenzoato-κ²O:O′)bis[(ethanol-κO)copper(II)](Cu—Cu)

Viviana Mollica Nardo,^a Francesco Nicoló,^a ^* Alessandro Saccà,^a Giuseppe Bruno ^a and Ileana Ielo ^a

^aDipartimento di Scienze Chimiche, Universitá di Messina, Viale F. Stagno d'Alcontres 31, 98166 Messina, Italy
^*Correspondence e-mail: fnicolo@unime.it

(Received 19 February 2013; accepted 12 March 2013; online 16 March 2013)

In the centrosymmetric dinuclear title Cu^II complex, [Cu₂(C₇H₄ClO₂)(C₂H₅OH)₂], the Cu—Cu distance is 2.5905 (4) Å. The two metal atoms are bridged by four 4-chlorobenzoate ligands and each has an ethanol molecule in the axial position of the overall octahedral coordination environment. The crystal packing features O—H⋯O hydrogen bonds.

Related literature

For general background to metal-coordination polymers, see: Deka et al. (2006 ); Eddaoudi et al. (2001 ); Casarin et al. (2005 ). For their coordination modes, see: Chen & Chen (2002 ). For related structures, see: Hauptmann et al. (2000 ); Ueda et al. (2005 ); Hökelek et al. (2008 ); Hu et al. (2004 ).

Experimental

Crystal data

[Cu₂(C₇H₄ClO₂)(C₂H₆O)₂]
M_r = 841.42
Triclinic, $[P \overline 1]$
a = 6.5766 (1) Å
b = 11.1792 (2) Å
c = 12.4355 (3) Å
α = 93.175 (1)°
β = 103.890 (1)°
γ = 98.688 (1)°
V = 873.34 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.58 mm⁻¹
T = 296 K
0.38 × 0.18 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ) T_min = 0.695, T_max = 0.746
36853 measured reflections
5070 independent reflections
4288 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.102
S = 1.03
5070 reflections
220 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O2ⁱ	0.82	2.35	3.073 (3)	148
O5—H5⋯O3ⁱⁱ	0.82	2.57	3.047 (3)	118
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y, -z.

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW (Siemens, 1996 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813006909/fj2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813006909/fj2617Isup2.hkl

checkCIF report

Comment top

The chemistry of metal-coordination polymers has been advanced due to their diverse topologies and potential applications in smart optoelectronic, magnetic, microporous and biomimetic materials with specific structures, properties, and reactivities (Deka et al., 2006; Eddaoudi et al., 2001). A coordination polymer contains one or more center of metal linked by coordinated ligands into an infinite array, in one/two or three dimension. Coordination polymers constitute one of the most important classes of organic–inorganic hybrid materials (Casarin et al., 2005) that have been the subject of intensive research in recent years. In this paper is presented a new dinuclear complex of copper(II).

The carboxylates ligands have different coordination modes so it is important to have control on the binding of carboxylate to a metal ion in specific manner in the presence of other ligand/s. Some benzoic acid derivatives, such as 4-aminobenzoic acid, have been extensively reported in coordination chemistry, as bifunctional organic ligands, due to the varieties of their coordination modes (Chen & Chen, 2002; Hauptmann et al., 2000). In this compound the copper have a octahedral coordination and combine another center of copper, four oxygen of four acid and one ethanol. The copper dimer has a perfect Ci symmetry and is placed on a crystallographic centre of inversion (Figure 1). The mean value of the distances Cu—O [1.953 (2) Å] is similar to that reported in other structures (Ueda et al., 2005; Hökelek et al., 2008). The structure is very similar to another already known (Hu et al., 2004) differing for the halogen atom bonded to the carboxylic acid.

The crystal packing is constituted by centrosymmetric couple (3 - x, -y, 1 - z) of the dinuclear complexes assembled by weak π-stacking interaction of the C2—C7 aromatic rings [C5 at 3.586 (4) Å from centroid of the other ring] and a chlorine Cl1 interaction with the C9—C14 ring of the other molecule [Cl1—C9 is 3.387 (3) Å] (Figure 2). The packing is further stabilized by intermolecular hydrogen bonds (Tables 1).

