{6,6'-Dimeth-oxy-2,2'-[6-bromo-pyridine-2,3-diylbis(nitrilo-methyl-idyne)]-diphenol-ato}-copper(II) methanol solvate.

In the title compound, [Cu(C(21)H(16)BrN(3)O(4))]·CH(3)OH, the Cu(II) ion is coordinated by two N [Cu-N = 1.814 (3) and 1.917 (3) Å] and two O [Cu-O = 1.805 (3) and 1.893 (3) Å] atoms from the tetra-dentate Schiff base ligand in a distorted square-planar geometry. In the crystal structure, the approximately planar Cu complex mol-ecules are paired into centrosymmetric dimers with short inter-molecular Cu⋯N distances of 3.162 (3) Å. Weak O---H...O hydrogen bonds may help to stabilize the structure.

Related literature

For a related crystal structure, see Saha et al. (2007 ▶). For general background, see: Ghosh et al. (2006 ▶); Nayak et al. (2006 ▶); Singh et al. (2007 ▶); Yu et al. (2007 ▶).

Experimental

Crystal data

[Cu(C21H16BrN3O4)]·CH4O

M = 549.86

Triclinic,

a = 7.4520 (8) Å

b = 11.5402 (13) Å

c = 12.9432 (14) Å

α = 104.345 (2)°

β = 96.467 (2)°

γ = 96.531 (2)°

V = 1059.9 (2) Å3

Z = 2

Mo Kα radiation

μ = 2.96 mm−1

T = 293 (2) K

0.15 × 0.13 × 0.11 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.665, T max = 0.737

5332 measured reflections

3705 independent reflections

2885 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.139

S = 1.06

3705 reflections

293 parameters

H-atom parameters constrained

Δρmax = 0.73 e Å−3

Δρmin = −0.45 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molen class="Chemical">cular graphics: XP (Sheldrick, 1998 ▶); software used to prepare material for publication: XP.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003316/cv2514sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003316/cv2514Isup2.hkl

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

[Cu(C21H16BrN3O4)]·CH4O	Z = 2
Mr = 549.86	F(000) = 554
Triclinic, P1	Dx = 1.723 Mg m−3Dm = 1.723 Mg m−3Dm measured by not measured
a = 7.4520 (8) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.5402 (13) Å	Cell parameters from 1770 reflections
c = 12.9432 (14) Å	θ = 3.0–24.5°
α = 104.345 (2)°	µ = 2.96 mm−1
β = 96.467 (2)°	T = 293 K
γ = 96.531 (2)°	Block, blue
V = 1059.9 (2) Å3	0.15 × 0.13 × 0.11 mm

Bruker APEXII CCD area-detector diffractometer	3705 independent reflections
Radiation source: fine-focus sealed tube	2885 reflections with I > 2σ(I)
graphite	Rint = 0.019
φ and ω scans	θmax = 25.0°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −8→8
Tmin = 0.665, Tmax = 0.737	k = −13→9
5332 measured reflections	l = −15→15

