Bis{(E)-4-bromo-2-[(2-chloro-3-pyrid­yl)imino­meth­yl]phenolato-κ2N,O}copper(II)

Dong, W.-K.; Tong, J.-F.; An, L.-L.; Wu, J.-C.; Yao, J.

doi:10.1107/S1600536809027792

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page m945

doi:10.1107/S1600536809027792

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Bis{(E)-4-bromo-2-[(2-chloro-3-pyridyl)iminomethyl]phenolato-κ²N,O}copper(II)

Wen-Kui Dong,^a ^* Jun-Feng Tong,^a Li-Li An,^a Jian-Chao Wu ^a and Jian Yao ^a

^aSchool of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: dongwk@mail.lzjtu.cn

(Received 13 July 2009; accepted 15 July 2009; online 18 July 2009)

In the title complex, [Cu(C₁₂H₇BrClN₂O)₂], the Cu^II center is tetracoordinated by two phenolate O and two azomethine N atoms from two independent bidentate 4-bromo-2-[(2-chloro-3-pyridyl)iminomethyl]phenolate (L) ligands. In the crystal structure, the Cu^II atom has a distorted square-planar coordination environment. The interplanar dihedral angles between the benzene and pyridine rings in the individual ligands are 63.83 (4) and 54.43 (3)°, indicating the pyridine ring to have considerably weaker steric hindrance.

Related literature

For the applications of phenoxyimines, see: John et al. (2007 ). For the structures of salen-type bisoxime complexes, see: Dong et al. (2009a ,b ). Due to their chelating ability and positive redox potential, many copper(II) complexes are biologically active, see: Karmaka et al. (2007 ). For the preparation of (E)-[4-bromo-2-((2-chloropyridin-3-ylimino)methyl)]phenol, see: Dong et al. (2009c ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

[Cu(C₁₂H₇BrClN₂O)₂]
M_r = 684.65
Monoclinic, P 2₁ /c
a = 20.406 (2) Å
b = 11.6378 (15) Å
c = 10.5787 (13) Å
β = 90.212 (2)°
V = 2512.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 4.29 mm⁻¹
T = 298 K
0.43 × 0.12 × 0.05 mm

Data collection

Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.260, T_max = 0.814
11575 measured reflections
4426 independent reflections
2340 reflections with I > 2σ(I)
R_int = 0.060

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.050
S = 0.88
4426 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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 global, I. DOI: 10.1107/S1600536809027792/hg2538sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809027792/hg2538Isup2.hkl

checkCIF report

Comment top

Phenoxy-imines are a versatile class of ligands that display a truly impressive range of diverse applications spanning from bioinorganic chemistry to coordination chemistry, chemical catalysis, and materials related applications (John et al., 2007). Due to their chelating ability and positive redox potential many copper(II) complexes are generally biologically active (Karmaka et al., 2007). As part of our ongoing research into the complexes between transition metals and phenoxy-imine ligands, we report here the synthesis and crystal structures of the title complex, bis{(E)-[4-bromo-2-((2-chloropyridin-3-ylimino)methyl-κN)] phenolato-κO¹}copper(II) (Fig. 1).

In the asymmetric molecule unit of the title complex, the Cu^II center is tetracoordinated by two phenolic O and two azomethine N atoms from two ligand (L^-) units and has a distorted square-planar coordination environment, which is similar to the salen-type bisoxime complexes (Dong et al., 2009a, Dong et al., 2009b). It was observed that all bond lengths are within normal ranges (Allen et al., 1987).

The interplane dihedral angles are found to be as follows: 63.83° between the phenyl ring (C2—C7) and pyridyl ring (N1/C8—C12), 54.43° between phenyl ring (C14—C19) and pyridyl ring (N3/C20—C24), indicating the pyridine ring having a considerable weaker steric hindrance. Besides, the dihedral angle between the coordination plane of O1—Cu1—N2 and O2—Cu1—N4 is 27.72 (3)°, indicating slight distortion toward tetrahedral geometry from the square planar structure.

Related literature top

For the applications of phenoxyimines, see: John et al. (2007). For the structures of salen-type bisoxime complexes, see: Dong et al. (2009a,b). Due to their chelating ability and positive redox

potential, many copper(II) complexes are biologically active, see: Karmaka et al. (2007). For the preparation of (E)-[4-bromo-2-((2-chloropyridin-3-ylimino)methyl)]phenol, see: Dong et al. (2009c). For bond-length data, see: Allen et al. (1987).

