Disentangling steric and electronic factors in monomeric bis­(2-bromo-4-chloro-6-{[(2-hy­droxy­eth­yl)imino]­meth­yl}phenolato-κ²N,O)copper(II)

The title compound, [Cu(C₉H₈BrClNO₂)₂], is a square-planar complex. The potentially tridentate dibasic 2-bromo-4-chloro-6-{[(2-hy­droxy­eth­yl)imino]­meth­yl}phenolate ligand coordinates in a trans-bis fashion to the Cu^II centre via the imine N and phenolate O atoms. The Cu^II atom lies on the centre of inversion of the mol­ecule. The potentially coordinating hy­droxy­ethyl group remains protonated and uncoordinated, taking part in inter­molecular hydrogen bonds with vicinal groups, leading to the formation of a two-dimensional hydrogen-bond network with sheets parallel to the (10) plane. Substituent effects on the crystal packing and coordination modes of the ligand are discussed.

Computing details

Data collection: CrysAlis PRO (Agilent, 2010); cell refinement: CrysAlis PRO (Agilent, 2010); data reduction: CrysAlis PRO (Agilent, 2010); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 2012).

Bis(2-bromo-4-chloro-6-{[(2-hydroxyethyl)imino]methyl}phenolato-κ²N,O)copper(II)

Crystal data

[Cu(C9H8BrClNO2)2]	F(000) = 606
Mr = 618.59	Dx = 1.985 Mg m^−3
Monoclinic, P21/n	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: -P 2yn	Cell parameters from 6191 reflections
a = 13.1298 (6) Å	θ = 4.2–70.7°
b = 4.6502 (1) Å	µ = 8.64 mm^−1
c = 16.957 (2) Å	T = 293 K
β = 90.977 (9)°	Needle, green
V = 1035.20 (13) Å^3	0.45 × 0.09 × 0.05 mm
Z = 2

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer	1998 independent reflections
Mirror monochromator	1774 reflections with I > 2σ(I)
Detector resolution: 10.3756 pixels mm^-1	Rint = 0.046
ω scans	θmax = 71.1°, θmin = 4.2°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	h = −15→15
Tmin = 0.266, Tmax = 1	k = −5→5
12608 measured reflections	l = −20→20

Refinement

Refinement on F^2	1 restraint
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.076	w = 1/[σ^2(Fo^2) + (0.0412P)^2 + 0.3308P] where P = (Fo^2 + 2Fc^2)/3
S = 1.11	(Δ/σ)max = 0.001
1998 reflections	Δρmax = 0.30 e Å^−3
137 parameters	Δρmin = −0.59 e Å^−3

Special details

Experimental. Absorption correction: CrysAlisPro, Version 1.171.36.24 (Agilent Technologies, 2010) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0	0.5	0.5	0.03380 (14)
Cl1	0.51349 (5)	0.0906 (2)	0.38758 (5)	0.0743 (3)
Br1	0.11786 (2)	−0.17824 (8)	0.30816 (2)	0.05847 (13)
N1	0.12873 (15)	0.6497 (4)	0.55269 (11)	0.0358 (4)
C2	0.21922 (18)	0.5765 (6)	0.53272 (14)	0.0390 (5)
H2	0.2725	0.6697	0.559	0.047*
C3	0.24752 (18)	0.3676 (6)	0.47457 (14)	0.0394 (5)
C4	0.17325 (18)	0.2105 (5)	0.43017 (13)	0.0367 (5)
C5	0.21223 (19)	0.0212 (5)	0.37315 (14)	0.0393 (5)
C6	0.3142 (2)	−0.0192 (6)	0.36112 (15)	0.0451 (6)
H6	0.3363	−0.1492	0.3234	0.054*
C7	0.38386 (19)	0.1368 (7)	0.40601 (16)	0.0477 (6)
C8	0.35205 (19)	0.3276 (6)	0.46146 (15)	0.0461 (6)
H8	0.3998	0.4319	0.4908	0.055*
O9	0.07575 (13)	0.2348 (4)	0.44007 (10)	0.0437 (4)
C10	0.12363 (19)	0.8628 (5)	0.61661 (14)	0.0391 (5)
H10A	0.0652	0.9871	0.6077	0.047*
H10B	0.1844	0.9813	0.6164	0.047*
C11	0.1148 (2)	0.7177 (6)	0.69618 (15)	0.0446 (6)
H11A	0.0952	0.8595	0.7351	0.053*
H11B	0.0615	0.5733	0.6932	0.053*
O12	0.20696 (17)	0.5858 (5)	0.72096 (13)	0.0584 (5)
H12	0.247 (3)	0.715 (7)	0.733 (2)	0.072 (12)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0316 (2)	0.0383 (3)	0.0313 (2)	0.00047 (18)	−0.00502 (17)	−0.00030 (19)
Cl1	0.0372 (3)	0.1123 (7)	0.0734 (5)	0.0143 (4)	0.0035 (3)	−0.0158 (5)
Br1	0.0540 (2)	0.0644 (2)	0.0569 (2)	−0.00257 (13)	−0.00077 (14)	−0.02250 (14)
N1	0.0371 (10)	0.0360 (11)	0.0341 (9)	−0.0002 (8)	−0.0061 (8)	0.0005 (8)
C2	0.0340 (11)	0.0430 (13)	0.0396 (12)	−0.0047 (10)	−0.0072 (9)	0.0034 (10)
C3	0.0368 (12)	0.0436 (14)	0.0377 (11)	0.0020 (10)	−0.0045 (9)	0.0038 (10)
C4	0.0361 (11)	0.0398 (13)	0.0341 (11)	0.0006 (9)	−0.0016 (9)	0.0047 (10)
C5	0.0441 (13)	0.0395 (13)	0.0341 (11)	−0.0005 (10)	−0.0010 (10)	0.0019 (10)
C6	0.0492 (14)	0.0491 (15)	0.0371 (12)	0.0083 (12)	0.0038 (10)	0.0049 (11)
C7	0.0350 (12)	0.0610 (17)	0.0473 (14)	0.0095 (11)	0.0015 (10)	0.0077 (12)
C8	0.0378 (13)	0.0559 (17)	0.0444 (13)	0.0005 (11)	−0.0049 (10)	0.0006 (12)
O9	0.0337 (9)	0.0526 (10)	0.0448 (9)	−0.0005 (7)	−0.0011 (7)	−0.0110 (8)
C10	0.0379 (12)	0.0377 (13)	0.0413 (12)	0.0001 (9)	−0.0092 (10)	−0.0029 (10)
C11	0.0466 (14)	0.0478 (15)	0.0390 (12)	−0.0039 (11)	−0.0079 (10)	−0.0018 (11)
O12	0.0664 (13)	0.0446 (11)	0.0631 (12)	0.0024 (10)	−0.0310 (10)	0.0025 (10)

