metal-organic compounds
Tetrakis[μ-2-(methoxycarbonyl)benzoato-κ2O1:O1′]bis[(acetonitrile-κN)copper(II)](Cu—Cu)
aDepartment of Chemistry, Changzhi University, Changzhi, Shanxi 046011, People's Republic of China, and bInstitute of Molecular Science, Shanxi University, Taiyuan, Shanxi 030006, People's Republic of China
*Correspondence e-mail: jlwangczu@163.com
In the binuclear copper(II) title complex, [Cu2(C9H7O4)4(C2H3N)2], an inversion centre is situtated at the mid-point of the Cu—Cu bond. The CuII atom together with its four coordinated O atoms are in a distorted planar square arrangement while the nitrogen and the other CuII atom are located in apical positions. The whole molecule looks like a paddle-wheel. In the crystal, chains are assembled along the b axis through C—H⋯O hydrogen bonds and slipped π–π interactions between the benzene rings of neighbouring molecules [centroid–centroid distance = 3.6929 (3) Å and slippage = 0.641 (1) Å].
Related literature
For a review on related binuclear CuII carboxylato compounds with subnormal magnetic moments, see: Kato et al. (1964). For the electrochemical behavior of related compounds, see: Reinhard et al. (2003). For the synthesis of related compounds, see: Liu et al. (2008).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1999); cell SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536812049410/lr2089sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049410/lr2089Isup2.hkl
The title complex was prepared by adapting a reported procedure (Liu et al., 2008) by stirring a methanolic solutions of 2-(methoxycarbonyl)benzoic acid (180.0 mg, 1.0 mmol) and NaOH (40.0 mg, 1.0 mmol) for 30 min at room temperature. Then, 10 ml of a methanol solution containing Cu(NO3)2.3H2O (121 mg, 0.5 mmol) was added to the mixture, the blue precipitate obtained was separated by filtration, washed with methanol and dried. The blue powder was dissolved in acetonitrile, and single crystals of the title complex suitable for X-ray analysis were obtained after slow evaporation at room temperature for several weeks.
H atoms attached to C atoms are placed in geometrically idealized position, with C–H=0.93 and 0.96 Å, for CH and CH3 groups, respectively, and with Uiso(H)=1.2Ueq (Csp2) or 1.5Ueq (Csp3).
A large number of binuclear CuII carboxylato compounds are an attractive target of chemical research due to their magnetism (Kato et al., 1964) and electrochemical behavior (Reinhard et al., 2003). In general, binuclear copper (II) carboxylates consist of four three-atom bridges, uniting two contiguous copper(II) ions and exhibit a paddle-wheel cage structure.
Herein we report synthesis and
of binuclear copper(II) carboxylato compound with 2-(methoxycarbonyl)benzoic acid acting as a bidentate chelating ligand. Each copper(II) is coordinated by four carboxylate O donor atoms from four ligands, and by N donor atoms from the solvent molecule, The Cu—O distances and related angles are all within expected ranges (Kato et al., 1964) and Cu—N distance is 2.186 (3) Å. A binuclear copper carboxylate unit is formed by four (HL) ligands and two Cu centres with a Cu—Cu separation of 2.6662 (7) Å.In the π-π interactions (centroid–centroid distance of 3.6929 (3) Å) link the molecules into an infinite one-dimensional chain extending along the b axis.
weak C—H···O hydrogen bonds (H···O distance of 2.5087 (22) Å) andFor a review on related binuclear CuII carboxylato compounds with subnormal magnetic moments, see: Kato et al. (1964). For the electrochemical behavior of related compounds, see: Reinhard et al. (2003). For the synthesis of related compounds, see: Liu et al. (2008).
