Di-μ-chlorido-bis­{[2-(8-quinol­yloxy)­acetato-κ3N,O1,O2]copper(II)}

Wang, Z.; Fan, J.; Zhang, W.; Wang, J.

doi:10.1107/S1600536808031656

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1446

doi:10.1107/S1600536808031656

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Di-μ-chlorido-bis{[2-(8-quinolyloxy)acetato-κ³N,O¹,O²]copper(II)}

Zhi-hong Wang,^a Jun Fan,^a Wei-guang Zhang ^a ^* and Jun Wang ^a

^aSchool of Chemistry and Environment, South China Normal University, Guangzhou 510006, People's Republic of China
^*Correspondence e-mail: wgzhang@scnu.edu.cn

(Received 8 September 2008; accepted 30 September 2008; online 18 October 2008)

The title compound, [Cu₂(C₁₁H₈NO₃)₂Cl₂], is a bicopper(II) complex. Each Cu^II ion is five-coordinated by two O atoms and one N atom from the (8-quinolyloxy)acetate ligand, and by two μ₂-chloride ligands, thus exhibiting a distorted square-pyramidal CuCl₂NO₂ coordination environment. Each (8-quinolyloxy)acetate anion acts as a tridentate chelating ligand. In the crystal structure, adjacent quinolyl rings are involved in strong π–π stacking interactions, with interplanar distances of 3.549 (5) and 3.763 (5) Å, thereby forming a two-dimensional planar network perpendicular to the ab plane. Furthermore, a weak interaction [2.750 (4) Å] is observed within these planes between one Cu^II ion and a carboxylate O atom from a ligand in an adjacent molecule, which also contributes to the stability of the structure.

Related literature

For general background, see: Hong et al. (2006 ); Sudik et al. (2005 ); Dong et al. (2007 ); Tong et al., 1999 . For related structures, see: Wang & Lu (2004 ); Wang et al. (2005 ). Koelsch (1931 ) reports the synthesis of the (8-quinolyloxy)acetate ligand.

Experimental

Crystal data

[Cu₂(C₁₁H₈NO₃)₂Cl₂]
M_r = 602.35
Monoclinic, P 2₁ /c
a = 8.3796 (17) Å
b = 19.195 (4) Å
c = 13.392 (3) Å
β = 98.85 (3)°
V = 2128.4 (8) Å³
Z = 4
Mo Kα radiation
μ = 2.29 mm⁻¹
T = 298 (2) K
0.36 × 0.30 × 0.24 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.462, T_max = 0.582
11625 measured reflections
4179 independent reflections
2737 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.087
S = 1.01
4179 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ); 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) and ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808031656/zl2140sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808031656/zl2140Isup2.hkl

checkCIF report

Comment top

Metal–polycarboxylate coordination polymers have attracted considerable attention in past decades, owing to their fascinating architectures and potential applications as new materials in gas absorption, catalysis and luminescence (Dong et al., 2007; Sudik et al., 2005). However, only a limited amount of work has been reported on the use of benzene polycarboxylate ligands that combine characteristics of both flexibility and rigidity (Hong et al., 2006; Wang & Lu, 2004; Wang et al., 2005).

Herein, we report the crystal structure of the title compound, (I). A perspective view of the binuclear copper complex (I), showing the atomic numbering scheme, is depicted in Fig. 1. The coordination geometry around the Cu^II ion may be described as a slightly distorted square pyramid, the basal plane being defined by one N atom, two O atoms from (8-quinolyloxy)acetate and one chloride anion; the apical position is occupied by another bridging chloride anion from the adjacent copper(II) unit, this atom being coordinated at a longer distance [Cu1—Cl2 = 2.823 (14) Å and Cu2—Cl1 = 2.776 (12) Å]. Thus, two chlorides form bi-bridges between two Cu^II ions, which link two Cu^II units to generate a binuclear complex. Each (8-quinolyloxy)acetate molecule acts as a tridentate chelating ligand. The inequivalence of the carboxylate C—O distances may be correlated with their involvement in bonding with the Cu^II centres.