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0831P)2 + 0.2066P] where P = (Fo2 + 2Fc2)/3
3705 reflections	(Δ/σ)max = 0.001
293 parameters	Δρmax = 0.73 e Å−3
0 restraints	Δρmin = −0.45 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	0.36241 (7)	−0.01108 (4)	0.60230 (4)	0.03577 (19)
Br1	0.23295 (10)	−0.51353 (5)	0.16747 (4)	0.0761 (3)
O1	0.2903 (4)	0.1323 (3)	0.5995 (2)	0.0383 (7)
O2	0.2316 (5)	0.3501 (3)	0.6365 (3)	0.0485 (8)
O3	0.4745 (4)	0.0684 (3)	0.7448 (2)	0.0405 (7)
O4	0.6350 (5)	0.2207 (3)	0.9307 (3)	0.0634 (10)
O5	0.1419 (5)	0.2035 (3)	0.8114 (3)	0.0625 (10)
H5	0.2014	0.1945	0.7612	0.075*
N1	0.4117 (5)	−0.3542 (3)	0.4995 (3)	0.0425 (9)
N2	0.4290 (4)	−0.1555 (3)	0.6099 (3)	0.0332 (8)
N3	0.2583 (4)	−0.0873 (3)	0.4554 (3)	0.0314 (7)
C1	0.3764 (5)	−0.2447 (4)	0.5091 (3)	0.0360 (9)
C2	0.2886 (5)	−0.2069 (3)	0.4228 (3)	0.0334 (9)
C3	0.2440 (6)	−0.2854 (4)	0.3183 (4)	0.0451 (11)
H3	0.1896	−0.2613	0.2603	0.054*
C4	0.2859 (6)	−0.3987 (4)	0.3081 (4)	0.0450 (11)
C5	0.3641 (6)	−0.4313 (4)	0.3988 (4)	0.0465 (11)
H5A	0.3850	−0.5109	0.3896	0.056*
C6	0.1301 (5)	0.0772 (4)	0.4117 (3)	0.0359 (9)
C7	0.1961 (5)	0.1589 (4)	0.5164 (3)	0.0342 (9)
C8	0.1615 (6)	0.2776 (4)	0.5331 (4)	0.0397 (10)
C9	0.0664 (6)	0.3116 (4)	0.4483 (4)	0.0478 (12)
H9	0.0452	0.3913	0.4597	0.057*
C10	0.0008 (6)	0.2296 (5)	0.3456 (4)	0.0501 (12)
H10	−0.0619	0.2564	0.2919	0.060*
C11	0.0288 (6)	0.1147 (4)	0.3262 (4)	0.0443 (11)
H11	−0.0153	0.0602	0.2598	0.053*
C12	0.1635 (5)	−0.0414 (4)	0.3872 (3)	0.0366 (10)
H12	0.1166	−0.0913	0.3191	0.044*
C13	0.2030 (8)	0.4705 (4)	0.6604 (4)	0.0583 (14)
H13A	0.2575	0.5096	0.6117	0.087*
H13B	0.2576	0.5108	0.7331	0.087*
H13C	0.0743	0.4741	0.6527	0.087*
C14	0.5858 (6)	−0.0953 (4)	0.7995 (3)	0.0379 (10)
C15	0.5660 (6)	0.0254 (4)	0.8168 (3)	0.0372 (10)
C16	0.6525 (6)	0.1045 (4)	0.9197 (4)	0.0446 (11)
C17	0.7470 (7)	0.0636 (5)	1.0005 (4)	0.0547 (13)
H17	0.7998	0.1177	1.0657	0.066*
C18	0.7609 (7)	−0.0570 (5)	0.9823 (4)	0.0546 (13)
H18	0.8209	−0.0859	1.0356	0.066*
C19	0.6857 (7)	−0.1340 (5)	0.8852 (4)	0.0501 (12)
H19	0.6988	−0.2152	0.8731	0.060*
C20	0.5175 (6)	−0.1781 (4)	0.6964 (3)	0.0380 (10)
H20	0.5376	−0.2576	0.6890	0.046*
C21	0.7138 (11)	0.3026 (5)	1.0320 (5)	0.088 (2)
H21A	0.6589	0.2793	1.0888	0.132*
H21B	0.6927	0.3831	1.0316	0.132*
H21C	0.8428	0.3006	1.0435	0.132*
C22	0.2129 (10)	0.3101 (5)	0.8876 (5)	0.0784 (18)
H22A	0.2649	0.2925	0.9523	0.118*
H22B	0.1175	0.3582	0.9032	0.118*
H22C	0.3060	0.3538	0.8604	0.118*