Data collection: SMART (Bruker, 1999); cell
SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).[Cu2(C9H7O4)4(C2H3N)2] | Z = 1 |
Mr = 925.77 | F(000) = 474 |
Triclinic, P1 | Dx = 1.525 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.2332 (10) Å | Cell parameters from 2861 reflections |
b = 10.5730 (13) Å | θ = 2.3–27.6° |
c = 12.6673 (15) Å | µ = 1.13 mm−1 |
α = 104.774 (1)° | T = 298 K |
β = 108.061 (2)° | Block, blue |
γ = 91.152 (1)° | 0.41 × 0.30 × 0.27 mm |
V = 1007.8 (2) Å3 |
Bruker SMART CCD area-detector diffractometer | 3466 independent reflections |
Radiation source: fine-focus sealed tube | 2906 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
phi and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −9→9 |
Tmin = 0.654, Tmax = 0.750 | k = −12→12 |
5143 measured reflections | l = −11→15 |
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) = 0.105 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0576P)2 + 0.2799P] where P = (Fo2 + 2Fc2)/3 |
3466 reflections | (Δ/σ)max = 0.001 |
271 parameters | Δρmax = 0.55 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[Cu2(C9H7O4)4(C2H3N)2] | γ = 91.152 (1)° |
Mr = 925.77 | V = 1007.8 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.2332 (10) Å | Mo Kα radiation |
b = 10.5730 (13) Å | µ = 1.13 mm−1 |
c = 12.6673 (15) Å | T = 298 K |
α = 104.774 (1)° | 0.41 × 0.30 × 0.27 mm |
β = 108.061 (2)° |
Bruker SMART CCD area-detector diffractometer | 3466 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2906 reflections with I > 2σ(I) |
Tmin = 0.654, Tmax = 0.750 | Rint = 0.022 |
5143 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.105 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.55 e Å−3 |
3466 reflections | Δρmin = −0.32 e Å−3 |
271 parameters |
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 > σ(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 | 0.66718 (4) | 0.48669 (3) | 0.52396 (3) | 0.02864 (14) | |
N1 | 0.9334 (4) | 0.4460 (3) | 0.5907 (3) | 0.0511 (7) | |
O1 | 0.5939 (3) | 0.33112 (19) | 0.56430 (17) | 0.0356 (5) | |
O2 | 0.3117 (3) | 0.3521 (2) | 0.52217 (19) | 0.0407 (5) | |
O3 | 0.6624 (3) | 0.3323 (2) | 0.8074 (2) | 0.0519 (6) | |
O4 | 0.8468 (4) | 0.1920 (3) | 0.7599 (3) | 0.0758 (9) | |
O5 | 0.6016 (3) | 0.3852 (2) | 0.36022 (17) | 0.0370 (5) | |
O6 | 0.3193 (3) | 0.4033 (2) | 0.32214 (17) | 0.0373 (5) | |
O7 | 0.1070 (3) | 0.1505 (2) | 0.2080 (2) | 0.0489 (6) | |
O8 | −0.0269 (3) | 0.2908 (3) | 0.1135 (2) | 0.0591 (7) | |