In the crystal structure, adjacent quinolinyl rings are involved in strong π-π stacking attractions by partial overlapping of π-electron densities (Tong et al., 1999). The centroid-centroid separation between rings A (atoms N1/C1—C4/C9) and Bⁱ [atoms C15—C20; symmetry code: (i): - x, 1/2 + y, 1/2 - z] is 3.763 (5) Å, and the other between rings C (atoms C4—C9) and D^j [atoms N2/C12—C15/C20; symmetry code: (j): 1- x, 1/2 + y, 1/2 - z] is 3.549 (5) Å. Considering these π-π intermolecular attractions, they imply the formation of a two-dimensional planar network perpendicular to the ab plane (Fig. 2). Furthermore, a weak interaction [2.750 (4) Å] is observed between the atom Cu1 and carboxylate oxygen atom O6^k [symmetry code: (k): -1+x,y,z] from the ligand in adjacent Cu^II unit, thus contributing to the two-dimensional network's stability (Fig. 2).

Related literature top

For general background, see: Hong et al. (2006); Sudik et al. (2005); Dong et al. (2007); Tong et al., 1999. For related structures, see: Wang & Lu (2004); Wang et al. (2005). Koelsch (1931) reports the synthesis of the (8-quinolyloxy)acetate ligand.

Experimental top

The ligand quinolin-8-yloxyacetic acid was prepared according to the general procedure reported by Koelsch (1931). An aqueous solution of CuCl₂.2 H₂O (0.057 g, 0.33 mmol) was added dropwise to the mixture of Y(NO₃)₃.6 H₂O (0.064 g, 0.17 mmol) and quinolin-8-yloxyacetic acid (0.103 g, 0.50 mmol) in aqueous solution at 343 K, and the pH value was adjusted to be about 5 with NaOH. After stirring for 0.5 h, the resulting green solution was filtered. Slow evaporation from the filtrate for several weeks yielded green block-like crystals suitable for X-ray analysis. IR (KBr pellet, cm^-1): 3051, 1650, 1628, 1505, 1429, 1379, 1317, 1263, 1115, 837, 772.

Computing details top

Data collection: SMART (Bruker, 1998); 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) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. An ORTEP-3 (Farrugia, 1997) plot of (I), with displacement ellipsoids at the 50% probability level. All H atoms are drawn as spheres of arbitrary radius.
	Fig. 2. The packing diagram of (I), viewed perpendicular to the ab plane, showing the two-dimensional planar network generated by the π-π and weak Cu···O interactions. All H atoms have been omitted for clarity. [Symmetry codes: (i): -x, 1/2 + y, 1/2 - z; (j): 1 - x, 1/2 + y, 1/2 - z].

Di-µ-chlorido-bis{[2-(8-quinolyloxy)acetato- κ³N,O¹,O²]copper(II)} top

Crystal data top

[Cu₂(C₁₁H₈NO₃)₂Cl₂]	F(000) = 1208
M_r = 602.35	D_x = 1.880 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2969 reflections
a = 8.3796 (17) Å	θ = 1.9–27.8°
b = 19.195 (4) Å	µ = 2.30 mm⁻¹
c = 13.392 (3) Å	T = 298 K
β = 98.85 (3)°	Block, green
V = 2128.4 (8) Å³	0.36 × 0.30 × 0.24 mm
Z = 4

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4179 independent reflections
Radiation source: fine-focus sealed tube	2737 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→10
T_min = 0.462, T_max = 0.582	k = −19→23
11625 measured reflections	l = −16→13

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0256P)² + 1.1172P] where P = (F_o² + 2F_c²)/3
4179 reflections	(Δ/σ)_max = 0.001
307 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

