Bis{(E)-4-bromo-2-[(2-chloro-3-pyrid-yl)imino-meth-yl]phenolato-κN,O}copper(II).

In the title complex, [Cu(C(12)H(7)BrClN(2)O)(2)], the Cu(II) center is tetra-coordinated by two phenolate O and two azomethine N atoms from two independent bidentate 4-bromo-2-[(2-chloro-3-pyrid-yl)imino-meth-yl]phenolate (L) ligands. In the crystal structure, the Cu(II) atom has a distorted square-planar coordination environment. The inter-planar 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 = 684.65

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.050

S = 0.88

4426 reflections

316 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027792/hg2538sup1.cif

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

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

[Cu(C12H7BrClN2O)2]	F(000) = 1340
Mr = 684.65	Dx = 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

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

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(Fo2) + (0.0002P)2] where P = (Fo2 + 2Fc2)/3
4426 reflections	(Δ/σ)max < 0.001
316 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.35 e Å−3

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	0.25248 (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*

	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)

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)