Experimental top

(E)-[4-Bromo-2-((2-chloropyridin-3-ylimino)methyl)]phenol(HL) was prepared according to previously reported procedure (Dong et al., 2009c). A blue solution of copper(II) acetate monohydrate (2.6 mg, 0.0013 mmol) in methanol (2 ml) was added dropwise to a pale-yellow solution of HL (8.1 mg, 0.0026 mmol) in methanol (4 ml) at room temperature. The color of the mixing solution turned to yellow immediately, then turned to brown slowly and allowed to stand at room temperature for several days. With evaporation of the solvent, dark-brown needle-like single crystals suitable for X-ray crystallographic analysis were obtained. IR: ν C=N, 1600 cm^-1, ν Ar—O, 1242 cm^-1, ν Cu—N, 445 cm^-1 and ν Cu—O, 424 cm^-1.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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. The molecular structure of the title complex with atom numbering scheme. Displacement ellipsoids for non-hydrogen atoms are drawn at the 30% probability level.

Bis{(E)-4-bromo-2-[(2-chloro-3-pyridyl)iminomethyl]phenolato- κ²N,O}copper(II) top

Crystal data top

[Cu(C₁₂H₇BrClN₂O)₂]	F(000) = 1340
M_r = 684.65	D_x = 1.810 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2128 reflections
a = 20.406 (2) Å	θ = 3.5–23.5°
b = 11.6378 (15) Å	µ = 4.29 mm⁻¹
c = 10.5787 (13) Å	T = 298 K
β = 90.212 (2)°	Needle-like, brown
V = 2512.2 (5) Å³	0.43 × 0.12 × 0.05 mm
Z = 4

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	4426 independent reflections
Radiation source: fine-focus sealed tube	2340 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.060
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→24
T_min = 0.260, T_max = 0.814	k = −13→13
11575 measured reflections	l = −11→12

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) = 0.050	H-atom parameters constrained
S = 0.88	w = 1/[σ²(F_o²) + (0.0002P)²] where P = (F_o² + 2F_c²)/3
4426 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Cu(C₁₂H₇BrClN₂O)₂]	V = 2512.2 (5) Å³
M_r = 684.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 20.406 (2) Å	µ = 4.29 mm⁻¹
b = 11.6378 (15) Å	T = 298 K
c = 10.5787 (13) Å	0.43 × 0.12 × 0.05 mm
β = 90.212 (2)°