[Cu₂(C₁₁H₈NO₃)₂Cl₂]	V = 2128.4 (8) Å³
M_r = 602.35	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.3796 (17) Å	µ = 2.30 mm⁻¹
b = 19.195 (4) Å	T = 298 K
c = 13.392 (3) Å	0.36 × 0.30 × 0.24 mm
β = 98.85 (3)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	4179 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2737 reflections with I > 2σ(I)
T_min = 0.462, T_max = 0.582	R_int = 0.049
11625 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.01	Δρ_max = 0.44 e Å⁻³
4179 reflections	Δρ_min = −0.47 e Å⁻³
307 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
C1	0.8714 (5)	−0.0068 (2)	0.8758 (3)	0.0368 (10)
H1	0.8366	0.0265	0.9181	0.044*
C2	0.8505 (5)	−0.0778 (2)	0.8966 (3)	0.0432 (12)
H2	0.8054	−0.0908	0.9531	0.052*
C3	0.8959 (5)	−0.1275 (2)	0.8345 (3)	0.0428 (12)
H3	0.8799	−0.1744	0.8473	0.051*
C4	0.9673 (5)	−0.10730 (19)	0.7508 (3)	0.0325 (10)
C5	1.0242 (5)	−0.1536 (2)	0.6825 (4)	0.0409 (12)
H5	1.0099	−0.2012	0.6900	0.049*
C6	1.0990 (5)	−0.1304 (2)	0.6066 (4)	0.0434 (12)
H6	1.1356	−0.1624	0.5631	0.052*
C7	1.1226 (5)	−0.05832 (19)	0.5921 (3)	0.0345 (10)
H7	1.1760	−0.0427	0.5403	0.041*
C8	1.0658 (5)	−0.01268 (18)	0.6549 (3)	0.0282 (9)
C9	0.9887 (4)	−0.03519 (19)	0.7356 (3)	0.0270 (9)
C10	1.1952 (5)	0.09524 (18)	0.6061 (3)	0.0322 (10)
H10A	1.1737	0.0926	0.5329	0.039*
H10B	1.3003	0.0748	0.6291	0.039*
C11	1.1912 (5)	0.17117 (19)	0.6411 (3)	0.0321 (10)
C12	0.6792 (5)	0.2987 (2)	0.6160 (3)	0.0381 (11)
H12	0.7235	0.2651	0.5784	0.046*
C13	0.6801 (5)	0.3683 (2)	0.5850 (3)	0.0437 (12)
H13	0.7255	0.3802	0.5282	0.052*
C14	0.6146 (5)	0.4184 (2)	0.6376 (3)	0.0404 (11)
H14	0.6133	0.4646	0.6163	0.049*
C15	0.5487 (5)	0.40025 (19)	0.7247 (3)	0.0302 (10)
C16	0.4806 (5)	0.4478 (2)	0.7871 (3)	0.0371 (11)
H16	0.4763	0.4950	0.7709	0.044*
C17	0.4217 (5)	0.4254 (2)	0.8700 (3)	0.0380 (11)
H17	0.3793	0.4578	0.9105	0.046*
C18	0.4230 (5)	0.35414 (19)	0.8967 (3)	0.0340 (10)
H18	0.3814	0.3392	0.9536	0.041*
C19	0.4869 (5)	0.30816 (18)	0.8366 (3)	0.0288 (9)
C20	0.5517 (4)	0.32890 (18)	0.7511 (3)	0.0273 (9)
C21	0.3712 (5)	0.20080 (18)	0.8940 (3)	0.0307 (10)
H21A	0.2681	0.2219	0.8677	0.037*
H21B	0.3863	0.2032	0.9672	0.037*
C22	0.3754 (5)	0.1251 (2)	0.8592 (3)	0.0323 (10)
Cl1	0.88233 (13)	0.17203 (5)	0.87627 (8)	0.0355 (3)
Cl2	0.68751 (13)	0.12051 (5)	0.62854 (8)	0.0378 (3)
Cu1	0.98473 (6)	0.11091 (2)	0.75955 (4)	0.03462 (16)
Cu2	0.59143 (6)	0.18353 (2)	0.74655 (4)	0.03365 (16)
N1	0.9383 (4)	0.01413 (15)	0.7986 (2)	0.0284 (8)
N2	0.6180 (4)	0.27902 (15)	0.6966 (2)	0.0284 (8)
O1	1.0725 (3)	0.05920 (12)	0.6493 (2)	0.0345 (7)
O2	1.0939 (3)	0.18630 (12)	0.7016 (2)	0.0350 (7)