Geometric parameters (Å, º)

Cu1—N1	2.0219 (19)	C4—C5	1.410 (3)
Cu1—O9	1.8913 (18)	C5—C6	1.371 (4)
Cu1—O9^i	1.8913 (18)	C6—C7	1.385 (4)
Cu1—N1^i	2.0219 (19)	C6—H6	0.93
Cl1—C7	1.749 (3)	C7—C8	1.363 (4)
Br1—C5	1.888 (2)	C8—H8	0.93
N1—C2	1.287 (3)	C10—C11	1.515 (3)
N1—C10	1.471 (3)	C10—H10A	0.97
C2—C3	1.438 (4)	C10—H10B	0.97
C2—H2	0.93	C11—O12	1.414 (3)
C3—C8	1.406 (4)	C11—H11A	0.97
C3—C4	1.423 (3)	C11—H11B	0.97
C4—O9	1.299 (3)	O12—H12	0.821 (19)
O9—Cu1—O9^i	180	C5—C6—H6	120.5
O9—Cu1—N1^i	88.93 (8)	C7—C6—H6	120.5
O9^i—Cu1—N1^i	91.07 (8)	C8—C7—C6	120.9 (2)
O9—Cu1—N1	91.07 (8)	C8—C7—Cl1	120.9 (2)
O9^i—Cu1—N1	88.93 (8)	C6—C7—Cl1	118.2 (2)
N1^i—Cu1—N1	180	C7—C8—C3	120.4 (2)
C2—N1—C10	115.2 (2)	C7—C8—H8	119.8
C2—N1—Cu1	124.15 (17)	C3—C8—H8	119.8
C10—N1—Cu1	120.62 (15)	C4—O9—Cu1	130.89 (17)
N1—C2—C3	127.6 (2)	N1—C10—C11	111.2 (2)
N1—C2—H2	116.2	N1—C10—H10A	109.4
C3—C2—H2	116.2	C11—C10—H10A	109.4
C8—C3—C4	120.7 (2)	N1—C10—H10B	109.4
C8—C3—C2	117.5 (2)	C11—C10—H10B	109.4
C4—C3—C2	121.8 (2)	H10A—C10—H10B	108
O9—C4—C5	120.9 (2)	O12—C11—C10	112.3 (2)
O9—C4—C3	123.7 (2)	O12—C11—H11A	109.1
C5—C4—C3	115.4 (2)	C10—C11—H11A	109.1
C6—C5—C4	123.7 (2)	O12—C11—H11B	109.1
C6—C5—Br1	118.62 (19)	C10—C11—H11B	109.1
C4—C5—Br1	117.70 (18)	H11A—C11—H11B	107.9
C5—C6—C7	118.9 (2)	C11—O12—H12	107 (3)
C10—N1—C2—C3	177.7 (2)	C5—C6—C7—C8	0.1 (4)
Cu1—N1—C2—C3	−4.2 (4)	C5—C6—C7—Cl1	−178.0 (2)
N1—C2—C3—C8	178.7 (2)	C6—C7—C8—C3	0.6 (4)
N1—C2—C3—C4	0.1 (4)	Cl1—C7—C8—C3	178.6 (2)
C8—C3—C4—O9	179.1 (2)	C4—C3—C8—C7	−0.2 (4)
C2—C3—C4—O9	−2.4 (4)	C2—C3—C8—C7	−178.7 (2)
C8—C3—C4—C5	−0.8 (3)	C5—C4—O9—Cu1	−170.48 (17)
C2—C3—C4—C5	177.6 (2)	C3—C4—O9—Cu1	9.6 (4)
O9—C4—C5—C6	−178.4 (2)	N1^i—Cu1—O9—C4	169.6 (2)
C3—C4—C5—C6	1.5 (4)	N1—Cu1—O9—C4	−10.4 (2)
O9—C4—C5—Br1	3.5 (3)	C2—N1—C10—C11	−93.3 (3)
C3—C4—C5—Br1	−176.59 (17)	Cu1—N1—C10—C11	88.6 (2)
C4—C5—C6—C7	−1.2 (4)	N1—C10—C11—O12	72.5 (3)
Br1—C5—C6—C7	176.9 (2)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O12—H12···O12^ii	0.821 (19)	1.98 (2)	2.760 (2)	158 (4)

Symmetry code: (ii) −x+1/2, y+1/2, −z+3/2.