Tetra-kis(μ-2-methyl-benzoato)bis-[(2-methyl-benzoic acid)copper(II)].

In the title centrosymmetric dinuclear compound, [Cu(2)(C(8)H(7)O(2))(4)(C(8)H(8)O(2))(2)], four o-toluate anions form a cage around two Cu atoms in a syn-syn configuration. Two more o-toluic acid mol-ecules are apically bonded to the Cu atoms, which show a square-pyramidal coordination geometry. The acid H atoms are hydrogen bonded to the cage carboxyl O atoms [O⋯O = 2.660 (2) Å]. The mol-ecular packing forms a puckered pseudo-hexa-gonal close-packed layer in the (h00) plane, with soft inter-molecular H⋯H contacts (2.46-2.58 Å).

Related literature

For the synthesis of aromatic carboxylic acids, see: Kaeding (1967 ▶). For tetra­kis(μ2-2-fluoro­benzoato)bis­(2-fluoro­benzoic acid)dicopper(II), see: Valach et al. (2000 ▶), For tetra­kis(μ2-benzoato)bis­(2-fluoro­benzoic acid)dicopper(II), see: Kawata et al. (1992 ▶).

Experimental

Crystal data

[Cu2(C8H7O2)4(C8H8O2)2]

M = 939.96

Triclinic,

a = 10.530 (3) Å

b = 10.579 (3) Å

c = 10.773 (4) Å

α = 109.248 (2)°

β = 93.156 (2)°

γ = 106.287 (2)°

V = 1073.0 (6) Å3

Z = 1

Mo Kα radiation

μ = 1.06 mm−1

T = 100 (2) K

0.25 × 0.08 × 0.06 mm

Data collection

Bruker X8 APEXII diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶b) T min = 0.778, T max = 0.939

17497 measured reflections

5138 independent reflections

4668 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.065

S = 1.05

5138 reflections

284 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.33 e Å−3

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808006661/ng2426sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808006661/ng2426Isup2.hkl

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

[Cu2(C8H7O2)4(C8H8O2)2]	Z = 1
Mr = 939.96	F000 = 486
Triclinic, P1	Dx = 1.455 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71069 Å
a = 10.530 (3) Å	Cell parameters from 8974 reflections
b = 10.579 (3) Å	θ = 2.6–28.3º
c = 10.773 (4) Å	µ = 1.06 mm−1
α = 109.248 (2)º	T = 100 (2) K
β = 93.156 (2)º	Needle, blue
γ = 106.287 (2)º	0.25 × 0.08 × 0.06 mm
V = 1073.0 (6) Å3

Bruker X8 APEXII 4K KappaCCD diffractometer	4668 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.026
T = 100(2) K	θmax = 28º
ω and φ scans	θmin = 2.2º
Absorption correction: multi-scan(SADABS; Bruker, 2004b)	h = −13→13
Tmin = 0.778, Tmax = 0.939	k = −13→13
17497 measured reflections	l = −14→14
5138 independent reflections

Refinement on F2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.024P)2 + 0.7431P] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.026	(Δ/σ)max = 0.001
wR(F2) = 0.065	Δρmax = 0.41 e Å−3
S = 1.05	Δρmin = −0.33 e Å−3
5138 reflections	Extinction correction: none
284 parameters

Experimental. The intensity data was collected on a Bruker X8 Apex II 4 K Kappa CCD diffractometer using an exposure time of 30 s/frame. The 1757 frames were collected with a frame width of 0.5° covering up to θ = 28° with 99.3% 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.