C1 | 0.4421 (4) | 0.2953 (3) | 0.5562 (2) | 0.0320 (7) | |
C2 | 0.4171 (4) | 0.1705 (3) | 0.5883 (3) | 0.0341 (7) | |
C3 | 0.2681 (4) | 0.0870 (3) | 0.5272 (3) | 0.0481 (9) | |
H3 | 0.1831 | 0.1115 | 0.4703 | 0.058* | |
C4 | 0.2426 (5) | −0.0317 (3) | 0.5485 (3) | 0.0531 (9) | |
H4 | 0.1406 | −0.0861 | 0.5072 | 0.064* | |
C5 | 0.3681 (5) | −0.0695 (3) | 0.6311 (3) | 0.0497 (9) | |
H5 | 0.3519 | −0.1502 | 0.6451 | 0.060* | |
C6 | 0.5178 (5) | 0.0117 (3) | 0.6930 (3) | 0.0475 (8) | |
H6 | 0.6026 | −0.0142 | 0.7490 | 0.057* | |
C7 | 0.5432 (4) | 0.1324 (3) | 0.6725 (3) | 0.0366 (7) | |
C8 | 0.7035 (5) | 0.2203 (4) | 0.7487 (3) | 0.0466 (8) | |
C9 | 0.8041 (6) | 0.4269 (4) | 0.8868 (3) | 0.0730 (13) | |
H9A | 0.8914 | 0.3821 | 0.9281 | 0.109* | |
H9B | 0.7641 | 0.4889 | 0.9405 | 0.109* | |
H9C | 0.8510 | 0.4726 | 0.8446 | 0.109* | |
C10 | 0.4473 (4) | 0.3629 (3) | 0.2946 (2) | 0.0314 (7) | |
C11 | 0.4130 (4) | 0.2844 (3) | 0.1715 (2) | 0.0340 (7) | |
C12 | 0.5451 (4) | 0.2722 (3) | 0.1247 (3) | 0.0458 (8) | |
H12 | 0.6562 | 0.3065 | 0.1721 | 0.055* | |
C13 | 0.5161 (5) | 0.2104 (4) | 0.0094 (3) | 0.0612 (10) | |
H13 | 0.6066 | 0.2032 | −0.0202 | 0.073* | |
C14 | 0.3510 (5) | 0.1593 (4) | −0.0613 (3) | 0.0667 (11) | |
H14 | 0.3299 | 0.1182 | −0.1392 | 0.080* | |
C15 | 0.2173 (5) | 0.1693 (4) | −0.0162 (3) | 0.0549 (10) | |
H15 | 0.1066 | 0.1344 | −0.0643 | 0.066* | |
C16 | 0.2458 (4) | 0.2306 (3) | 0.0994 (3) | 0.0380 (7) | |
C17 | 0.0956 (4) | 0.2320 (3) | 0.1417 (3) | 0.0413 (8) | |
C18 | −0.0319 (5) | 0.1442 (4) | 0.2536 (3) | 0.0629 (11) | |
H18A | −0.0247 | 0.2246 | 0.3119 | 0.094* | |
H18B | −0.0240 | 0.0716 | 0.2869 | 0.094* | |
H18C | −0.1396 | 0.1323 | 0.1925 | 0.094* | |
C19 | 1.0408 (4) | 0.4208 (4) | 0.6578 (3) | 0.0467 (8) | |
C20 | 1.1799 (5) | 0.3891 (5) | 0.7485 (4) | 0.0714 (12) | |
H20A | 1.1928 | 0.4511 | 0.8214 | 0.107* | |
H20B | 1.2852 | 0.3933 | 0.7313 | 0.107* | |
H20C | 1.1531 | 0.3019 | 0.7524 | 0.107* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0319 (2) | 0.0312 (2) | 0.0265 (2) | 0.00672 (14) | 0.01079 (15) | 0.01251 (15) |
N1 | 0.0412 (16) | 0.062 (2) | 0.0581 (19) | 0.0198 (14) | 0.0169 (14) | 0.0284 (16) |
O1 | 0.0416 (12) | 0.0331 (11) | 0.0384 (12) | 0.0063 (9) | 0.0153 (9) | 0.0181 (9) |
O2 | 0.0420 (12) | 0.0384 (12) | 0.0496 (13) | 0.0073 (10) | 0.0158 (10) | 0.0245 (10) |
O3 | 0.0625 (15) | 0.0520 (15) | 0.0372 (13) | 0.0001 (12) | 0.0093 (11) | 0.0144 (11) |