Related literature top

For general background to metal-coordination polymers, see Deka et al. (2006); Eddaoudi et al. (2001); Casarin et al. (2005). For their coordination modes, see Chen & Chen (2002). For related structures, see Hauptmann et al. (2000); Ueda et al. (2005); Hökelek et al. (2008); Hu et al. (2004).

Experimental top

The reagents used here were purchased from commercial sources (Sigma–Aldrich). To synthetize the title complex 1 ml of Copper(II) Chloride (0,1 mmol; 100mM) were added to a water (3 ml) / ethanol (3 ml) mixture containing 0,0134 g of melanine and 0,017 g of acid p-Chlorobenzoic. The reaction was sealed in a Teflon-lined stainless steel autoclave, which was heated at 130°C for 3 days under autogenous pressure. After slow cooling to room temperature in 6 h. In this conditions are formed green crystals of the complex and colourless crystal of melamine. A suitable sample of the green crystals has been selected by optical microscope and used in X-Ray structure determination.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XPW (Siemens, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Perspective view of the title molecule with the corresponding atom labelling of the crystallographic asymmetric unit. The equivalent centrosymmetric fragment (2 - x, -y, -z) is represented by empty style. Displacement ellipsoids are plotted at a 30% probability level while H atom size is arbitrary.
	Fig. 2. Crystal packing of the dinuclear units showing the centrosymmetric arrangement of each complex couple (3 - x, -y, 1 - z) assembled by weak π-stacking and chlorine-phenyl interactions. Displacement ellipsoids are plotted at a 30% probability level and H atoms are drawn with an arbitrary radius.

Tetrakis(µ-4-chlorobenzoato-κ²O:O')bis[(ethanol-κO)copper(II)](Cu—Cu) top

Crystal data top

[Cu₂(C₇H₄ClO₂)(C₂H₆O)₂]	Z = 1
M_r = 841.42	F(000) = 426
Triclinic, P1	D_x = 1.600 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.5766 (1) Å	Cell parameters from 9962 reflections
b = 11.1792 (2) Å	θ = 2.6–28.9°
c = 12.4355 (3) Å	µ = 1.58 mm⁻¹
α = 93.175 (1)°	T = 296 K
β = 103.890 (1)°	Irregular, green
γ = 98.688 (1)°	0.38 × 0.18 × 0.10 mm
V = 873.34 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	5070 independent reflections
Radiation source: fine-focus sealed tube	4288 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 30.1°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −9→9
T_min = 0.695, T_max = 0.746	k = −15→15
36853 measured reflections	l = −17→17

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.102	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0523P)² + 0.4776P] where P = (F_o² + 2F_c²)/3
5070 reflections	(Δ/σ)_max = 0.004
220 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

[Cu₂(C₇H₄ClO₂)(C₂H₆O)₂]	γ = 98.688 (1)°
M_r = 841.42	V = 873.34 (3) Å³
Triclinic, P1	Z = 1
a = 6.5766 (1) Å	Mo Kα radiation
b = 11.1792 (2) Å	µ = 1.58 mm⁻¹
c = 12.4355 (3) Å	T = 296 K
α = 93.175 (1)°	0.38 × 0.18 × 0.10 mm
β = 103.890 (1)°

Data collection top

Bruker APEXII CCD diffractometer	5070 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	4288 reflections with I > 2σ(I)
T_min = 0.695, T_max = 0.746	R_int = 0.033
36853 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.03	Δρ_max = 0.50 e Å⁻³
5070 reflections	Δρ_min = −0.42 e Å⁻³
220 parameters

Special details top

Experimental. SADABS-2008/1 - Bruker AXS area detector scaling and absorption correction. wR2(int) was 0.0889 before and 0.0361 after correction.