O3	1.2868 (4)	0.21096 (14)	0.6113 (2)	0.0504 (9)
O4	0.5008 (3)	0.23677 (12)	0.85579 (19)	0.0296 (6)
O5	0.4801 (3)	0.10898 (12)	0.8035 (2)	0.0369 (7)
O6	0.2728 (4)	0.08555 (14)	0.8829 (2)	0.0501 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.037 (3)	0.038 (2)	0.040 (3)	−0.0059 (19)	0.018 (2)	−0.001 (2)
C2	0.047 (3)	0.042 (3)	0.043 (3)	−0.010 (2)	0.017 (2)	0.015 (2)
C3	0.045 (3)	0.028 (2)	0.055 (3)	−0.005 (2)	0.006 (2)	0.007 (2)
C4	0.031 (3)	0.025 (2)	0.040 (3)	−0.0021 (17)	0.001 (2)	0.0057 (19)
C5	0.042 (3)	0.017 (2)	0.062 (3)	0.0001 (18)	0.002 (2)	−0.002 (2)
C6	0.048 (3)	0.031 (2)	0.049 (3)	0.009 (2)	0.001 (2)	−0.015 (2)
C7	0.039 (3)	0.032 (2)	0.032 (3)	0.0041 (18)	0.006 (2)	−0.0038 (19)
C8	0.029 (2)	0.021 (2)	0.034 (2)	0.0002 (16)	0.0036 (19)	−0.0039 (17)
C9	0.025 (2)	0.026 (2)	0.030 (2)	0.0031 (16)	0.0046 (18)	0.0019 (18)
C10	0.035 (3)	0.033 (2)	0.032 (2)	−0.0030 (18)	0.0151 (19)	0.0014 (19)
C11	0.034 (3)	0.029 (2)	0.034 (3)	−0.0018 (18)	0.008 (2)	0.0014 (19)
C12	0.042 (3)	0.039 (2)	0.036 (3)	−0.007 (2)	0.015 (2)	−0.004 (2)
C13	0.054 (3)	0.043 (3)	0.037 (3)	−0.009 (2)	0.016 (2)	0.006 (2)
C14	0.048 (3)	0.031 (2)	0.043 (3)	−0.006 (2)	0.009 (2)	0.008 (2)
C15	0.028 (2)	0.028 (2)	0.033 (3)	−0.0051 (17)	0.0011 (19)	0.0008 (18)
C16	0.040 (3)	0.022 (2)	0.047 (3)	0.0005 (18)	0.000 (2)	−0.004 (2)
C17	0.042 (3)	0.027 (2)	0.048 (3)	0.0005 (19)	0.014 (2)	−0.009 (2)
C18	0.038 (3)	0.030 (2)	0.037 (3)	−0.0006 (18)	0.017 (2)	−0.0072 (19)
C19	0.031 (2)	0.023 (2)	0.032 (2)	−0.0030 (17)	0.0058 (19)	0.0014 (18)
C20	0.028 (2)	0.022 (2)	0.032 (2)	−0.0033 (16)	0.0042 (18)	−0.0042 (17)
C21	0.032 (2)	0.028 (2)	0.036 (3)	−0.0038 (17)	0.0158 (19)	−0.0004 (18)
C22	0.038 (3)	0.029 (2)	0.030 (3)	−0.0011 (18)	0.005 (2)	0.0003 (18)
Cl1	0.0459 (7)	0.0303 (5)	0.0342 (6)	0.0017 (4)	0.0184 (5)	−0.0031 (4)
Cl2	0.0448 (7)	0.0367 (6)	0.0346 (6)	0.0054 (5)	0.0142 (5)	−0.0073 (5)
Cu1	0.0460 (3)	0.0222 (3)	0.0414 (3)	−0.0020 (2)	0.0248 (2)	−0.0008 (2)
Cu2	0.0420 (3)	0.0234 (3)	0.0405 (3)	−0.0009 (2)	0.0220 (2)	−0.0033 (2)
N1	0.0268 (19)	0.0278 (17)	0.033 (2)	−0.0023 (14)	0.0128 (15)	0.0011 (15)
N2	0.030 (2)	0.0251 (17)	0.032 (2)	−0.0029 (14)	0.0101 (16)	−0.0027 (15)
O1	0.0459 (19)	0.0225 (14)	0.0404 (18)	−0.0029 (12)	0.0241 (14)	0.0024 (12)
O2	0.0457 (19)	0.0259 (14)	0.0383 (18)	−0.0044 (13)	0.0220 (14)	−0.0003 (13)
O3	0.055 (2)	0.0372 (17)	0.067 (2)	−0.0154 (15)	0.0353 (18)	−0.0038 (16)
O4	0.0359 (17)	0.0216 (13)	0.0355 (17)	−0.0016 (11)	0.0192 (13)	−0.0022 (12)
O5	0.0466 (19)	0.0231 (14)	0.0464 (19)	−0.0008 (13)	0.0240 (15)	−0.0021 (13)
O6	0.055 (2)	0.0334 (16)	0.070 (2)	−0.0102 (15)	0.0363 (18)	−0.0018 (16)