Data collection top

Siemens SMART 1000 CCD area-detector diffractometer	4426 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2340 reflections with I > 2σ(I)
T_min = 0.260, T_max = 0.814	R_int = 0.060
11575 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.050	H-atom parameters constrained
S = 0.88	Δρ_max = 0.37 e Å⁻³
4426 reflections	Δρ_min = −0.36 e Å⁻³
316 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	0.25248 (3)	0.22385 (4)	0.41801 (5)	0.04108 (16)
Br1	0.13387 (3)	−0.36645 (4)	0.54348 (6)	0.0734 (2)
Br2	0.35180 (3)	0.81346 (4)	0.23403 (5)	0.06505 (18)
Cl1	0.37963 (6)	0.12525 (11)	0.20905 (11)	0.0646 (4)
Cl2	0.20549 (7)	0.12485 (9)	0.15999 (12)	0.0644 (4)
N1	0.4802 (2)	0.1582 (3)	0.3542 (4)	0.0521 (11)
N2	0.31148 (17)	0.0920 (3)	0.4578 (3)	0.0363 (9)
N3	0.0797 (3)	0.1474 (4)	0.1537 (4)	0.0752 (15)
N4	0.19682 (17)	0.3327 (3)	0.3208 (3)	0.0358 (9)
O1	0.17657 (13)	0.1421 (2)	0.4686 (3)	0.0435 (8)
O2	0.32382 (13)	0.3273 (2)	0.4265 (3)	0.0437 (8)
C1	0.2900 (2)	−0.0104 (3)	0.4797 (3)	0.0356 (11)
H1	0.3217	−0.0666	0.4935	0.043*
C2	0.2227 (2)	−0.0477 (3)	0.4853 (4)	0.0366 (12)
C3	0.1698 (2)	0.0308 (4)	0.4827 (4)	0.0371 (12)
C4	0.1058 (2)	−0.0135 (3)	0.4983 (4)	0.0480 (13)
H4	0.0702	0.0364	0.4982	0.058*
C5	0.0954 (2)	−0.1300 (4)	0.5138 (4)	0.0551 (14)
H5	0.0530	−0.1578	0.5230	0.066*
C6	0.1480 (2)	−0.2060 (3)	0.5158 (4)	0.0486 (13)
C7	0.2108 (2)	−0.1670 (3)	0.5022 (4)	0.0444 (13)
H7	0.2457	−0.2185	0.5041	0.053*
C8	0.4174 (2)	0.1324 (3)	0.3550 (4)	0.0378 (12)
C9	0.3807 (2)	0.1104 (3)	0.4641 (4)	0.0354 (12)
C10	0.4137 (2)	0.1121 (3)	0.5773 (4)	0.0438 (12)
H10	0.3916	0.0960	0.6520	0.053*
C11	0.4796 (2)	0.1377 (4)	0.5798 (5)	0.0547 (14)
H11	0.5028	0.1389	0.6556	0.066*
C12	0.5103 (2)	0.1615 (4)	0.4666 (6)	0.0524 (14)
H12	0.5545	0.1809	0.4688	0.063*
C13	0.2121 (2)	0.4391 (4)	0.3010 (4)	0.0396 (12)
H13	0.1802	0.4851	0.2636	0.048*
C14	0.2736 (2)	0.4933 (3)	0.3312 (4)	0.0353 (11)
C15	0.3267 (2)	0.4341 (4)	0.3864 (4)	0.0348 (11)
C16	0.3869 (2)	0.4935 (3)	0.3971 (4)	0.0442 (12)
H16	0.4226	0.4569	0.4346	0.053*
C17	0.3941 (2)	0.6050 (4)	0.3531 (4)	0.0505 (14)
H17	0.4345	0.6416	0.3590	0.061*
C18	0.3414 (3)	0.6615 (3)	0.3007 (4)	0.0443 (13)
C19	0.2818 (2)	0.6099 (3)	0.2905 (4)	0.0434 (13)
H19	0.2464	0.6503	0.2572	0.052*
C20	0.1335 (2)	0.1942 (4)	0.2005 (5)	0.0523 (14)
C21	0.1350 (2)	0.2933 (4)	0.2745 (4)	0.0417 (12)
C22	0.0771 (3)	0.3453 (4)	0.3016 (5)	0.0582 (15)
H22	0.0757	0.4103	0.3526	0.070*
C23	0.0194 (3)	0.2987 (5)	0.2509 (6)	0.0788 (18)
H23	−0.0209	0.3340	0.2644	0.095*
C24	0.0237 (3)	0.2009 (6)	0.1816 (6)	0.093 (2)
H24	−0.0151	0.1688	0.1514	0.112*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0426 (4)	0.0358 (3)	0.0447 (4)	−0.0020 (3)	−0.0014 (3)	0.0047 (3)
Br1	0.0707 (4)	0.0367 (3)	0.1127 (5)	−0.0049 (3)	0.0121 (4)	0.0083 (3)
Br2	0.0813 (5)	0.0403 (3)	0.0736 (4)	−0.0137 (3)	0.0085 (3)	0.0061 (3)
Cl1	0.0733 (10)	0.0825 (9)	0.0381 (8)	−0.0144 (8)	0.0027 (7)	0.0040 (7)
Cl2	0.0823 (11)	0.0519 (7)	0.0589 (9)	−0.0004 (7)	−0.0031 (7)	−0.0107 (7)
N1	0.039 (3)	0.066 (3)	0.051 (3)	−0.008 (2)	0.009 (2)	0.000 (2)
N2	0.041 (3)	0.036 (2)	0.033 (2)	−0.0018 (19)	0.0009 (19)	0.0046 (18)
N3	0.072 (4)	0.074 (3)	0.080 (4)	−0.023 (3)	−0.024 (3)	0.008 (3)
N4	0.041 (3)	0.035 (2)	0.032 (2)	−0.0039 (19)	−0.0021 (19)	0.0037 (18)
O1	0.039 (2)	0.0334 (16)	0.058 (2)	−0.0003 (15)	0.0065 (15)	0.0095 (16)
O2	0.042 (2)	0.0348 (16)	0.054 (2)	−0.0035 (15)	−0.0072 (15)	0.0078 (16)
C1	0.043 (3)	0.036 (3)	0.028 (3)	0.010 (2)	−0.005 (2)	0.001 (2)
C2	0.034 (3)	0.036 (3)	0.039 (3)	−0.003 (2)	0.002 (2)	0.004 (2)
C3	0.042 (3)	0.037 (3)	0.033 (3)	−0.002 (3)	0.005 (2)	0.001 (2)
C4	0.041 (4)	0.038 (3)	0.065 (4)	0.001 (2)	0.003 (3)	0.006 (3)
C5	0.035 (3)	0.048 (3)	0.082 (4)	−0.008 (3)	0.001 (3)	0.003 (3)
C6	0.053 (4)	0.032 (3)	0.061 (4)	−0.005 (3)	0.004 (3)	0.003 (3)
C7	0.050 (4)	0.035 (3)	0.048 (3)	0.006 (2)	0.002 (3)	0.001 (2)
C8	0.045 (3)	0.036 (2)	0.033 (3)	0.006 (2)	0.002 (3)	0.004 (2)
C9	0.035 (3)	0.034 (3)	0.037 (3)	0.001 (2)	−0.001 (3)	−0.005 (2)
C10	0.047 (4)	0.052 (3)	0.032 (3)	0.001 (3)	0.000 (3)	0.008 (3)
C11	0.046 (4)	0.062 (3)	0.055 (4)	0.005 (3)	−0.012 (3)	−0.003 (3)
C12	0.029 (3)	0.051 (3)	0.078 (4)	0.002 (2)	0.009 (3)	−0.006 (3)
C13	0.042 (3)	0.046 (3)	0.031 (3)	0.008 (3)	0.001 (2)	0.008 (2)
C14	0.038 (3)	0.040 (3)	0.027 (3)	0.000 (3)	0.005 (2)	0.001 (2)
C15	0.032 (3)	0.043 (3)	0.029 (3)	−0.006 (3)	0.005 (2)	−0.001 (2)
C16	0.048 (4)	0.045 (3)	0.040 (3)	−0.006 (3)	−0.002 (2)	−0.003 (2)
C17	0.048 (4)	0.051 (3)	0.053 (4)	−0.018 (3)	0.010 (3)	−0.015 (3)
C18	0.053 (4)	0.032 (3)	0.048 (3)	−0.010 (3)	0.007 (3)	0.003 (2)
C19	0.054 (4)	0.032 (3)	0.044 (3)	0.006 (2)	0.006 (3)	0.002 (2)
C20	0.054 (4)	0.052 (3)	0.051 (4)	−0.017 (3)	−0.012 (3)	0.015 (3)
C21	0.042 (4)	0.045 (3)	0.038 (3)	−0.010 (3)	−0.007 (3)	0.008 (3)
C22	0.043 (4)	0.062 (3)	0.070 (4)	−0.001 (3)	−0.004 (3)	0.009 (3)
C23	0.048 (4)	0.094 (5)	0.094 (5)	0.001 (4)	−0.003 (4)	0.033 (4)
C24	0.062 (5)	0.106 (6)	0.110 (6)	−0.044 (5)	−0.039 (4)	0.026 (5)

