Tetra­kis[μ-2-(meth­oxy­carbon­yl)benzoato-κ2O1:O1′]bis­[(acetonitrile-κN)copper(II)](Cu—Cu)

Wang, J.; Wang, C.; Wang, Z.; Yang, B.

doi:10.1107/S1600536812049410

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 1| January 2013| Page m19

https://doi.org/10.1107/S1600536812049410

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Tetrakis[μ-2-(methoxycarbonyl)benzoato-κ²O¹:O^1′]bis[(acetonitrile-κN)copper(II)](Cu—Cu)

Jing-lin Wang,^a ^* Cai-rong Wang,^a Zhi-jun Wang ^a and Bin-sheng Yang ^b

^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

(Received 5 November 2012; accepted 2 December 2012; online 8 December 2012)

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 Cu^II atom together with its four coordinated O atoms are in a distorted planar square arrangement while the nitrogen and the other Cu^II 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 Cu^II 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

[Cu₂(C₉H₇O₄)₄(C₂H₃N)₂]
M_r = 925.77
Triclinic, $[P \overline 1]$
a = 8.2332 (10) Å
b = 10.5730 (13) Å
c = 12.6673 (15) Å
α = 104.774 (1)°
β = 108.061 (2)°
γ = 91.152 (1)°
V = 1007.8 (2) Å³
Z = 1
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 298 K
0.41 × 0.30 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.654, T_max = 0.750
5143 measured reflections
3466 independent reflections
2906 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.105
S = 1.07
3466 reflections
271 parameters
H-atom parameters constrained
Δρ_max = 0.55 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O5ⁱ	0.93	2.51	3.379 (4)	156
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 1999 ); cell refinement: 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

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812049410/lr2089sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812049410/lr2089Isup2.hkl

checkCIF report

Comment top

A large number of binuclear Cu^II 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.

Related literature top

For a review on related binuclear Cu^II 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 top

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.

Structure description top

For a review on related binuclear Cu^II 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).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: 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).

Figures top

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. The H atoms attached to C atoms were omitted for clarity. Atoms with the A label are generated by the (1 - x, 1 - y, 1 - z) symmetry operation.
	Fig. 2. View of the crystal packing along the a axis. Hydrogen-bonding and π-π interactions are represented by black dashed lines and pink dashed lines, respectively (all distances in Å). For the sake of clarity, H atoms not involved in hydrogen bonding have been omitted.

Tetrakis[µ-2-(methoxycarbonyl)benzoato- κ²O¹:O^1']bis[(acetonitrile- κN)copper(II)](Cu—Cu) top

Crystal data top

[Cu₂(C₉H₇O₄)₄(C₂H₃N)₂]	Z = 1
M_r = 925.77	F(000) = 474
Triclinic, P1	D_x = 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

Data collection top

Bruker SMART CCD area-detector diffractometer	3466 independent reflections
Radiation source: fine-focus sealed tube	2906 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
phi and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.654, T_max = 0.750	k = −12→12
5143 measured reflections	l = −11→15

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) = 0.105	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0576P)² + 0.2799P] where P = (F_o² + 2F_c²)/3
3466 reflections	(Δ/σ)_max = 0.001
271 parameters	Δρ_max = 0.55 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Cu₂(C₉H₇O₄)₄(C₂H₃N)₂]	γ = 91.152 (1)°
M_r = 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)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3466 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2906 reflections with I > 2σ(I)
T_min = 0.654, T_max = 0.750	R_int = 0.022
5143 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.105	H-atom parameters constrained
S = 1.07	Δρ_max = 0.55 e Å⁻³
3466 reflections	Δρ_min = −0.32 e Å⁻³
271 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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.

Hydrogen-bond geometry (Å, º) top

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]
M_r	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)
T_min, T_max	0.654, 0.750
No. of measured, independent and observed [I > 2σ(I)] reflections	5143, 3466, 2906
R_int	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
Δρ_max, Δρ_min (e Å⁻³)	0.55, −0.32

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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
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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

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