	U11	U22	U33	U12	U13	U23
Cu1	0.0395 (3)	0.0311 (3)	0.0352 (3)	0.0046 (2)	0.0021 (2)	0.0076 (2)
Br1	0.1168 (6)	0.0451 (3)	0.0517 (4)	0.0169 (3)	−0.0020 (3)	−0.0105 (3)
O1	0.0485 (17)	0.0308 (15)	0.0337 (15)	0.0054 (13)	−0.0022 (13)	0.0085 (12)
O2	0.066 (2)	0.0302 (16)	0.0483 (19)	0.0142 (15)	0.0021 (16)	0.0084 (14)
O3	0.0484 (17)	0.0341 (16)	0.0364 (16)	0.0062 (13)	−0.0035 (14)	0.0086 (13)
O4	0.092 (3)	0.039 (2)	0.047 (2)	0.0006 (18)	−0.0166 (19)	0.0059 (16)
O5	0.071 (2)	0.062 (2)	0.048 (2)	0.0059 (19)	0.0110 (18)	0.0016 (18)
N1	0.045 (2)	0.032 (2)	0.050 (2)	0.0079 (16)	0.0042 (18)	0.0097 (18)
N2	0.0338 (18)	0.0295 (18)	0.0352 (19)	0.0026 (14)	0.0053 (15)	0.0074 (15)
N3	0.0306 (17)	0.0291 (18)	0.0335 (18)	0.0022 (14)	0.0043 (14)	0.0078 (15)
C1	0.032 (2)	0.035 (2)	0.039 (2)	0.0020 (18)	0.0081 (18)	0.0070 (19)
C2	0.033 (2)	0.028 (2)	0.036 (2)	−0.0014 (17)	0.0079 (18)	0.0032 (18)
C3	0.050 (3)	0.038 (3)	0.045 (3)	0.007 (2)	0.002 (2)	0.007 (2)
C4	0.054 (3)	0.034 (2)	0.039 (2)	0.006 (2)	0.007 (2)	−0.003 (2)
C5	0.051 (3)	0.034 (2)	0.054 (3)	0.011 (2)	0.014 (2)	0.006 (2)
C6	0.030 (2)	0.043 (3)	0.037 (2)	0.0034 (18)	0.0054 (18)	0.017 (2)
C7	0.032 (2)	0.034 (2)	0.039 (2)	0.0039 (17)	0.0082 (18)	0.0132 (19)
C8	0.038 (2)	0.039 (2)	0.043 (3)	0.0040 (19)	0.005 (2)	0.014 (2)
C9	0.045 (3)	0.048 (3)	0.059 (3)	0.015 (2)	0.009 (2)	0.024 (2)
C10	0.047 (3)	0.059 (3)	0.050 (3)	0.015 (2)	−0.002 (2)	0.026 (3)
C11	0.040 (2)	0.051 (3)	0.041 (3)	0.005 (2)	0.001 (2)	0.015 (2)
C12	0.035 (2)	0.040 (2)	0.033 (2)	−0.0013 (18)	0.0057 (18)	0.0082 (19)
C13	0.077 (4)	0.034 (3)	0.066 (3)	0.015 (2)	0.011 (3)	0.014 (2)
C14	0.037 (2)	0.043 (3)	0.036 (2)	0.0122 (19)	0.0084 (19)	0.011 (2)
C15	0.037 (2)	0.041 (2)	0.035 (2)	0.0035 (18)	0.0057 (18)	0.0137 (19)
C16	0.046 (3)	0.045 (3)	0.040 (3)	0.002 (2)	0.000 (2)	0.010 (2)
C17	0.053 (3)	0.065 (3)	0.040 (3)	0.001 (2)	−0.005 (2)	0.011 (2)
C18	0.063 (3)	0.059 (3)	0.042 (3)	0.020 (3)	−0.007 (2)	0.017 (2)
C19	0.057 (3)	0.052 (3)	0.049 (3)	0.020 (2)	0.006 (2)	0.022 (2)
C20	0.040 (2)	0.035 (2)	0.043 (2)	0.0151 (19)	0.009 (2)	0.014 (2)
C21	0.139 (6)	0.042 (3)	0.060 (4)	−0.012 (3)	−0.032 (4)	0.002 (3)
C22	0.104 (5)	0.064 (4)	0.053 (3)	0.016 (3)	−0.008 (3)	−0.004 (3)