Geometric parameters (Å, º) top

C1—N1	1.312 (5)	C14—C15	1.409 (6)
C1—C2	1.409 (5)	C14—H14	0.9300
C1—H1	0.9300	C15—C20	1.414 (5)
C2—C3	1.357 (6)	C15—C16	1.416 (5)
C2—H2	0.9300	C16—C17	1.353 (6)
C3—C4	1.405 (6)	C16—H16	0.9300
C3—H3	0.9300	C17—C18	1.414 (5)
C4—C5	1.408 (6)	C17—H17	0.9300
C4—C9	1.414 (5)	C18—C19	1.359 (5)
C5—C6	1.349 (6)	C18—H18	0.9300
C5—H5	0.9300	C19—O4	1.396 (4)
C6—C7	1.416 (5)	C19—C20	1.398 (5)
C6—H6	0.9300	C20—N2	1.372 (5)
C7—C8	1.351 (5)	C21—O4	1.445 (4)
C7—H7	0.9300	C21—C22	1.528 (5)
C8—O1	1.383 (4)	C21—H21A	0.9700
C8—C9	1.409 (5)	C21—H21B	0.9700
C9—N1	1.377 (5)	C22—O6	1.224 (5)
C10—O1	1.433 (4)	C22—O5	1.274 (5)
C10—C11	1.533 (5)	Cl1—Cu1	2.2290 (12)
C10—H10A	0.9700	Cl2—Cu2	2.2362 (12)
C10—H10B	0.9700	Cu1—O2	1.937 (3)
C11—O3	1.218 (5)	Cu1—N1	1.985 (3)
C11—O2	1.269 (5)	Cu1—O1	2.011 (3)
C12—N2	1.320 (5)	Cu2—O5	1.929 (3)
C12—C13	1.400 (5)	Cu2—N2	1.976 (3)
C12—H12	0.9300	Cu2—O4	2.026 (3)
C13—C14	1.357 (6)	Cu1—Cl2	2.8232 (14)
C13—H13	0.9300	Cu2—Cl1	2.7761 (12)

N1—C1—C2	122.2 (4)	C17—C16—H16	119.6
N1—C1—H1	118.9	C15—C16—H16	119.6
C2—C1—H1	118.9	C16—C17—C18	121.7 (4)
C3—C2—C1	120.2 (4)	C16—C17—H17	119.1
C3—C2—H2	119.9	C18—C17—H17	119.1
C1—C2—H2	119.9	C19—C18—C17	117.8 (4)
C2—C3—C4	119.4 (4)	C19—C18—H18	121.1
C2—C3—H3	120.3	C17—C18—H18	121.1
C4—C3—H3	120.3	C18—C19—O4	123.9 (4)
C3—C4—C5	124.9 (4)	C18—C19—C20	122.6 (4)
C3—C4—C9	117.6 (4)	O4—C19—C20	113.5 (3)
C5—C4—C9	117.4 (4)	N2—C20—C19	118.5 (3)
C6—C5—C4	121.6 (4)	N2—C20—C15	122.4 (4)
C6—C5—H5	119.2	C19—C20—C15	119.1 (4)
C4—C5—H5	119.2	O4—C21—C22	107.0 (3)
C5—C6—C7	121.1 (4)	O4—C21—H21A	110.3
C5—C6—H6	119.5	C22—C21—H21A	110.3
C7—C6—H6	119.5	O4—C21—H21B	110.3
C8—C7—C6	118.6 (4)	C22—C21—H21B	110.3
C8—C7—H7	120.7	H21A—C21—H21B	108.6
C6—C7—H7	120.7	O6—C22—O5	125.1 (4)
C7—C8—O1	126.2 (4)	O6—C22—C21	117.4 (4)
C7—C8—C9	121.7 (3)	O5—C22—C21	117.3 (3)
O1—C8—C9	112.0 (3)	O2—Cu1—N1	158.25 (12)
N1—C9—C8	118.6 (3)	O2—Cu1—O1	79.98 (11)
N1—C9—C4	121.8 (4)	N1—Cu1—O1	80.80 (12)
C8—C9—C4	119.6 (4)	O2—Cu1—Cl1	98.29 (9)
O1—C10—C11	106.5 (3)	N1—Cu1—Cl1	101.28 (10)
O1—C10—H10A	110.4	O1—Cu1—Cl1	177.22 (8)
C11—C10—H10A	110.4	O5—Cu2—N2	155.37 (13)
O1—C10—H10B	110.4	O5—Cu2—O4	80.24 (11)
C11—C10—H10B	110.4	N2—Cu2—O4	81.42 (12)
H10A—C10—H10B	108.6	O5—Cu2—Cl2	97.29 (9)
O3—C11—O2	125.9 (4)	N2—Cu2—Cl2	101.01 (10)
O3—C11—C10	116.7 (4)	O4—Cu2—Cl2	177.52 (8)
O2—C11—C10	117.3 (3)	C1—N1—C9	118.8 (3)
N2—C12—C13	122.4 (4)	C1—N1—Cu1	128.2 (3)
N2—C12—H12	118.8	C9—N1—Cu1	113.0 (2)
C13—C12—H12	118.8	C12—N2—C20	118.4 (3)
C14—C13—C12	120.1 (4)	C12—N2—Cu2	128.4 (3)
C14—C13—H13	119.9	C20—N2—Cu2	113.0 (3)
C12—C13—H13	119.9	C8—O1—C10	122.8 (3)
C13—C14—C15	119.7 (4)	C8—O1—Cu1	115.4 (2)
C13—C14—H14	120.2	C10—O1—Cu1	115.1 (2)
C15—C14—H14	120.2	C11—O2—Cu1	118.3 (2)
C14—C15—C20	117.0 (4)	C19—O4—C21	119.2 (3)
C14—C15—C16	125.0 (4)	C19—O4—Cu2	113.1 (2)
C20—C15—C16	118.0 (4)	C21—O4—Cu2	113.6 (2)
C17—C16—C15	120.7 (4)	C22—O5—Cu2	118.1 (2)