The crystals suitable for the X-ray analysis were obtained by solvothermal synthesis of the reaction of p-Chlorobenzoate with Copper(II) salt in water/ethanol (1:1) mixed together with melanin.

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 > 2σ(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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.83458 (4)	−0.06609 (2)	0.018444 (19)	0.02666 (8)
O1	1.0314 (3)	−0.10047 (19)	0.15327 (16)	0.0579 (5)
O2	1.3138 (3)	0.00860 (19)	0.11950 (14)	0.0505 (5)
C1	1.2246 (3)	−0.05778 (18)	0.17776 (17)	0.0314 (4)
C2	1.3598 (3)	−0.08960 (19)	0.28342 (17)	0.0327 (4)
C3	1.2696 (4)	−0.1556 (2)	0.3558 (2)	0.0430 (5)
H3	1.1231	−0.1805	0.3386	0.052*
C4	1.3950 (5)	−0.1850 (3)	0.4537 (2)	0.0519 (6)
H4	1.3341	−0.2293	0.5026	0.062*
C5	1.6119 (5)	−0.1476 (2)	0.47747 (19)	0.0473 (6)
C6	1.7056 (4)	−0.0834 (2)	0.4065 (2)	0.0470 (6)
H6	1.8524	−0.0603	0.4236	0.056*
C7	1.5796 (4)	−0.0530 (2)	0.30873 (19)	0.0404 (5)
H7	1.6414	−0.0085	0.2604	0.048*
Cl1	1.77151 (15)	−0.18454 (8)	0.59985 (6)	0.0714 (2)
O3	0.8063 (3)	0.08393 (16)	0.09854 (16)	0.0508 (5)
O4	1.0913 (3)	0.19567 (16)	0.06969 (19)	0.0601 (6)
C8	0.9365 (3)	0.18035 (19)	0.11129 (16)	0.0318 (4)
C9	0.9026 (4)	0.28429 (19)	0.18188 (18)	0.0348 (4)
C10	0.7242 (4)	0.2754 (2)	0.2238 (2)	0.0407 (5)
H10	0.6230	0.2049	0.2069	0.049*
C11	0.6966 (5)	0.3717 (2)	0.2911 (2)	0.0503 (6)
H11	0.5771	0.3663	0.3193	0.060*
C12	0.8467 (6)	0.4743 (2)	0.3154 (2)	0.0579 (7)
C13	1.0244 (6)	0.4853 (3)	0.2747 (3)	0.0663 (8)
H13	1.1250	0.5561	0.2922	0.080*
C14	1.0514 (5)	0.3897 (2)	0.2074 (2)	0.0512 (6)
H14	1.1707	0.3963	0.1790	0.061*
Cl2	0.8148 (2)	0.59368 (9)	0.40221 (10)	0.0981 (4)
O5	0.5654 (2)	−0.17863 (14)	0.04837 (14)	0.0397 (3)
H5	0.4613	−0.1549	0.0620	0.060*
C15	0.5781 (8)	−0.2948 (4)	0.0851 (5)	0.1087 (17)
H15A	0.6283	−0.3412	0.0316	0.130*
H15B	0.6867	−0.2846	0.1548	0.130*
C16	0.3962 (8)	−0.3657 (4)	0.1019 (5)	0.1163 (18)
H16A	0.4349	−0.4090	0.1663	0.174*
H16B	0.3314	−0.4227	0.0378	0.174*
H16C	0.2975	−0.3141	0.1132	0.174*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02393 (12)	0.02850 (13)	0.02705 (13)	0.00328 (8)	0.00589 (8)	0.00402 (8)
O1	0.0326 (8)	0.0750 (13)	0.0550 (11)	−0.0070 (8)	−0.0070 (7)	0.0366 (10)
O2	0.0298 (8)	0.0832 (13)	0.0354 (8)	0.0014 (8)	0.0030 (6)	0.0257 (9)
