Tetra-kis(μ-4-chloro-benzoato-κ(2) O:O')bis-[(ethanol-κO)copper(II)](Cu-Cu).

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-chloro-benzoate ligands and each has an ethanol mol-ecule 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 = 841.42

Triclinic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.102

S = 1.03

5070 reflections

220 parameters

H-atom parameters constrained

Δρmax = 0.50 e Å−3

Δρmin = −0.42 e Å−3

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813006909/fj2617sup1.cif

Click here for additional data file.

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cu2(C7H4ClO2)(C2H6O)2]	Z = 1
Mr = 841.42	F(000) = 426
Triclinic, P1	Dx = 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

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

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(Fo2) + (0.0523P)2 + 0.4776P] where P = (Fo2 + 2Fc2)/3
5070 reflections	(Δ/σ)max = 0.004
220 parameters	Δρmax = 0.50 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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

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) ; (ii) .