	x	y	z	Uiso*/Ueq
Cu1	0.444832 (17)	0.389154 (17)	0.395103 (17)	0.01027 (6)
O32	0.51055 (11)	0.07974 (12)	0.26534 (12)	0.0217 (2)
H32	0.5525	0.1594	0.3175	0.033*
O31	0.36065 (11)	0.18596 (11)	0.23619 (10)	0.0154 (2)
O21	0.47477 (11)	0.50089 (11)	0.70973 (10)	0.0175 (2)
O22	0.38457 (10)	0.65099 (11)	0.57571 (11)	0.0168 (2)
O11	0.38005 (11)	0.30802 (11)	0.52758 (10)	0.0157 (2)
O12	0.29312 (10)	0.46128 (11)	0.39073 (10)	0.0150 (2)
C16	0.36586 (15)	0.36861 (16)	0.87485 (15)	0.0161 (3)
H16	0.3999	0.4666	0.9049	0.019*
C31	0.31192 (15)	−0.05882 (15)	0.11267 (14)	0.0142 (3)
C11	0.35899 (14)	0.29021 (15)	0.74017 (14)	0.0126 (3)
C36	0.37677 (17)	−0.14773 (16)	0.03537 (16)	0.0189 (3)
H36	0.4698	−0.1226	0.0517	0.023*
C25	0.00903 (16)	0.72093 (17)	0.56202 (18)	0.0235 (3)
H25	−0.0326	0.7479	0.6358	0.028*
C321	0.09555 (16)	−0.00753 (18)	0.17572 (17)	0.0229 (3)
H32A	0.0954	0.0674	0.1443	0.034*
H32B	0.138	0.0318	0.2672	0.034*
H32C	0.0049	−0.065	0.1684	0.034*
C1	0.40786 (14)	0.37152 (15)	0.65233 (14)	0.0127 (3)
C12	0.30930 (15)	0.14154 (15)	0.69355 (15)	0.0143 (3)
C15	0.32315 (16)	0.30349 (17)	0.96407 (16)	0.0183 (3)
H15	0.3285	0.3569	1.0533	0.022*
C2	0.29274 (14)	0.57566 (15)	0.47500 (14)	0.0119 (3)
C13	0.26600 (15)	0.07881 (16)	0.78583 (16)	0.0166 (3)
H13	0.2318	−0.0191	0.7571	0.02*
C32	0.17142 (16)	−0.09665 (16)	0.09292 (15)	0.0168 (3)
C21	0.17807 (14)	0.62904 (14)	0.45946 (15)	0.0131 (3)
C33	0.10027 (17)	−0.22517 (17)	−0.00704 (16)	0.0229 (3)
H33	0.0071	−0.2536	−0.0213	0.027*
C22	0.13237 (16)	0.63473 (16)	0.33772 (16)	0.0182 (3)
C121	0.30291 (18)	0.04573 (16)	0.55228 (16)	0.0211 (3)
H12A	0.278	−0.0505	0.5475	0.032*
H12B	0.3892	0.0707	0.5256	0.032*
H12C	0.2375	0.0561	0.4939	0.032*
C26	0.11778 (16)	0.67358 (16)	0.57076 (16)	0.0175 (3)
H26	0.151	0.6714	0.6516	0.021*
C34	0.16490 (19)	−0.31154 (17)	−0.08566 (16)	0.0254 (4)
H34	0.1149	−0.396	−0.1525	0.03*
C3	0.39545 (15)	0.08020 (15)	0.21105 (14)	0.0137 (3)
C35	0.30350 (19)	−0.27297 (17)	−0.06539 (16)	0.0238 (4)
H35	0.3469	−0.3305	−0.1189	0.029*
C14	0.27235 (15)	0.15762 (17)	0.91873 (16)	0.0177 (3)
H14	0.2425	0.1125	0.9775	0.021*
C24	−0.03711 (16)	0.72774 (17)	0.44262 (19)	0.0261 (4)
H24	−0.11	0.7598	0.436	0.031*
C221	0.1966 (2)	0.5912 (2)	0.21626 (17)	0.0314 (4)
H22A	0.2917	0.6378	0.2388	0.047*
H22B	0.1603	0.6173	0.1481	0.047*
H22C	0.1789	0.4909	0.1842	0.047*
C23	0.02467 (17)	0.68697 (17)	0.33293 (18)	0.0250 (4)
H23	−0.0062	0.6945	0.2539	0.03*