C1	0.0303 (9)	0.0317 (9)	0.0305 (10)	0.0082 (8)	0.0029 (8)	0.0016 (8)
C2	0.0348 (10)	0.0335 (10)	0.0280 (9)	0.0098 (8)	0.0025 (8)	0.0013 (8)
C3	0.0413 (12)	0.0516 (13)	0.0373 (12)	0.0128 (10)	0.0077 (9)	0.0110 (10)
C4	0.0640 (17)	0.0570 (15)	0.0372 (13)	0.0175 (13)	0.0101 (11)	0.0165 (11)
C5	0.0621 (16)	0.0478 (13)	0.0279 (11)	0.0255 (12)	−0.0055 (10)	0.0002 (9)
C6	0.0396 (12)	0.0535 (14)	0.0394 (12)	0.0118 (10)	−0.0073 (10)	−0.0024 (10)
C7	0.0356 (11)	0.0462 (12)	0.0349 (11)	0.0072 (9)	0.0001 (9)	0.0034 (9)
Cl1	0.0926 (6)	0.0776 (5)	0.0369 (3)	0.0401 (4)	−0.0136 (3)	0.0065 (3)
O3	0.0396 (9)	0.0434 (9)	0.0689 (12)	−0.0044 (7)	0.0257 (8)	−0.0206 (8)
O4	0.0695 (12)	0.0341 (8)	0.0897 (15)	−0.0028 (8)	0.0556 (12)	−0.0083 (9)
C8	0.0324 (10)	0.0350 (10)	0.0287 (9)	0.0106 (8)	0.0056 (8)	0.0046 (8)
C9	0.0398 (11)	0.0344 (10)	0.0310 (10)	0.0099 (8)	0.0084 (8)	0.0024 (8)
C10	0.0451 (12)	0.0394 (11)	0.0407 (12)	0.0100 (9)	0.0152 (10)	0.0024 (9)
C11	0.0614 (16)	0.0510 (14)	0.0484 (14)	0.0202 (12)	0.0264 (12)	0.0032 (11)
C12	0.086 (2)	0.0420 (13)	0.0532 (16)	0.0204 (14)	0.0275 (15)	−0.0057 (12)
C13	0.080 (2)	0.0396 (14)	0.079 (2)	−0.0028 (14)	0.0324 (18)	−0.0152 (14)
C14	0.0545 (15)	0.0406 (13)	0.0612 (16)	0.0033 (11)	0.0251 (13)	−0.0039 (11)
Cl2	0.1417 (10)	0.0610 (5)	0.1054 (8)	0.0210 (6)	0.0633 (7)	−0.0266 (5)
O5	0.0338 (8)	0.0368 (8)	0.0509 (9)	0.0031 (6)	0.0159 (7)	0.0103 (7)
C15	0.102 (3)	0.060 (2)	0.181 (5)	0.008 (2)	0.061 (3)	0.056 (3)
C16	0.114 (4)	0.081 (3)	0.161 (5)	−0.006 (3)	0.056 (4)	0.045 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.9530 (16)	O4—C8	1.243 (3)
Cu1—O2ⁱ	1.9535 (16)	O4—Cu1ⁱ	1.9572 (17)
Cu1—O4ⁱ	1.9572 (17)	C8—C9	1.493 (3)
Cu1—O3	1.9590 (16)	C9—C14	1.381 (3)
Cu1—O5	2.1334 (15)	C9—C10	1.387 (3)
Cu1—Cu1ⁱ	2.5905 (4)	C10—C11	1.387 (3)
O1—C1	1.245 (3)	C10—H10	0.9300
O2—C1	1.246 (3)	C11—C12	1.363 (4)
O2—Cu1ⁱ	1.9535 (16)	C11—H11	0.9300
C1—C2	1.493 (3)	C12—C13	1.373 (4)
C2—C3	1.380 (3)	C12—Cl2	1.740 (3)
C2—C7	1.394 (3)	C13—C14	1.380 (4)
C3—C4	1.384 (3)	C13—H13	0.9300
C3—H3	0.9300	C14—H14	0.9300
C4—C5	1.379 (4)	O5—C15	1.408 (4)
C4—H4	0.9300	O5—H5	0.8200
C5—C6	1.368 (4)	C15—C16	1.398 (6)
C5—Cl1	1.738 (2)	C15—H15A	0.9700
C6—C7	1.388 (3)	C15—H15B	0.9700
C6—H6	0.9300	C16—H16A	0.9600
C7—H7	0.9300	C16—H16B	0.9600
O3—C8	1.248 (3)	C16—H16C	0.9600