O4 | 0.0478 (16) | 0.082 (2) | 0.093 (2) | 0.0159 (15) | 0.0066 (15) | 0.0341 (18) |
O5 | 0.0397 (12) | 0.0452 (13) | 0.0268 (11) | 0.0078 (10) | 0.0105 (9) | 0.0111 (9) |
O6 | 0.0379 (12) | 0.0428 (13) | 0.0302 (11) | 0.0077 (10) | 0.0123 (9) | 0.0067 (9) |
O7 | 0.0455 (13) | 0.0544 (15) | 0.0515 (14) | 0.0058 (11) | 0.0150 (11) | 0.0236 (12) |
O8 | 0.0462 (14) | 0.0785 (19) | 0.0617 (17) | 0.0205 (13) | 0.0176 (12) | 0.0339 (14) |
C1 | 0.0418 (18) | 0.0336 (16) | 0.0242 (14) | 0.0047 (14) | 0.0140 (13) | 0.0099 (12) |
C2 | 0.0412 (17) | 0.0319 (16) | 0.0350 (16) | 0.0061 (13) | 0.0179 (13) | 0.0123 (13) |
C3 | 0.050 (2) | 0.045 (2) | 0.048 (2) | −0.0028 (16) | 0.0097 (16) | 0.0195 (16) |
C4 | 0.059 (2) | 0.042 (2) | 0.061 (2) | −0.0027 (17) | 0.0232 (18) | 0.0148 (17) |
C5 | 0.071 (2) | 0.0314 (18) | 0.065 (2) | 0.0131 (17) | 0.041 (2) | 0.0215 (17) |
C6 | 0.061 (2) | 0.045 (2) | 0.054 (2) | 0.0211 (17) | 0.0298 (18) | 0.0284 (17) |
C7 | 0.0462 (18) | 0.0360 (17) | 0.0393 (17) | 0.0120 (14) | 0.0237 (14) | 0.0176 (14) |
C8 | 0.049 (2) | 0.051 (2) | 0.048 (2) | 0.0102 (17) | 0.0129 (16) | 0.0299 (17) |
C9 | 0.084 (3) | 0.063 (3) | 0.051 (2) | −0.009 (2) | −0.011 (2) | 0.020 (2) |
C10 | 0.0415 (17) | 0.0281 (15) | 0.0292 (15) | 0.0069 (13) | 0.0129 (14) | 0.0142 (12) |
C11 | 0.0412 (17) | 0.0329 (16) | 0.0287 (15) | 0.0074 (13) | 0.0118 (13) | 0.0089 (12) |
C12 | 0.0457 (19) | 0.055 (2) | 0.0348 (18) | 0.0047 (16) | 0.0144 (15) | 0.0086 (15) |
C13 | 0.063 (2) | 0.081 (3) | 0.042 (2) | 0.010 (2) | 0.0296 (19) | 0.0068 (19) |
C14 | 0.072 (3) | 0.086 (3) | 0.0330 (19) | 0.011 (2) | 0.0174 (19) | −0.0013 (19) |
C15 | 0.051 (2) | 0.065 (2) | 0.0349 (19) | 0.0045 (18) | 0.0053 (16) | 0.0020 (17) |
C16 | 0.0424 (17) | 0.0359 (17) | 0.0335 (17) | 0.0065 (14) | 0.0110 (14) | 0.0076 (13) |
C17 | 0.0405 (18) | 0.0426 (19) | 0.0361 (17) | 0.0053 (15) | 0.0070 (14) | 0.0094 (14) |
C18 | 0.054 (2) | 0.081 (3) | 0.061 (3) | −0.002 (2) | 0.0207 (19) | 0.030 (2) |
C19 | 0.0412 (19) | 0.057 (2) | 0.053 (2) | 0.0121 (16) | 0.0240 (17) | 0.0224 (18) |
C20 | 0.059 (2) | 0.107 (4) | 0.061 (3) | 0.027 (2) | 0.018 (2) | 0.045 (2) |
Cu1—O2i | 1.959 (2) | C5—H5 | 0.9300 |
Cu1—O6i | 1.967 (2) | C6—C7 | 1.390 (4) |
Cu1—O5 | 1.973 (2) | C6—H6 | 0.9300 |
Cu1—O1 | 1.9775 (19) | C7—C8 | 1.497 (5) |
Cu1—N1 | 2.186 (3) | C9—H9A | 0.9600 |
Cu1—Cu1i | 2.6662 (7) | C9—H9B | 0.9600 |
N1—C19 | 1.111 (4) | C9—H9C | 0.9600 |
O1—C1 | 1.264 (4) | C10—C11 | 1.503 (4) |
O2—C1 | 1.253 (4) | C11—C12 | 1.385 (5) |
