{4,4'-Dibromo-2,2'-[2,2-dimethyl-propane-1,3-diylbis(nitrilo-methyl-idyne)]diphenolato-κO,N,N',O'}copper(II).

In the title compound, [Cu(C(19)H(18)Br(2)N(2)O(2))], the Cu(II) ion is in a tetra-hedrally distorted planar geometry, involving two N and two O atoms from the tetra-dentate Schiff base ligand. Inter-molecular C-H⋯O hydrogen bonds form an eight-membered R(2) (2)(8) motif. The dihedral angle betwen two benzene rings is 36.34 (9)°. There are inter-molecular Cu⋯Br [3.4566 (5) Å] and Cu⋯·N [3.569 (3) Å] contacts, which are significantly shorter than the sum of van der Waals radii of the relevant atoms. These inter-actions, along with the inter-molecular C-H⋯π and π-π [centroid-centroid distances of 3.709 (1) and 3.968 (2) Å] inter-actions, link neighbouring mol-ecules into a one-dimensional infinite chain along the c axis.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For values of van der Waals radii, see: Bondi (1964 ▶). For related structures, see: Arıcı et al. (2001 ▶); Elmali et al. (2000 ▶); Hodgson (1975 ▶); Granovski et al. (1993 ▶). For the application of transition-metal complexes with Schiff base ligands, see: Blower (1998 ▶); Shahrokhian et al. (2000 ▶).

Experimental

Crystal data

[Cu(C19H18Br2N2O2)]

M = 529.71

Triclinic,

a = 9.1416 (3) Å

b = 9.6398 (3) Å

c = 11.5382 (3) Å

α = 75.210 (2)°

β = 78.913 (2)°

γ = 73.435 (2)°

V = 934.42 (5) Å3

Z = 2

Mo Kα radiation

μ = 5.46 mm−1

T = 100.0 (1) K

0.41 × 0.21 × 0.15 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2001 ▶) T min = 0.195, T max = 0.443

29164 measured reflections

5410 independent reflections

4345 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.093

S = 1.07

5410 reflections

235 parameters

H-atom parameters constrained

Δρmax = 1.27 e Å−3

Δρmin = −0.61 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808036635/hy2161sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036635/hy2161Isup2.hkl

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

[Cu(C19H18Br2N2O2)]	Z = 2
Mr = 529.71	F000 = 522
Triclinic, P1	Dx = 1.883 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 9.1416 (3) Å	Cell parameters from 9921 reflections
b = 9.6398 (3) Å	θ = 2.2–33.8º
c = 11.5382 (3) Å	µ = 5.46 mm−1
α = 75.210 (2)º	T = 100.0 (1) K
β = 78.913 (2)º	Block, red
γ = 73.435 (2)º	0.41 × 0.21 × 0.15 mm
V = 934.42 (5) Å3

Bruker SMART APEXII CCD area-detector diffractometer	5410 independent reflections
Radiation source: fine-focus sealed tube	4345 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.037
T = 100.0(1) K	θmax = 30.0º
φ and ω scans	θmin = 1.8º
Absorption correction: multi-scan(SADABS; Bruker, 2001)	h = −12→12
Tmin = 0.195, Tmax = 0.443	k = −13→13
29164 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033	H-atom parameters constrained
wR(F2) = 0.093	w = 1/[σ2(Fo2) + (0.0524P)2 + 0.5947P] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.002
5410 reflections	Δρmax = 1.27 e Å−3
235 parameters	Δρmin = −0.61 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