N1—C1—C2—C3	−1.9 (7)	O1—Cu1—N1—C1	179.2 (4)
C1—C2—C3—C4	1.5 (7)	Cl1—Cu1—N1—C1	−2.7 (4)
C2—C3—C4—C5	177.9 (4)	O2—Cu1—N1—C9	−27.2 (5)
C2—C3—C4—C9	0.1 (6)	O1—Cu1—N1—C9	0.9 (3)
C3—C4—C5—C6	−176.6 (4)	Cl1—Cu1—N1—C9	179.0 (2)
C9—C4—C5—C6	1.2 (6)	C13—C12—N2—C20	0.6 (6)
C4—C5—C6—C7	−0.4 (7)	C13—C12—N2—Cu2	175.1 (3)
C5—C6—C7—C8	−1.2 (6)	C19—C20—N2—C12	−179.9 (4)
C6—C7—C8—O1	−177.3 (4)	C15—C20—N2—C12	−0.8 (6)
C6—C7—C8—C9	1.9 (6)	C19—C20—N2—Cu2	4.7 (4)
C7—C8—C9—N1	178.0 (3)	C15—C20—N2—Cu2	−176.2 (3)
O1—C8—C9—N1	−2.7 (5)	O5—Cu2—N2—C12	−138.4 (4)
C7—C8—C9—C4	−1.0 (6)	O4—Cu2—N2—C12	179.4 (4)
O1—C8—C9—C4	178.2 (3)	Cl2—Cu2—N2—C12	−1.1 (4)
C3—C4—C9—N1	−1.6 (6)	O5—Cu2—N2—C20	36.4 (5)
C5—C4—C9—N1	−179.5 (3)	O4—Cu2—N2—C20	−5.8 (2)
C3—C4—C9—C8	177.4 (4)	Cl2—Cu2—N2—C20	173.7 (2)
C5—C4—C9—C8	−0.5 (6)	C7—C8—O1—C10	−27.5 (6)
O1—C10—C11—O3	−179.3 (4)	C9—C8—O1—C10	153.3 (3)
O1—C10—C11—O2	3.5 (5)	C7—C8—O1—Cu1	−177.4 (3)
N2—C12—C13—C14	−0.8 (7)	C9—C8—O1—Cu1	3.4 (4)
C12—C13—C14—C15	1.2 (7)	C11—C10—O1—C8	−163.9 (3)
C13—C14—C15—C20	−1.4 (6)	C11—C10—O1—Cu1	−13.9 (4)
C13—C14—C15—C16	178.5 (4)	O2—Cu1—O1—C8	167.3 (3)
C14—C15—C16—C17	−179.3 (4)	N1—Cu1—O1—C8	−2.5 (2)
C20—C15—C16—C17	0.6 (6)	O2—Cu1—O1—C10	15.1 (2)
C15—C16—C17—C18	−1.1 (6)	N1—Cu1—O1—C10	−154.7 (3)
C16—C17—C18—C19	0.5 (6)	O3—C11—O2—Cu1	−167.7 (3)
C17—C18—C19—O4	177.8 (3)	C10—C11—O2—Cu1	9.2 (5)
C17—C18—C19—C20	0.6 (6)	N1—Cu1—O2—C11	14.9 (5)
C18—C19—C20—N2	178.1 (4)	O1—Cu1—O2—C11	−13.4 (3)
O4—C19—C20—N2	0.6 (5)	Cl1—Cu1—O2—C11	168.8 (3)
C18—C19—C20—C15	−1.0 (6)	C18—C19—O4—C21	39.6 (5)
O4—C19—C20—C15	−178.5 (3)	C20—C19—O4—C21	−143.0 (3)
C14—C15—C20—N2	1.3 (6)	C18—C19—O4—Cu2	177.1 (3)
C16—C15—C20—N2	−178.7 (3)	C20—C19—O4—Cu2	−5.4 (4)
C14—C15—C20—C19	−179.6 (4)	C22—C21—O4—C19	152.5 (3)
C16—C15—C20—C19	0.4 (5)	C22—C21—O4—Cu2	15.1 (4)
O4—C21—C22—O6	−179.0 (3)	O5—Cu2—O4—C19	−157.3 (2)
O4—C21—C22—O5	−2.6 (5)	N2—Cu2—O4—C19	6.2 (2)
C2—C1—N1—C9	0.5 (6)	O5—Cu2—O4—C21	−17.3 (2)
C2—C1—N1—Cu1	−177.8 (3)	N2—Cu2—O4—C21	146.2 (3)
C8—C9—N1—C1	−177.7 (3)	O6—C22—O5—Cu2	163.8 (3)
C4—C9—N1—C1	1.3 (6)	C21—C22—O5—Cu2	−12.3 (5)
C8—C9—N1—Cu1	0.7 (4)	N2—Cu2—O5—C22	−25.9 (5)
C4—C9—N1—Cu1	179.7 (3)	O4—Cu2—O5—C22	16.5 (3)
O2—Cu1—N1—C1	151.1 (3)	Cl2—Cu2—O5—C22	−163.8 (3)