O2—Cu1i | 1.9590 (19) | C11—C16 | 1.405 (4) |
O3—C8 | 1.338 (4) | C12—C13 | 1.380 (5) |
O3—C9 | 1.445 (4) | C12—H12 | 0.9300 |
O4—C8 | 1.197 (4) | C13—C14 | 1.382 (6) |
O5—C10 | 1.263 (3) | C13—H13 | 0.9300 |
O6—C10 | 1.259 (4) | C14—C15 | 1.383 (5) |
O6—Cu1i | 1.967 (2) | C14—H14 | 0.9300 |
O7—C17 | 1.335 (4) | C15—C16 | 1.385 (4) |
O7—C18 | 1.439 (4) | C15—H15 | 0.9300 |
O8—C17 | 1.202 (4) | C16—C17 | 1.492 (5) |
C1—C2 | 1.505 (4) | C18—H18A | 0.9600 |
C2—C3 | 1.380 (4) | C18—H18B | 0.9600 |
C2—C7 | 1.388 (4) | C18—H18C | 0.9600 |
C3—C4 | 1.375 (5) | C19—C20 | 1.464 (5) |
C3—H3 | 0.9300 | C20—H20A | 0.9600 |
C4—C5 | 1.371 (5) | C20—H20B | 0.9600 |
C4—H4 | 0.9300 | C20—H20C | 0.9600 |
C5—C6 | 1.373 (5) | ||
O2i—Cu1—O6i | 88.57 (9) | O3—C8—C7 | 109.7 (3) |
O2i—Cu1—O5 | 89.00 (9) | O3—C9—H9A | 109.5 |
O6i—Cu1—O5 | 167.59 (8) | O3—C9—H9B | 109.5 |
O2i—Cu1—O1 | 167.74 (9) | H9A—C9—H9B | 109.5 |
O6i—Cu1—O1 | 89.31 (9) | O3—C9—H9C | 109.5 |
O5—Cu1—O1 | 90.49 (9) | H9A—C9—H9C | 109.5 |
O2i—Cu1—N1 | 103.49 (10) | H9B—C9—H9C | 109.5 |
O6i—Cu1—N1 | 90.66 (10) | O6—C10—O5 | 125.9 (3) |
O5—Cu1—N1 | 101.74 (10) | O6—C10—C11 | 116.7 (2) |
O1—Cu1—N1 | 88.60 (10) | O5—C10—C11 | 117.3 (3) |
O2i—Cu1—Cu1i | 86.83 (6) | C12—C11—C16 | 118.7 (3) |
O6i—Cu1—Cu1i | 83.15 (6) | C12—C11—C10 | 120.0 (3) |
O5—Cu1—Cu1i | 84.57 (6) | C16—C11—C10 | 121.2 (3) |
O1—Cu1—Cu1i | 80.93 (6) | C13—C12—C11 | 121.7 (3) |
N1—Cu1—Cu1i | 167.87 (8) | C13—C12—H12 | 119.1 |
C19—N1—Cu1 | 151.4 (3) | C11—C12—H12 | 119.1 |
C1—O1—Cu1 | 125.83 (19) | C12—C13—C14 | 119.3 (4) |
C1—O2—Cu1i | 120.03 (19) | C12—C13—H13 | 120.3 |
C8—O3—C9 | 116.4 (3) | C14—C13—H13 | 120.3 |
C10—O5—Cu1 | 122.1 (2) | C13—C14—C15 | 120.0 (3) |
C10—O6—Cu1i | 124.20 (19) | C13—C14—H14 | 120.0 |
C17—O7—C18 | 115.9 (3) | C15—C14—H14 | 120.0 |
O2—C1—O1 | 126.4 (3) | C14—C15—C16 | 120.9 (3) |
O2—C1—C2 | 117.5 (3) | C14—C15—H15 | 119.5 |
O1—C1—C2 | 116.1 (3) | C16—C15—H15 | 119.5 |
C3—C2—C7 | 118.7 (3) | C15—C16—C11 | 119.4 (3) |
C3—C2—C1 | 118.9 (3) | C15—C16—C17 | 117.3 (3) |
C7—C2—C1 | 122.3 (3) | C11—C16—C17 | 123.3 (3) |
C4—C3—C2 | 121.3 (3) | O8—C17—O7 | 123.6 (3) |
C4—C3—H3 | 119.3 | O8—C17—C16 | 124.9 (3) |
C2—C3—H3 | 119.3 | O7—C17—C16 | 111.3 (3) |
C5—C4—C3 | 119.7 (3) | O7—C18—H18A | 109.5 |
C5—C4—H4 | 120.1 | O7—C18—H18B | 109.5 |
C3—C4—H4 | 120.1 | H18A—C18—H18B | 109.5 |
C4—C5—C6 | 120.1 (3) | O7—C18—H18C | 109.5 |
C4—C5—H5 | 120.0 | H18A—C18—H18C | 109.5 |
C6—C5—H5 | 120.0 | H18B—C18—H18C | 109.5 |