Cu1—O1	1.805 (3)	C7—C8	1.392 (6)
Cu1—N2	1.814 (3)	C8—C9	1.400 (6)
Cu1—O3	1.893 (3)	C9—C10	1.423 (7)
Cu1—N3	1.917 (3)	C9—H9	0.9300
Br1—C4	1.936 (4)	C10—C11	1.332 (6)
O1—C7	1.337 (5)	C10—H10	0.9300
O2—C13	1.393 (5)	C11—H11	0.9300
O2—C8	1.398 (5)	C12—H12	0.9300
O3—C15	1.320 (5)	C13—H13A	0.9600
O4—C16	1.335 (6)	C13—H13B	0.9600
O4—C21	1.430 (6)	C13—H13C	0.9600
O5—C22	1.378 (6)	C14—C15	1.382 (6)
O5—H5	0.8200	C14—C20	1.434 (6)
N1—C1	1.298 (5)	C14—C19	1.456 (6)
N1—C5	1.366 (6)	C15—C16	1.447 (6)
N2—C20	1.331 (5)	C16—C17	1.402 (6)
N2—C1	1.430 (5)	C17—C18	1.371 (7)
N3—C12	1.317 (5)	C17—H17	0.9300
N3—C2	1.392 (5)	C18—C19	1.364 (7)
C1—C2	1.417 (6)	C18—H18	0.9300
C2—C3	1.408 (6)	C19—H19	0.9300
C3—C4	1.356 (6)	C20—H20	0.9300
C3—H3	0.9300	C21—H21A	0.9600
C4—C5	1.405 (7)	C21—H21B	0.9600
C5—H5A	0.9300	C21—H21C	0.9600
C6—C12	1.385 (6)	C22—H22A	0.9600
C6—C7	1.441 (6)	C22—H22B	0.9600
C6—C11	1.451 (6)	C22—H22C	0.9600
O1—Cu1—N2	177.45 (14)	C9—C10—H10	119.9
O1—Cu1—O3	85.51 (12)	C10—C11—C6	118.1 (4)
N2—Cu1—O3	93.31 (13)	C10—C11—H11	121.0
O1—Cu1—N3	93.72 (13)	C6—C11—H11	121.0
N2—Cu1—N3	87.57 (14)	N3—C12—C6	123.4 (4)
O3—Cu1—N3	177.17 (13)	N3—C12—H12	118.3
C7—O1—Cu1	127.0 (3)	C6—C12—H12	118.3
C13—O2—C8	117.2 (4)	O2—C13—H13A	109.5
C15—O3—Cu1	129.7 (3)	O2—C13—H13B	109.5
C16—O4—C21	116.2 (4)	H13A—C13—H13B	109.5
C22—O5—H5	109.5	O2—C13—H13C	109.5
C1—N1—C5	115.7 (4)	H13A—C13—H13C	109.5
C20—N2—C1	123.0 (3)	H13B—C13—H13C	109.5
C20—N2—Cu1	125.7 (3)	C15—C14—C20	119.8 (4)
C1—N2—Cu1	111.3 (3)	C15—C14—C19	118.7 (4)
C12—N3—C2	119.4 (3)	C20—C14—C19	121.3 (4)
C12—N3—Cu1	128.3 (3)	O3—C15—C14	123.0 (4)
C2—N3—Cu1	112.3 (3)	O3—C15—C16	120.7 (4)
N1—C1—C2	123.0 (4)	C14—C15—C16	116.2 (4)
N1—C1—N2	120.0 (4)	O4—C16—C17	122.9 (4)
C2—C1—N2	116.9 (4)	O4—C16—C15	113.8 (4)
N3—C2—C3	127.0 (4)	C17—C16—C15	123.3 (4)
N3—C2—C1	111.8 (3)	C18—C17—C16	119.3 (5)
C3—C2—C1	121.3 (4)	C18—C17—H17	120.3
C4—C3—C2	115.3 (4)	C16—C17—H17	120.3
C4—C3—H3	122.4	C19—C18—C17	119.1 (4)
C2—C3—H3	122.4	C19—C18—H18	120.4
C3—C4—C5	120.1 (4)	C17—C18—H18	120.4
C3—C4—Br1	118.7 (4)	C18—C19—C14	123.2 (4)
C5—C4—Br1	121.2 (3)	C18—C19—H19	118.4
N1—C5—C4	124.5 (4)	C14—C19—H19	118.4
N1—C5—H5A	117.7	N2—C20—C14	128.2 (4)
C4—C5—H5A	117.7	N2—C20—H20	115.9
C12—C6—C7	121.2 (4)	C14—C20—H20	115.9
C12—C6—C11	116.5 (4)	O4—C21—H21A	109.5
C7—C6—C11	122.3 (4)	O4—C21—H21B	109.5
O1—C7—C8	116.2 (4)	H21A—C21—H21B	109.5
O1—C7—C6	126.3 (4)	O4—C21—H21C	109.5
C8—C7—C6	117.5 (4)	H21A—C21—H21C	109.5
C7—C8—O2	113.3 (4)	H21B—C21—H21C	109.5
C7—C8—C9	118.9 (4)	O5—C22—H22A	109.5
O2—C8—C9	127.8 (4)	O5—C22—H22B	109.5
C8—C9—C10	123.0 (4)	H22A—C22—H22B	109.5
C8—C9—H9	118.5	O5—C22—H22C	109.5
C10—C9—H9	118.5	H22A—C22—H22C	109.5
C11—C10—C9	120.3 (4)	H22B—C22—H22C	109.5
C11—C10—H10	119.9

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1	0.82	2.24	3.033 (5)	163
O5—H5···O3	0.82	2.63	3.165 (5)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O1	0.82	2.24	3.033 (5)	163
O5—H5⋯O3	0.82	2.63	3.165 (5)	124