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₁H₈NO₃)₂Cl₂]
M_r	602.35
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.3796 (17), 19.195 (4), 13.392 (3)
β (°)	98.85 (3)
V (Å³)	2128.4 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.30
Crystal size (mm)	0.36 × 0.30 × 0.24

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.462, 0.582
No. of measured, independent and observed [I > 2σ(I)] reflections	11625, 4179, 2737
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.087, 1.01
No. of reflections	4179
No. of parameters	307
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.47

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and ORTEP-3 (Farrugia, 1997), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work has been supported by the National Natural Science Foundation of China (grant No. 20771040).

References

Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dong, Y. B., Jiang, Y. Y., Li, J., Ma, J. P., Liu, F. L., Tang, B., Huang, R. Q. & Batten, S. R. (2007). J. Am. Chem. Soc. 129, 4520–4521. Web of Science CSD CrossRef PubMed CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hong, X. L., Li, Y. Z., Hu, H. M., Pan, Y., Bai, J. F. & You, X. Z. (2006). Cryst. Growth Des. 6, 1221–1226. Web of Science CSD CrossRef CAS Google Scholar
Koelsch, C. F. (1931). J. Am. Chem. Soc. 53, 304–305. CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sudik, A. C., Millward, A. R., Ockwig, N. W., Cote, A. P., Kim, J. & Yaghi, O. M. (2005). J. Am. Chem. Soc. 127, 7110–7118. Web of Science CSD CrossRef PubMed CAS Google Scholar
Tong, M. L., Lee, H. K., Chen, X. M., Huang, R. B. & Mak, T. C. W. (1999). J. Chem. Soc. Dalton Trans. pp. 3657–3659. Web of Science CSD CrossRef Google Scholar
Wang, Y.-H. & Lu, F. (2004). Acta Cryst. C60, m557–m559. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Wang, Y. H., Song, R. F. & Zhang, F. Y. (2005). J. Mol. Struct. 752, 104–109. Web of Science CSD CrossRef CAS Google Scholar