C5—C6—C7 | 120.3 (3) | N1—C19—C20 | 178.4 (4) |
C5—C6—H6 | 119.8 | C19—C20—H20A | 109.5 |
C7—C6—H6 | 119.8 | C19—C20—H20B | 109.5 |
C2—C7—C6 | 119.8 (3) | H20A—C20—H20B | 109.5 |
C2—C7—C8 | 122.5 (3) | C19—C20—H20C | 109.5 |
C6—C7—C8 | 117.6 (3) | H20A—C20—H20C | 109.5 |
O4—C8—O3 | 125.1 (4) | H20B—C20—H20C | 109.5 |
O4—C8—C7 | 125.1 (4) | ||
O2i—Cu1—N1—C19 | 131.8 (6) | C5—C6—C7—C8 | 175.7 (3) |
O6i—Cu1—N1—C19 | 43.1 (7) | C9—O3—C8—O4 | 2.5 (5) |
O5—Cu1—N1—C19 | −136.4 (7) | C9—O3—C8—C7 | 178.8 (3) |
O1—Cu1—N1—C19 | −46.2 (7) | C2—C7—C8—O4 | −125.1 (4) |
Cu1i—Cu1—N1—C19 | −15.9 (10) | C6—C7—C8—O4 | 58.7 (5) |
O2i—Cu1—O1—C1 | 4.0 (5) | C2—C7—C8—O3 | 58.5 (4) |
O6i—Cu1—O1—C1 | 84.0 (2) | C6—C7—C8—O3 | −117.7 (3) |
O5—Cu1—O1—C1 | −83.6 (2) | Cu1i—O6—C10—O5 | 0.6 (4) |
N1—Cu1—O1—C1 | 174.7 (2) | Cu1i—O6—C10—C11 | −177.57 (17) |
Cu1i—Cu1—O1—C1 | 0.8 (2) | Cu1—O5—C10—O6 | 1.9 (4) |
O2i—Cu1—O5—C10 | −89.3 (2) | Cu1—O5—C10—C11 | −179.96 (17) |
O6i—Cu1—O5—C10 | −10.6 (5) | O6—C10—C11—C12 | 159.6 (3) |
O1—Cu1—O5—C10 | 78.5 (2) | O5—C10—C11—C12 | −18.8 (4) |
N1—Cu1—O5—C10 | 167.1 (2) | O6—C10—C11—C16 | −15.6 (4) |
Cu1i—Cu1—O5—C10 | −2.4 (2) | O5—C10—C11—C16 | 166.0 (3) |
Cu1i—O2—C1—O1 | −0.4 (4) | C16—C11—C12—C13 | 0.8 (5) |
Cu1i—O2—C1—C2 | −178.87 (18) | C10—C11—C12—C13 | −174.5 (3) |
Cu1—O1—C1—O2 | −0.5 (4) | C11—C12—C13—C14 | 0.0 (6) |
Cu1—O1—C1—C2 | 177.95 (18) | C12—C13—C14—C15 | −0.6 (7) |
O2—C1—C2—C3 | 34.7 (4) | C13—C14—C15—C16 | 0.3 (6) |
O1—C1—C2—C3 | −143.9 (3) | C14—C15—C16—C11 | 0.6 (5) |
O2—C1—C2—C7 | −149.3 (3) | C14—C15—C16—C17 | −177.5 (4) |
O1—C1—C2—C7 | 32.1 (4) | C12—C11—C16—C15 | −1.1 (5) |
C7—C2—C3—C4 | 0.3 (5) | C10—C11—C16—C15 | 174.1 (3) |
C1—C2—C3—C4 | 176.4 (3) | C12—C11—C16—C17 | 176.8 (3) |
C2—C3—C4—C5 | −0.9 (6) | C10—C11—C16—C17 | −7.9 (4) |
C3—C4—C5—C6 | 0.8 (6) | C18—O7—C17—O8 | −5.2 (5) |
C4—C5—C6—C7 | −0.1 (5) | C18—O7—C17—C16 | 180.0 (3) |
C3—C2—C7—C6 | 0.4 (5) | C15—C16—C17—O8 | −66.9 (5) |
C1—C2—C7—C6 | −175.5 (3) | C11—C16—C17—O8 | 115.1 (4) |
C3—C2—C7—C8 | −175.7 (3) | C15—C16—C17—O7 | 107.8 (3) |
C1—C2—C7—C8 | 8.4 (5) | C11—C16—C17—O7 | −70.2 (4) |
C5—C6—C7—C2 | −0.5 (5) | Cu1—N1—C19—C20 | −23 (16) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O5ii | 0.93 | 2.51 | 3.379 (4) | 156 |
Symmetry code: (ii) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C9H7O4)4(C2H3N)2] |
Mr | 925.77 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 8.2332 (10), 10.5730 (13), 12.6673 (15) |