	x	y	z	Uiso*/Ueq
Cu1	0.60215 (4)	0.07295 (3)	0.63222 (3)	0.01866 (8)
Br1	0.15151 (3)	−0.15996 (3)	1.22034 (2)	0.02498 (8)
Br2	0.80441 (4)	0.43866 (3)	−0.00230 (2)	0.02942 (9)
O1	0.4262 (2)	0.1481 (2)	0.73927 (16)	0.0210 (4)
O2	0.5974 (2)	0.2636 (2)	0.53114 (17)	0.0226 (4)
N1	0.6688 (3)	−0.1090 (2)	0.7503 (2)	0.0195 (4)
N2	0.6996 (3)	−0.0301 (2)	0.5008 (2)	0.0193 (4)
C1	0.3696 (3)	0.0739 (3)	0.8409 (2)	0.0187 (5)
C2	0.2233 (3)	0.1404 (3)	0.8980 (2)	0.0216 (5)
H2A	0.1701	0.2336	0.8604	0.026*
C3	0.1577 (3)	0.0712 (3)	1.0073 (2)	0.0222 (5)
H3A	0.0617	0.1176	1.0423	0.027*
C4	0.2363 (3)	−0.0692 (3)	1.0654 (2)	0.0209 (5)
C5	0.3765 (3)	−0.1391 (3)	1.0130 (2)	0.0202 (5)
H5A	0.4274	−0.2325	1.0520	0.024*
C6	0.4441 (3)	−0.0708 (3)	0.9004 (2)	0.0182 (5)
C7	0.5935 (3)	−0.1509 (3)	0.8535 (2)	0.0195 (5)
H7A	0.6390	−0.2402	0.9019	0.023*
C8	0.8231 (3)	−0.1986 (3)	0.7167 (3)	0.0220 (5)
H8A	0.8583	−0.2707	0.7877	0.026*
H8B	0.8935	−0.1347	0.6889	0.026*
C9	0.8276 (3)	−0.2804 (3)	0.6167 (2)	0.0215 (5)
C10	0.7088 (3)	−0.1897 (3)	0.5308 (2)	0.0208 (5)
H10A	0.7350	−0.2262	0.4566	0.025*
H10B	0.6084	−0.2049	0.5677	0.025*
C11	0.7379 (3)	0.0315 (3)	0.3905 (2)	0.0191 (5)
H11A	0.7818	−0.0304	0.3364	0.023*
C12	0.7183 (3)	0.1880 (3)	0.3441 (2)	0.0184 (5)
C13	0.7662 (3)	0.2337 (3)	0.2195 (2)	0.0200 (5)
H13A	0.8138	0.1630	0.1734	0.024*
C14	0.7432 (3)	0.3807 (3)	0.1663 (2)	0.0206 (5)
C15	0.6701 (3)	0.4888 (3)	0.2346 (2)	0.0221 (5)
H15A	0.6534	0.5887	0.1975	0.026*
C16	0.6231 (3)	0.4473 (3)	0.3559 (2)	0.0221 (5)
H16A	0.5755	0.5202	0.3999	0.027*
C17	0.6454 (3)	0.2960 (3)	0.4160 (2)	0.0193 (5)
C18	0.7856 (3)	−0.4283 (3)	0.6727 (3)	0.0255 (6)
H18A	0.7886	−0.4782	0.6098	0.038*
H18B	0.6840	−0.4106	0.7165	0.038*
H18C	0.8580	−0.4889	0.7268	0.038*
C19	0.9898 (3)	−0.3061 (3)	0.5469 (3)	0.0267 (6)
H19A	0.9944	−0.3565	0.4841	0.040*
H19B	1.0627	−0.3653	0.6011	0.040*
H19C	1.0142	−0.2124	0.5118	0.040*