Geometric parameters (Å, º) top

Cu1—O2	1.891 (3)	C6—C7	1.368 (5)
Cu1—O1	1.897 (2)	C7—H7	0.9300
Cu1—N4	1.986 (3)	C8—C9	1.402 (5)
Cu1—N2	1.994 (3)	C9—C10	1.372 (5)
Br1—C6	1.912 (4)	C10—C11	1.378 (5)
Br2—C18	1.916 (4)	C10—H10	0.9300
Cl1—C8	1.726 (4)	C11—C12	1.381 (5)
Cl2—C20	1.731 (5)	C11—H11	0.9300
N1—C8	1.316 (5)	C12—H12	0.9300
N1—C12	1.336 (6)	C13—C14	1.439 (5)
N2—C1	1.291 (4)	C13—H13	0.9300
N2—C9	1.429 (5)	C14—C15	1.410 (5)
N3—C20	1.320 (5)	C14—C19	1.434 (5)
N3—C24	1.335 (6)	C15—C16	1.415 (5)
N4—C13	1.295 (4)	C16—C17	1.387 (5)
N4—C21	1.427 (5)	C16—H16	0.9300
O1—C3	1.311 (4)	C17—C18	1.376 (6)
O2—C15	1.314 (4)	C17—H17	0.9300
C1—C2	1.442 (5)	C18—C19	1.361 (5)
C1—H1	0.9300	C19—H19	0.9300
C2—C3	1.414 (5)	C20—C21	1.395 (6)
C2—C7	1.421 (5)	C21—C22	1.359 (5)
C3—C4	1.416 (5)	C22—C23	1.400 (6)
C4—C5	1.382 (5)	C22—H22	0.9300
C4—H4	0.9300	C23—C24	1.358 (7)
C5—C6	1.390 (5)	C23—H23	0.9300
C5—H5	0.9300	C24—H24	0.9300