α, β, γ (°) | 104.774 (1), 108.061 (2), 91.152 (1) |
V (Å3) | 1007.8 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.41 × 0.30 × 0.27 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.654, 0.750 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5143, 3466, 2906 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.105, 1.07 |
No. of reflections | 3466 |
No. of parameters | 271 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.32 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···O5i | 0.93 | 2.51 | 3.3793 (40) | 156 |
Symmetry code: (i) −x+1, −y, −z+1. |
Acknowledgements
The authors thank the National Natural Science Foundation of the People's Republic of China (grant No. 21201024), the Natural Science Foundation of Shanxi Province (grant No. 2012021009–1), and the Scientific Research Foundation for PhDs of Changzhi University.
References
Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kato, M., Jonassen, H. B. & Fanning, J. C. (1964). Chem. Rev. 64, 99–128. CrossRef CAS Web of Science Google Scholar
Liu, T.-H., Huang, L., Chen, F.-J., Xi, P.-X., Xu, Z.-H., Xu, M. & Zeng, Z.-Z. (2008). Anal. Sci. 24, x303–x304. Google Scholar
Reinhard, P., Stefan, L., Carsten, T., Michael, A. O. & Ekkehard, S. (2003). Inorg. Chem. 42, 8230–8240. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
A large number of binuclear CuII carboxylato compounds are an attractive target of chemical research due to their magnetism (Kato et al., 1964) and electrochemical behavior (Reinhard et al., 2003). In general, binuclear copper (II) carboxylates consist of four three-atom bridges, uniting two contiguous copper(II) ions and exhibit a paddle-wheel cage structure.
Herein we report synthesis and crystal structure of binuclear copper(II) carboxylato compound with 2-(methoxycarbonyl)benzoic acid acting as a bidentate chelating ligand. Each copper(II) is coordinated by four carboxylate O donor atoms from four ligands, and by N donor atoms from the solvent molecule, The Cu—O distances and related angles are all within expected ranges (Kato et al., 1964) and Cu—N distance is 2.186 (3) Å. A binuclear copper carboxylate unit is formed by four (HL) ligands and two Cu centres with a Cu—Cu separation of 2.6662 (7) Å.
In the crystal structure, weak C—H···O hydrogen bonds (H···O distance of 2.5087 (22) Å) and π-π interactions (centroid–centroid distance of 3.6929 (3) Å) link the molecules into an infinite one-dimensional chain extending along the b axis.