O1—Cu1—O2ⁱ	168.55 (7)	C8—O3—Cu1	123.45 (14)
O1—Cu1—O4ⁱ	91.24 (10)	C8—O4—Cu1ⁱ	122.94 (15)
O2ⁱ—Cu1—O4ⁱ	89.13 (10)	O4—C8—O3	124.7 (2)
O1—Cu1—O3	88.85 (9)	O4—C8—C9	118.06 (19)
O2ⁱ—Cu1—O3	88.55 (9)	O3—C8—C9	117.20 (19)
O4ⁱ—Cu1—O3	168.69 (7)	C14—C9—C10	119.4 (2)
O1—Cu1—O5	94.39 (7)	C14—C9—C8	120.0 (2)
O2ⁱ—Cu1—O5	96.99 (7)	C10—C9—C8	120.6 (2)
O4ⁱ—Cu1—O5	94.10 (7)	C11—C10—C9	120.0 (2)
O3—Cu1—O5	97.17 (7)	C11—C10—H10	120.0
O1—Cu1—Cu1ⁱ	85.05 (5)	C9—C10—H10	120.0
O2ⁱ—Cu1—Cu1ⁱ	83.59 (5)	C12—C11—C10	119.2 (2)
O4ⁱ—Cu1—Cu1ⁱ	84.70 (5)	C12—C11—H11	120.4
O3—Cu1—Cu1ⁱ	84.04 (5)	C10—C11—H11	120.4
O5—Cu1—Cu1ⁱ	178.66 (5)	C11—C12—C13	121.8 (2)
C1—O1—Cu1	122.56 (15)	C11—C12—Cl2	119.2 (2)
C1—O2—Cu1ⁱ	124.19 (14)	C13—C12—Cl2	119.0 (2)
O1—C1—O2	124.5 (2)	C12—C13—C14	118.9 (3)
O1—C1—C2	117.91 (19)	C12—C13—H13	120.5
O2—C1—C2	117.55 (18)	C14—C13—H13	120.5
C3—C2—C7	119.7 (2)	C13—C14—C9	120.5 (3)
C3—C2—C1	120.6 (2)	C13—C14—H14	119.7
C7—C2—C1	119.6 (2)	C9—C14—H14	119.7
C2—C3—C4	120.6 (2)	C15—O5—Cu1	121.5 (2)
C2—C3—H3	119.7	C15—O5—H5	109.5
C4—C3—H3	119.7	Cu1—O5—H5	125.7
C5—C4—C3	118.8 (2)	C16—C15—O5	119.3 (4)
C5—C4—H4	120.6	C16—C15—H15A	107.5
C3—C4—H4	120.6	O5—C15—H15A	107.5
C6—C5—C4	121.7 (2)	C16—C15—H15B	107.5
C6—C5—Cl1	119.0 (2)	O5—C15—H15B	107.5
C4—C5—Cl1	119.3 (2)	H15A—C15—H15B	107.0
C5—C6—C7	119.5 (2)	C15—C16—H16A	109.5
C5—C6—H6	120.3	C15—C16—H16B	109.5
C7—C6—H6	120.3	H16A—C16—H16B	109.5
C6—C7—C2	119.7 (2)	C15—C16—H16C	109.5
C6—C7—H7	120.2	H16A—C16—H16C	109.5
C2—C7—H7	120.2	H16B—C16—H16C	109.5