	U11	U22	U33	U12	U13	U23
Cu1	0.02588 (17)	0.01331 (15)	0.01503 (15)	−0.00383 (12)	−0.00011 (12)	−0.00300 (12)
Br1	0.03447 (15)	0.02289 (14)	0.01814 (13)	−0.01260 (11)	0.00257 (10)	−0.00364 (10)
Br2	0.04858 (18)	0.01898 (14)	0.01683 (13)	−0.00907 (12)	0.00283 (11)	−0.00148 (10)
O1	0.0275 (9)	0.0161 (9)	0.0166 (9)	−0.0040 (7)	0.0010 (7)	−0.0029 (7)
O2	0.0316 (10)	0.0154 (9)	0.0182 (9)	−0.0037 (8)	0.0001 (7)	−0.0036 (7)
N1	0.0240 (11)	0.0159 (10)	0.0180 (10)	−0.0030 (8)	−0.0029 (8)	−0.0047 (9)
N2	0.0282 (11)	0.0131 (10)	0.0166 (10)	−0.0057 (8)	−0.0023 (8)	−0.0032 (8)
C1	0.0268 (13)	0.0156 (11)	0.0162 (11)	−0.0069 (10)	−0.0036 (9)	−0.0055 (9)
C2	0.0268 (13)	0.0164 (12)	0.0211 (13)	−0.0055 (10)	−0.0031 (10)	−0.0031 (10)
C3	0.0245 (13)	0.0219 (13)	0.0217 (13)	−0.0070 (10)	−0.0001 (10)	−0.0080 (11)
C4	0.0287 (13)	0.0198 (12)	0.0161 (12)	−0.0103 (10)	−0.0011 (10)	−0.0037 (10)
C5	0.0286 (13)	0.0170 (12)	0.0160 (12)	−0.0079 (10)	−0.0029 (10)	−0.0027 (10)
C6	0.0251 (12)	0.0154 (11)	0.0155 (11)	−0.0062 (9)	−0.0023 (9)	−0.0045 (10)
C7	0.0258 (13)	0.0154 (11)	0.0171 (12)	−0.0039 (10)	−0.0046 (10)	−0.0028 (10)
C8	0.0236 (12)	0.0184 (12)	0.0230 (13)	−0.0033 (10)	−0.0027 (10)	−0.0048 (11)
C9	0.0262 (13)	0.0162 (12)	0.0213 (13)	−0.0040 (10)	−0.0029 (10)	−0.0042 (10)
C10	0.0302 (13)	0.0137 (11)	0.0185 (12)	−0.0066 (10)	−0.0011 (10)	−0.0036 (10)
C11	0.0256 (12)	0.0147 (11)	0.0170 (12)	−0.0049 (9)	−0.0026 (9)	−0.0037 (9)
C12	0.0227 (12)	0.0152 (11)	0.0175 (12)	−0.0057 (9)	−0.0010 (9)	−0.0040 (10)
C13	0.0246 (12)	0.0187 (12)	0.0173 (12)	−0.0057 (10)	−0.0012 (10)	−0.0056 (10)
C14	0.0272 (13)	0.0188 (12)	0.0158 (12)	−0.0082 (10)	−0.0014 (10)	−0.0021 (10)
C15	0.0303 (14)	0.0137 (11)	0.0212 (13)	−0.0059 (10)	−0.0039 (10)	−0.0011 (10)
C16	0.0289 (13)	0.0147 (12)	0.0217 (13)	−0.0043 (10)	0.0001 (10)	−0.0056 (10)
C17	0.0232 (12)	0.0162 (11)	0.0181 (12)	−0.0052 (9)	−0.0013 (9)	−0.0038 (10)
C18	0.0361 (15)	0.0163 (12)	0.0230 (13)	−0.0064 (11)	−0.0042 (11)	−0.0020 (11)
C19	0.0269 (14)	0.0234 (14)	0.0287 (15)	−0.0048 (11)	0.0008 (11)	−0.0083 (12)