O2—Cu1—O1	159.31 (12)	C9—C10—H10	120.2
O2—Cu1—N4	93.27 (13)	C11—C10—H10	120.2
O1—Cu1—N4	89.99 (13)	C10—C11—C12	118.2 (5)
O2—Cu1—N2	90.91 (13)	C10—C11—H11	120.9
O1—Cu1—N2	92.73 (13)	C12—C11—H11	120.9
N4—Cu1—N2	160.68 (13)	N1—C12—C11	123.8 (5)
C8—N1—C12	116.4 (4)	N1—C12—H12	118.1
C1—N2—C9	117.8 (3)	C11—C12—H12	118.1
C1—N2—Cu1	122.9 (3)	N4—C13—C14	126.4 (4)
C9—N2—Cu1	119.3 (2)	N4—C13—H13	116.8
C20—N3—C24	115.8 (5)	C14—C13—H13	116.8
C13—N4—C21	117.7 (4)	C15—C14—C19	119.8 (4)
C13—N4—Cu1	123.8 (3)	C15—C14—C13	123.1 (4)
C21—N4—Cu1	118.4 (3)	C19—C14—C13	116.8 (4)
C3—O1—Cu1	127.9 (3)	O2—C15—C14	124.1 (4)
C15—O2—Cu1	128.5 (3)	O2—C15—C16	118.4 (4)
N2—C1—C2	127.5 (4)	C14—C15—C16	117.4 (4)
N2—C1—H1	116.2	C17—C16—C15	121.6 (4)
C2—C1—H1	116.2	C17—C16—H16	119.2
C3—C2—C7	120.2 (4)	C15—C16—H16	119.2
C3—C2—C1	122.1 (4)	C18—C17—C16	119.9 (4)
C7—C2—C1	117.5 (4)	C18—C17—H17	120.0
O1—C3—C2	124.0 (4)	C16—C17—H17	120.0
O1—C3—C4	118.1 (4)	C19—C18—C17	121.3 (4)
C2—C3—C4	117.9 (4)	C19—C18—Br2	118.6 (4)
C5—C4—C3	120.8 (4)	C17—C18—Br2	120.1 (4)
C5—C4—H4	119.6	C18—C19—C14	119.9 (4)
C3—C4—H4	119.6	C18—C19—H19	120.0
C4—C5—C6	120.5 (4)	C14—C19—H19	120.0
C4—C5—H5	119.7	N3—C20—C21	124.6 (5)
C6—C5—H5	119.7	N3—C20—Cl2	114.8 (5)
C7—C6—C5	120.7 (4)	C21—C20—Cl2	120.5 (4)
C7—C6—Br1	118.8 (3)	C22—C21—C20	118.0 (4)
C5—C6—Br1	120.4 (4)	C22—C21—N4	123.6 (4)
C6—C7—C2	119.8 (4)	C20—C21—N4	118.4 (4)
C6—C7—H7	120.1	C21—C22—C23	118.5 (5)
C2—C7—H7	120.1	C21—C22—H22	120.7
N1—C8—C9	124.8 (4)	C23—C22—H22	120.7
N1—C8—Cl1	115.9 (3)	C24—C23—C22	118.4 (6)
C9—C8—Cl1	119.3 (4)	C24—C23—H23	120.8
C10—C9—C8	117.0 (4)	C22—C23—H23	120.8
C10—C9—N2	121.6 (4)	N3—C24—C23	124.6 (6)
C8—C9—N2	121.4 (4)	N3—C24—H24	117.7
C9—C10—C11	119.7 (4)	C23—C24—H24	117.7