O2ⁱ—Cu1—O1—C1	−7.8 (6)	O5—Cu1—O3—C8	176.32 (19)
O4ⁱ—Cu1—O1—C1	83.9 (2)	Cu1ⁱ—Cu1—O3—C8	−3.11 (19)
O3—Cu1—O1—C1	−84.8 (2)	Cu1ⁱ—O4—C8—O3	−3.1 (4)
O5—Cu1—O1—C1	178.1 (2)	Cu1ⁱ—O4—C8—C9	176.85 (15)
Cu1ⁱ—Cu1—O1—C1	−0.6 (2)	Cu1—O3—C8—O4	4.6 (4)
Cu1—O1—C1—O2	−1.3 (4)	Cu1—O3—C8—C9	−175.33 (14)
Cu1—O1—C1—C2	179.60 (15)	O4—C8—C9—C14	−5.8 (3)
Cu1ⁱ—O2—C1—O1	3.4 (4)	O3—C8—C9—C14	174.2 (2)
Cu1ⁱ—O2—C1—C2	−177.55 (15)	O4—C8—C9—C10	175.3 (2)
O1—C1—C2—C3	−5.4 (3)	O3—C8—C9—C10	−4.7 (3)
O2—C1—C2—C3	175.4 (2)	C14—C9—C10—C11	−0.2 (4)
O1—C1—C2—C7	174.1 (2)	C8—C9—C10—C11	178.7 (2)
O2—C1—C2—C7	−5.0 (3)	C9—C10—C11—C12	−0.2 (4)
C7—C2—C3—C4	0.5 (4)	C10—C11—C12—C13	0.3 (5)
C1—C2—C3—C4	−180.0 (2)	C10—C11—C12—Cl2	−178.6 (2)
C2—C3—C4—C5	−0.2 (4)	C11—C12—C13—C14	0.0 (5)
C3—C4—C5—C6	−0.6 (4)	Cl2—C12—C13—C14	178.9 (3)
C3—C4—C5—Cl1	−179.7 (2)	C12—C13—C14—C9	−0.4 (5)
C4—C5—C6—C7	1.1 (4)	C10—C9—C14—C13	0.5 (4)
Cl1—C5—C6—C7	−179.76 (19)	C8—C9—C14—C13	−178.4 (3)
C5—C6—C7—C2	−0.8 (4)	O1—Cu1—O5—C15	−43.4 (3)
C3—C2—C7—C6	0.0 (4)	O2ⁱ—Cu1—O5—C15	137.8 (3)
C1—C2—C7—C6	−179.5 (2)	O4ⁱ—Cu1—O5—C15	48.1 (3)
O1—Cu1—O3—C8	82.0 (2)	O3—Cu1—O5—C15	−132.8 (3)
O2ⁱ—Cu1—O3—C8	−86.8 (2)	Cu1—O5—C15—C16	−179.0 (4)
O4ⁱ—Cu1—O3—C8	−8.6 (6)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2ⁱⁱ	0.82	2.35	3.073 (3)	148
O5—H5···O3ⁱⁱⁱ	0.82	2.57	3.047 (3)	118

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₇H₄ClO₂)(C₂H₆O)₂]
M_r	841.42
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.5766 (1), 11.1792 (2), 12.4355 (3)
α, β, γ (°)	93.175 (1), 103.890 (1), 98.688 (1)
V (Å³)	873.34 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.58
Crystal size (mm)	0.38 × 0.18 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2007)
T_min, T_max	0.695, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	36853, 5070, 4288
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.102, 1.03
No. of reflections	5070
No. of parameters	220
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.42

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XPW (Siemens, 1996), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2ⁱ	0.82	2.35	3.073 (3)	148
O5—H5···O3ⁱⁱ	0.82	2.57	3.047 (3)	118

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

References

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Volume 69| Part 4| April 2013| Page m221

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