Cu1—O2	1.9027 (19)	C8—H8A	0.9700
Cu1—O1	1.9146 (18)	C8—H8B	0.9700
Cu1—N1	1.948 (2)	C9—C18	1.530 (4)
Cu1—N2	1.955 (2)	C9—C19	1.531 (4)
Br1—C4	1.902 (3)	C9—C10	1.535 (4)
Br2—C14	1.901 (3)	C10—H10A	0.9700
O1—C1	1.305 (3)	C10—H10B	0.9700
O2—C17	1.303 (3)	C11—C12	1.437 (4)
N1—C7	1.286 (3)	C11—H11A	0.9300
N1—C8	1.467 (3)	C12—C13	1.413 (4)
N2—C11	1.287 (3)	C12—C17	1.432 (3)
N2—C10	1.470 (3)	C13—C14	1.366 (4)
C1—C2	1.422 (4)	C13—H13A	0.9300
C1—C6	1.425 (4)	C14—C15	1.405 (4)
C2—C3	1.379 (4)	C15—C16	1.373 (4)
C2—H2A	0.9300	C15—H15A	0.9300
C3—C4	1.402 (4)	C16—C17	1.420 (4)
C3—H3A	0.9300	C16—H16A	0.9300
C4—C5	1.371 (4)	C18—H18A	0.9600
C5—C6	1.411 (4)	C18—H18B	0.9600
C5—H5A	0.9300	C18—H18C	0.9600
C6—C7	1.442 (4)	C19—H19A	0.9600
C7—H7A	0.9300	C19—H19B	0.9600
C8—C9	1.544 (4)	C19—H19C	0.9600
O2—Cu1—O1	92.77 (8)	C19—C9—C10	110.3 (2)
O2—Cu1—N1	160.11 (9)	C18—C9—C8	110.1 (2)
O1—Cu1—N1	93.32 (9)	C19—C9—C8	108.4 (2)
O2—Cu1—N2	93.40 (8)	C10—C9—C8	110.7 (2)
O1—Cu1—N2	151.78 (9)	N2—C10—C9	113.6 (2)
N1—Cu1—N2	90.14 (9)	N2—C10—H10A	108.8
C1—O1—Cu1	126.57 (17)	C9—C10—H10A	108.8
C17—O2—Cu1	128.01 (16)	N2—C10—H10B	108.8
C7—N1—C8	119.4 (2)	C9—C10—H10B	108.8
C7—N1—Cu1	125.97 (19)	H10A—C10—H10B	107.7
C8—N1—Cu1	114.58 (17)	N2—C11—C12	125.4 (2)
C11—N2—C10	118.7 (2)	N2—C11—H11A	117.3
C11—N2—Cu1	125.90 (18)	C12—C11—H11A	117.3
C10—N2—Cu1	114.85 (16)	C13—C12—C17	120.1 (2)
O1—C1—C2	118.6 (2)	C13—C12—C11	116.7 (2)
O1—C1—C6	124.7 (2)	C17—C12—C11	123.1 (2)
C2—C1—C6	116.7 (2)	C14—C13—C12	120.7 (2)
C3—C2—C1	122.2 (3)	C14—C13—H13A	119.7
C3—C2—H2A	118.9	C12—C13—H13A	119.7
C1—C2—H2A	118.9	C13—C14—C15	120.3 (2)
C2—C3—C4	119.7 (2)	C13—C14—Br2	119.65 (19)
C2—C3—H3A	120.1	C15—C14—Br2	120.0 (2)
C4—C3—H3A	120.1	C16—C15—C14	120.2 (2)
C5—C4—C3	120.3 (2)	C16—C15—H15A	119.9
C5—C4—Br1	119.8 (2)	C14—C15—H15A	119.9
C3—C4—Br1	119.8 (2)	C15—C16—C17	121.8 (2)
C4—C5—C6	120.7 (3)	C15—C16—H16A	119.1
C4—C5—H5A	119.7	C17—C16—H16A	119.1
C6—C5—H5A	119.7	O2—C17—C16	118.9 (2)
C5—C6—C1	120.4 (2)	O2—C17—C12	124.1 (2)
C5—C6—C7	116.8 (2)	C16—C17—C12	117.0 (2)
C1—C6—C7	122.7 (2)	C9—C18—H18A	109.5
N1—C7—C6	125.3 (2)	C9—C18—H18B	109.5
N1—C7—H7A	117.3	H18A—C18—H18B	109.5
C6—C7—H7A	117.3	C9—C18—H18C	109.5
N1—C8—C9	112.7 (2)	H18A—C18—H18C	109.5
N1—C8—H8A	109.0	H18B—C18—H18C	109.5