	U11	U22	U33	U12	U13	U23
Cu1	0.01089 (9)	0.00896 (9)	0.01017 (9)	0.00293 (6)	0.00121 (6)	0.00270 (6)
O32	0.0162 (5)	0.0158 (5)	0.0258 (6)	0.0068 (4)	−0.0053 (5)	−0.0019 (5)
O31	0.0165 (5)	0.0124 (5)	0.0150 (5)	0.0054 (4)	−0.0001 (4)	0.0019 (4)
O21	0.0211 (6)	0.0135 (5)	0.0143 (5)	0.0004 (4)	0.0038 (4)	0.0047 (4)
O22	0.0126 (5)	0.0159 (5)	0.0178 (5)	0.0056 (4)	−0.0018 (4)	0.0006 (4)
O11	0.0205 (5)	0.0135 (5)	0.0122 (5)	0.0031 (4)	0.0019 (4)	0.0053 (4)
O12	0.0145 (5)	0.0132 (5)	0.0157 (5)	0.0058 (4)	−0.0003 (4)	0.0025 (4)
C16	0.0170 (7)	0.0144 (7)	0.0160 (7)	0.0042 (6)	0.0020 (6)	0.0052 (6)
C31	0.0177 (7)	0.0117 (6)	0.0126 (7)	0.0041 (6)	0.0018 (6)	0.0043 (5)
C11	0.0099 (6)	0.0153 (7)	0.0139 (7)	0.0045 (5)	0.0023 (5)	0.0066 (6)
C36	0.0235 (8)	0.0156 (7)	0.0187 (8)	0.0083 (6)	0.0057 (6)	0.0057 (6)
C25	0.0163 (8)	0.0180 (8)	0.0319 (9)	0.0058 (6)	0.0088 (7)	0.0026 (7)
C321	0.0146 (7)	0.0262 (8)	0.0265 (9)	0.0060 (6)	0.0035 (6)	0.0082 (7)
C1	0.0115 (7)	0.0141 (7)	0.0142 (7)	0.0061 (5)	0.0027 (5)	0.0055 (5)
C12	0.0121 (7)	0.0154 (7)	0.0158 (7)	0.0048 (6)	0.0011 (5)	0.0057 (6)
C15	0.0197 (8)	0.0227 (8)	0.0139 (7)	0.0081 (6)	0.0042 (6)	0.0067 (6)
C2	0.0121 (7)	0.0116 (6)	0.0131 (7)	0.0026 (5)	0.0035 (5)	0.0066 (5)
C13	0.0134 (7)	0.0149 (7)	0.0216 (8)	0.0028 (6)	0.0021 (6)	0.0083 (6)
C32	0.0190 (7)	0.0156 (7)	0.0152 (7)	0.0028 (6)	0.0008 (6)	0.0073 (6)
C21	0.0109 (6)	0.0093 (6)	0.0169 (7)	0.0015 (5)	0.0013 (5)	0.0038 (5)
C33	0.0232 (8)	0.0182 (8)	0.0211 (8)	−0.0025 (6)	−0.0041 (7)	0.0082 (6)
C22	0.0196 (8)	0.0158 (7)	0.0181 (8)	0.0072 (6)	−0.0005 (6)	0.0038 (6)
C121	0.0297 (9)	0.0130 (7)	0.0189 (8)	0.0054 (6)	0.0039 (7)	0.0048 (6)
C26	0.0165 (7)	0.0151 (7)	0.0191 (7)	0.0040 (6)	0.0038 (6)	0.0044 (6)
C34	0.0394 (10)	0.0137 (7)	0.0149 (8)	−0.0004 (7)	−0.0029 (7)	0.0034 (6)
C3	0.0138 (7)	0.0146 (7)	0.0120 (7)	0.0041 (6)	0.0036 (5)	0.0043 (5)
C35	0.0401 (10)	0.0146 (7)	0.0167 (8)	0.0110 (7)	0.0069 (7)	0.0034 (6)
C14	0.0147 (7)	0.0242 (8)	0.0194 (8)	0.0063 (6)	0.0046 (6)	0.0141 (6)
C24	0.0141 (7)	0.0183 (8)	0.0399 (10)	0.0076 (6)	−0.0033 (7)	0.0022 (7)
C221	0.0442 (11)	0.0427 (11)	0.0175 (8)	0.0258 (9)	0.0062 (8)	0.0134 (8)
C23	0.0246 (9)	0.0205 (8)	0.0264 (9)	0.0094 (7)	−0.0085 (7)	0.0041 (7)