O2—Cu1—N2—C1	172.5 (3)	C1—N2—C9—C10	−72.8 (5)
O1—Cu1—N2—C1	12.8 (3)	Cu1—N2—C9—C10	106.5 (4)
N4—Cu1—N2—C1	−84.9 (5)	C1—N2—C9—C8	109.8 (4)
O2—Cu1—N2—C9	−6.8 (3)	Cu1—N2—C9—C8	−70.8 (4)
O1—Cu1—N2—C9	−166.4 (3)	C8—C9—C10—C11	1.7 (6)
N4—Cu1—N2—C9	95.8 (5)	N2—C9—C10—C11	−175.7 (4)
O2—Cu1—N4—C13	−9.1 (3)	C9—C10—C11—C12	0.2 (6)
O1—Cu1—N4—C13	150.5 (3)	C8—N1—C12—C11	1.1 (7)
N2—Cu1—N4—C13	−111.3 (5)	C10—C11—C12—N1	−1.8 (7)
O2—Cu1—N4—C21	173.9 (3)	C21—N4—C13—C14	−175.0 (4)
O1—Cu1—N4—C21	−26.6 (3)	Cu1—N4—C13—C14	7.9 (6)
N2—Cu1—N4—C21	71.7 (5)	N4—C13—C14—C15	0.9 (7)
O2—Cu1—O1—C3	−117.9 (4)	N4—C13—C14—C19	174.6 (4)
N4—Cu1—O1—C3	142.8 (4)	Cu1—O2—C15—C14	2.2 (6)
N2—Cu1—O1—C3	−18.0 (4)	Cu1—O2—C15—C16	−176.8 (3)
O1—Cu1—O2—C15	−94.3 (5)	C19—C14—C15—O2	180.0 (3)
N4—Cu1—O2—C15	4.4 (3)	C13—C14—C15—O2	−6.6 (6)
N2—Cu1—O2—C15	165.5 (3)	C19—C14—C15—C16	−1.0 (6)
C9—N2—C1—C2	176.4 (4)	C13—C14—C15—C16	172.4 (4)
Cu1—N2—C1—C2	−2.9 (6)	O2—C15—C16—C17	177.9 (4)
N2—C1—C2—C3	−8.4 (7)	C14—C15—C16—C17	−1.2 (6)
N2—C1—C2—C7	175.7 (4)	C15—C16—C17—C18	1.8 (6)
Cu1—O1—C3—C2	12.6 (6)	C16—C17—C18—C19	−0.2 (7)
Cu1—O1—C3—C4	−168.5 (3)	C16—C17—C18—Br2	−177.7 (3)
C7—C2—C3—O1	179.4 (4)	C17—C18—C19—C14	−2.0 (7)
C1—C2—C3—O1	3.6 (7)	Br2—C18—C19—C14	175.5 (3)
C7—C2—C3—C4	0.5 (6)	C15—C14—C19—C18	2.6 (6)
C1—C2—C3—C4	−175.3 (4)	C13—C14—C19—C18	−171.3 (4)
O1—C3—C4—C5	−179.9 (4)	C24—N3—C20—C21	−0.3 (7)
C2—C3—C4—C5	−0.9 (6)	C24—N3—C20—Cl2	−178.6 (4)
C3—C4—C5—C6	0.8 (7)	N3—C20—C21—C22	0.6 (7)
C4—C5—C6—C7	−0.2 (7)	Cl2—C20—C21—C22	178.8 (3)
C4—C5—C6—Br1	177.7 (3)	N3—C20—C21—N4	178.7 (4)
C5—C6—C7—C2	−0.3 (7)	Cl2—C20—C21—N4	−3.0 (5)
Br1—C6—C7—C2	−178.1 (3)	C13—N4—C21—C22	−53.4 (6)
C3—C2—C7—C6	0.1 (7)	Cu1—N4—C21—C22	123.8 (4)
C1—C2—C7—C6	176.1 (4)	C13—N4—C21—C20	128.5 (4)
C12—N1—C8—C9	1.1 (6)	Cu1—N4—C21—C20	−54.3 (5)
C12—N1—C8—Cl1	−178.6 (3)	C20—C21—C22—C23	−1.8 (7)
N1—C8—C9—C10	−2.5 (6)	N4—C21—C22—C23	−179.9 (4)
Cl1—C8—C9—C10	177.1 (3)	C21—C22—C23—C24	2.8 (8)
N1—C8—C9—N2	174.9 (4)	C20—N3—C24—C23	1.4 (9)
Cl1—C8—C9—N2	−5.4 (5)	C22—C23—C24—N3	−2.7 (9)

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₇BrClN₂O)₂]
M_r	684.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	20.406 (2), 11.6378 (15), 10.5787 (13)
β (°)	90.212 (2)
V (Å³)	2512.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.29
Crystal size (mm)	0.43 × 0.12 × 0.05

Data collection
Diffractometer	Siemens SMART 1000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.260, 0.814
No. of measured, independent and observed [I > 2σ(I)] reflections	11575, 4426, 2340
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.050, 0.88
No. of reflections	4426
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.36

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Foundation of the Education Department of Gansu Province and the `Jing Lan' Talent Engineering Funds of Lanzhou Jiaotong University, which are gratefully acknowledged.

References

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