C9—C8—H8A	109.0	C9—C19—H19A	109.5
N1—C8—H8B	109.0	C9—C19—H19B	109.5
C9—C8—H8B	109.0	H19A—C19—H19B	109.5
H8A—C8—H8B	107.8	C9—C19—H19C	109.5
C18—C9—C19	110.4 (2)	H19A—C19—H19C	109.5
C18—C9—C10	106.9 (2)	H19B—C19—H19C	109.5
O2—Cu1—O1—C1	−174.0 (2)	C8—N1—C7—C6	177.2 (2)
N1—Cu1—O1—C1	−12.9 (2)	Cu1—N1—C7—C6	0.6 (4)
N2—Cu1—O1—C1	83.6 (3)	C5—C6—C7—N1	176.6 (2)
O1—Cu1—O2—C17	−151.9 (2)	C1—C6—C7—N1	−6.7 (4)
N1—Cu1—O2—C17	100.4 (3)	C7—N1—C8—C9	108.8 (3)
N2—Cu1—O2—C17	0.6 (2)	Cu1—N1—C8—C9	−74.2 (2)
O2—Cu1—N1—C7	114.8 (3)	N1—C8—C9—C18	−86.0 (3)
O1—Cu1—N1—C7	7.2 (2)	N1—C8—C9—C19	153.1 (2)
N2—Cu1—N1—C7	−144.8 (2)	N1—C8—C9—C10	32.0 (3)
O2—Cu1—N1—C8	−61.9 (3)	C11—N2—C10—C9	115.7 (3)
O1—Cu1—N1—C8	−169.52 (17)	Cu1—N2—C10—C9	−72.2 (2)
N2—Cu1—N1—C8	38.50 (18)	C18—C9—C10—N2	160.8 (2)
O2—Cu1—N2—C11	0.1 (2)	C19—C9—C10—N2	−79.2 (3)
O1—Cu1—N2—C11	102.4 (3)	C8—C9—C10—N2	40.8 (3)
N1—Cu1—N2—C11	−160.3 (2)	C10—N2—C11—C12	172.3 (2)
O2—Cu1—N2—C10	−171.27 (18)	Cu1—N2—C11—C12	1.2 (4)
O1—Cu1—N2—C10	−69.0 (3)	N2—C11—C12—C13	−179.2 (3)
N1—Cu1—N2—C10	28.31 (19)	N2—C11—C12—C17	−3.2 (4)
Cu1—O1—C1—C2	−169.15 (18)	C17—C12—C13—C14	−0.2 (4)
Cu1—O1—C1—C6	11.1 (4)	C11—C12—C13—C14	175.9 (2)
O1—C1—C2—C3	−178.0 (2)	C12—C13—C14—C15	−0.6 (4)
C6—C1—C2—C3	1.9 (4)	C12—C13—C14—Br2	−178.50 (19)
C1—C2—C3—C4	0.1 (4)	C13—C14—C15—C16	0.9 (4)
C2—C3—C4—C5	−1.3 (4)	Br2—C14—C15—C16	178.8 (2)
C2—C3—C4—Br1	176.5 (2)	C14—C15—C16—C17	−0.4 (4)
C3—C4—C5—C6	0.4 (4)	Cu1—O2—C17—C16	176.52 (18)
Br1—C4—C5—C6	−177.39 (19)	Cu1—O2—C17—C12	−2.5 (4)
C4—C5—C6—C1	1.7 (4)	C15—C16—C17—O2	−179.5 (2)
C4—C5—C6—C7	178.5 (2)	C15—C16—C17—C12	−0.4 (4)
O1—C1—C6—C5	177.1 (2)	C13—C12—C17—O2	179.8 (2)
C2—C1—C6—C5	−2.7 (4)	C11—C12—C17—O2	3.9 (4)
O1—C1—C6—C7	0.5 (4)	C13—C12—C17—C16	0.7 (4)
C2—C1—C6—C7	−179.3 (2)	C11—C12—C17—C16	−175.2 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···O2i	0.93	2.44	3.342 (3)	163
C10—H10B···Cg1ii	0.97	2.50	3.324 (3)	142

Table 1

Selected bond lengths (Å)

Cu1—O2	1.9027 (19)
Cu1—O1	1.9146 (18)
Cu1—N1	1.948 (2)
Cu1—N2	1.955 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯O2i	0.93	2.44	3.342 (3)	163
C10—H10B⋯Cg1ii	0.97	2.50	3.324 (3)	142

Symmetry codes: (i) ; (ii) . Cg1 is the centroid of the Cu1, N2, O2, C11, C12, C17 ring.