Cu1—O21i	1.9402 (12)	C321—H32B	0.96
Cu1—O11	1.9559 (12)	C321—H32C	0.96
Cu1—O12	1.9585 (13)	C12—C13	1.397 (2)
Cu1—O22i	1.9900 (13)	C12—C121	1.510 (2)
Cu1—O31	2.1622 (13)	C15—C14	1.385 (2)
Cu1—Cu1i	2.5780 (9)	C15—H15	0.93
O32—C3	1.3184 (19)	C2—C21	1.492 (2)
O32—H32	0.82	C13—C14	1.386 (2)
O31—C3	1.2250 (18)	C13—H13	0.93
O21—C1	1.2670 (18)	C32—C33	1.394 (2)
O21—Cu1i	1.9402 (12)	C21—C26	1.394 (2)
O22—C2	1.2764 (18)	C21—C22	1.398 (2)
O22—Cu1i	1.9900 (13)	C33—C34	1.385 (3)
O11—C1	1.2626 (18)	C33—H33	0.93
O12—C2	1.2518 (18)	C22—C23	1.399 (2)
C16—C15	1.382 (2)	C22—C221	1.502 (2)
C16—C11	1.400 (2)	C121—H12A	0.96
C16—H16	0.93	C121—H12B	0.96
C31—C36	1.397 (2)	C121—H12C	0.96
C31—C32	1.404 (2)	C26—H26	0.93
C31—C3	1.485 (2)	C34—C35	1.384 (3)
C11—C12	1.410 (2)	C34—H34	0.93
C11—C1	1.497 (2)	C35—H35	0.93
C36—C35	1.384 (2)	C14—H14	0.93
C36—H36	0.93	C24—C23	1.383 (3)
C25—C24	1.381 (3)	C24—H24	0.93
C25—C26	1.383 (2)	C221—H22A	0.96
C25—H25	0.93	C221—H22B	0.96
C321—C32	1.506 (2)	C221—H22C	0.96
C321—H32A	0.96	C23—H23	0.93
O21i—Cu1—O11	170.01 (4)	O12—C2—O22	124.23 (14)
O21i—Cu1—O12	87.99 (5)	O12—C2—C21	118.96 (13)
O11—Cu1—O12	91.79 (5)	O22—C2—C21	116.81 (13)
O21i—Cu1—O22i	89.93 (5)	C14—C13—C12	122.17 (14)
O11—Cu1—O22i	88.55 (5)	C14—C13—H13	118.9
O12—Cu1—O22i	169.88 (4)	C12—C13—H13	118.9
O21i—Cu1—O31	98.74 (6)	C33—C32—C31	117.35 (15)
O11—Cu1—O31	91.16 (6)	C33—C32—C321	119.26 (15)
O12—Cu1—O31	99.14 (5)	C31—C32—C321	123.37 (14)
O22i—Cu1—O31	90.97 (5)	C26—C21—C22	120.83 (14)
O21i—Cu1—Cu1i	87.75 (5)	C26—C21—C2	117.76 (13)
O11—Cu1—Cu1i	82.27 (5)	C22—C21—C2	121.41 (13)
O12—Cu1—Cu1i	86.61 (4)	C34—C33—C32	121.67 (16)
O22i—Cu1—Cu1i	83.41 (4)	C34—C33—H33	119.2
O31—Cu1—Cu1i	171.44 (3)	C32—C33—H33	119.2
C3—O32—H32	109.5	C21—C22—C23	117.30 (15)
C3—O31—Cu1	129.50 (10)	C21—C22—C221	122.57 (15)
C1—O21—Cu1i	119.83 (10)	C23—C22—C221	120.12 (15)
C2—O22—Cu1i	123.41 (10)	C12—C121—H12A	109.5
C1—O11—Cu1	125.45 (10)	C12—C121—H12B	109.5
C2—O12—Cu1	122.02 (10)	H12A—C121—H12B	109.5
C15—C16—C11	121.39 (14)	C12—C121—H12C	109.5
C15—C16—H16	119.3	H12A—C121—H12C	109.5
C11—C16—H16	119.3	H12B—C121—H12C	109.5
C36—C31—C32	120.86 (14)	C25—C26—C21	120.55 (15)
C36—C31—C3	118.27 (14)	C25—C26—H26	119.7
C32—C31—C3	120.78 (13)	C21—C26—H26	119.7
C16—C11—C12	119.90 (13)	C35—C34—C33	120.44 (15)
C16—C11—C1	116.94 (13)	C35—C34—H34	119.8
C12—C11—C1	123.16 (13)	C33—C34—H34	119.8
C35—C36—C31	120.42 (16)	O31—C3—O32	123.59 (13)
C35—C36—H36	119.8	O31—C3—C31	122.29 (14)
C31—C36—H36	119.8	O32—C3—C31	114.10 (13)
C24—C25—C26	119.35 (16)	C36—C35—C34	119.22 (16)
C24—C25—H25	120.3	C36—C35—H35	120.4
C26—C25—H25	120.3	C34—C35—H35	120.4
C32—C321—H32A	109.5	C15—C14—C13	120.05 (14)
C32—C321—H32B	109.5	C15—C14—H14	120
H32A—C321—H32B	109.5	C13—C14—H14	120
C32—C321—H32C	109.5	C25—C24—C23	120.20 (16)
H32A—C321—H32C	109.5	C25—C24—H24	119.9
H32B—C321—H32C	109.5	C23—C24—H24	119.9
O11—C1—O21	124.51 (13)	C22—C221—H22A	109.5
O11—C1—C11	118.61 (13)	C22—C221—H22B	109.5
O21—C1—C11	116.88 (13)	H22A—C221—H22B	109.5
C13—C12—C11	117.39 (14)	C22—C221—H22C	109.5
C13—C12—C121	117.89 (14)	H22A—C221—H22C	109.5
C11—C12—C121	124.70 (13)	H22B—C221—H22C	109.5
C16—C15—C14	119.09 (15)	C24—C23—C22	121.72 (16)
C16—C15—H15	120.5	C24—C23—H23	119.1
C14—C15—H15	120.5	C22—C23—H23	119.1
O21i—Cu1—O31—C3	108.89 (13)	C11—C12—C13—C14	−0.8 (2)
O11—Cu1—O31—C3	−69.75 (13)	C121—C12—C13—C14	177.70 (14)
O12—Cu1—O31—C3	−161.75 (13)	C36—C31—C32—C33	−0.5 (2)
O22i—Cu1—O31—C3	18.81 (13)	C3—C31—C32—C33	176.08 (14)
O12—Cu1—O11—C1	−88.41 (12)	C36—C31—C32—C321	178.06 (14)
O22i—Cu1—O11—C1	81.47 (12)	C3—C31—C32—C321	−5.4 (2)
O31—Cu1—O11—C1	172.41 (12)	O12—C2—C21—C26	131.59 (15)
Cu1i—Cu1—O11—C1	−2.08 (11)	O22—C2—C21—C26	−47.95 (19)
O21i—Cu1—O12—C2	−87.01 (12)	O12—C2—C21—C22	−48.5 (2)
O11—Cu1—O12—C2	83.00 (12)	O22—C2—C21—C22	131.91 (15)
O22i—Cu1—O12—C2	−8.8 (3)	C31—C32—C33—C34	−1.1 (2)
O31—Cu1—O12—C2	174.46 (11)	C321—C32—C33—C34	−179.70 (15)
Cu1i—Cu1—O12—C2	0.85 (11)	C26—C21—C22—C23	0.1 (2)
C15—C16—C11—C12	−0.8 (2)	C2—C21—C22—C23	−179.71 (14)
C15—C16—C11—C1	179.95 (14)	C26—C21—C22—C221	178.43 (16)
C32—C31—C36—C35	2.2 (2)	C2—C21—C22—C221	−1.4 (2)
C3—C31—C36—C35	−174.48 (14)	C24—C25—C26—C21	−1.9 (2)
Cu1—O11—C1—O21	5.1 (2)	C22—C21—C26—C25	1.7 (2)
Cu1—O11—C1—C11	−175.02 (9)	C2—C21—C26—C25	−178.42 (14)
Cu1i—O21—C1—O11	−5.4 (2)	C32—C33—C34—C35	1.0 (2)
Cu1i—O21—C1—C11	174.78 (9)	Cu1—O31—C3—O32	−13.1 (2)
C16—C11—C1—O11	−166.58 (13)	Cu1—O31—C3—C31	168.70 (10)
C12—C11—C1—O11	14.2 (2)	C36—C31—C3—O31	144.89 (15)
C16—C11—C1—O21	13.27 (19)	C32—C31—C3—O31	−31.8 (2)
C12—C11—C1—O21	−165.91 (14)	C36—C31—C3—O32	−33.43 (19)
C16—C11—C12—C13	1.3 (2)	C32—C31—C3—O32	149.91 (14)
C1—C11—C12—C13	−179.57 (13)	C31—C36—C35—C34	−2.2 (2)
C16—C11—C12—C121	−177.11 (14)	C33—C34—C35—C36	0.7 (2)
C1—C11—C12—C121	2.1 (2)	C16—C15—C14—C13	0.6 (2)
C11—C16—C15—C14	−0.1 (2)	C12—C13—C14—C15	−0.2 (2)
Cu1—O12—C2—O22	−5.0 (2)	C26—C25—C24—C23	0.3 (2)
Cu1—O12—C2—C21	175.52 (9)	C25—C24—C23—C22	1.6 (3)
Cu1i—O22—C2—O12	7.4 (2)	C21—C22—C23—C24	−1.8 (2)
Cu1i—O22—C2—C21	−173.12 (9)	C221—C22—C23—C24	179.87 (17)

D—H···A	D—H	H···A	D···A	D—H···A
O32—H32···O22i	0.82	1.85	2.6604 (18)	168
C16—H16···O21	0.93	2.39	2.721 (2)	101

Table 1

Selected bond lengths (Å)

Cu1—O21i	1.9402 (12)
Cu1—O11	1.9559 (12)
Cu1—O12	1.9585 (13)
Cu1—O22i	1.9900 (13)
Cu1—O31	2.1622 (13)
Cu1⋯Cu1i	2.5780 (9)

Symmetry code: (i) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O32—H32⋯O22i	0.82	1.85	2.6604 (18)	168
C16—H16⋯O21	0.93	2.39	2.721 (2)	101

Symmetry code: (i) .