Bis[μ-N'-(5-bromo-3-meth-oxy-2-oxido-benzyl-idene)-2-hydroxybenzohydra-zidato]bis[(N,N-dimethyl-formamide)-copper(II)].

The title compound, [Cu(2)(C(15)H(11)BrN(2)O(4))(2)(C(3)H(7)NO)(2)], is derived from the reaction of N'-(5-bromo-2-hy-droxy-3-meth-oxy-benzyl-idene)-2-hy-droxy-benzohydrazide and copper nitrate in a dimethyl-formamide solution in the presence of sodium hydroxide. The compound can be regarded as a binuclear centrosymmetric complex. In the crystal, the Cu(II) atom is fivefold surrounded and adopts a distorted square-pyramidal coordination environment. An intra-molecular O-H⋯N hydrogen bond stabilizes the mol-ecular conformation.

Related literature

For the synthesis of N′-(5-bromo-2-hy­droxy-3-meth­oxy­benzyl­idene)-2-hy­droxy­benzohydrazide and its crystal structure, see: Zhao et al. (2012 ▶). For the crystal structure of a complex with a similar coordination environment, see: Huang et al. (2010 ▶).

Experimental

Crystal data

[Cu2(C15H11BrN2O4)2(C3H7NO)2]

M = 999.61

Triclinic,

a = 8.3861 (17) Å

b = 9.5795 (19) Å

c = 12.275 (3) Å

α = 90.446 (3)°

β = 97.850 (3)°

γ = 101.688 (3)°

V = 956.0 (3) Å3

Z = 1

Mo Kα radiation

μ = 3.27 mm−1

T = 296 K

0.38 × 0.25 × 0.16 mm

Data collection

Bruker SMART 1K CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.371, T max = 0.620

5880 measured reflections

4354 independent reflections

2957 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.123

S = 0.99

4354 reflections

256 parameters

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.58 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); 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 and local programs.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812036100/bt5995sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812036100/bt5995Isup2.hkl

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

[Cu2(C15H11BrN2O4)2(C3H7NO)2]	Z = 1
Mr = 999.61	F(000) = 502
Triclinic, P1	Dx = 1.736 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3861 (17) Å	Cell parameters from 3650 reflections
b = 9.5795 (19) Å	θ = 1.8–26.5°
c = 12.275 (3) Å	µ = 3.27 mm−1
α = 90.446 (3)°	T = 296 K
β = 97.850 (3)°	Block, green
γ = 101.688 (3)°	0.38 × 0.25 × 0.16 mm
V = 956.0 (3) Å3

Bruker SMART 1K CCD area-detector diffractometer	4354 independent reflections
Radiation source: fine-focus sealed tube	2957 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
thin–slice ω scans	θmax = 29.5°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −10→9
Tmin = 0.371, Tmax = 0.620	k = −13→9
5880 measured reflections	l = −15→16

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H-atom parameters constrained
S = 0.99	w = 1/[σ2(Fo2) + (0.069P)2] where P = (Fo2 + 2Fc2)/3
4354 reflections	(Δ/σ)max = 0.001
256 parameters	Δρmax = 0.59 e Å−3
0 restraints	Δρmin = −0.58 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	0.08579 (5)	0.69096 (4)	1.00600 (3)	0.04176 (15)
Br1	−0.38768 (6)	1.16095 (5)	1.23139 (4)	0.0821 (2)
O2	0.1023 (3)	0.8271 (2)	1.11968 (18)	0.0456 (6)
O3	0.0529 (3)	0.5575 (2)	0.88176 (17)	0.0472 (6)
N1	−0.1145 (3)	0.7314 (3)	0.9327 (2)	0.0383 (6)
C8	−0.1977 (4)	0.8182 (4)	0.9650 (3)	0.0435 (8)
H8A	−0.2920	0.8293	0.9194	0.052*
N2	−0.1691 (3)	0.6616 (3)	0.8310 (2)	0.0397 (6)
O4	−0.3540 (3)	0.5853 (3)	0.6472 (2)	0.0592 (7)
H4A	−0.3231	0.6295	0.7064	0.089*
O1	0.1737 (3)	0.9882 (3)	1.29675 (19)	0.0532 (6)
C7	−0.0064 (4)	0.8995 (3)	1.1382 (2)	0.0373 (7)
C5	−0.2652 (4)	0.9817 (4)	1.0956 (3)	0.0473 (8)
H5A	−0.3618	0.9825	1.0485	0.057*
C2	0.0244 (4)	0.9885 (4)	1.2357 (3)	0.0427 (8)
C15	−0.0090 (4)	0.4028 (4)	0.6826 (3)	0.0503 (9)
H15A	0.0814	0.3948	0.7334	0.060*
C9	−0.0709 (4)	0.5740 (3)	0.8131 (2)	0.0378 (7)
C10	−0.1099 (4)	0.4926 (3)	0.7074 (3)	0.0404 (7)
C3	−0.0851 (4)	1.0652 (4)	1.2625 (3)	0.0463 (8)
H3A	−0.0634	1.1207	1.3274	0.056*
C13	−0.1735 (5)	0.3340 (5)	0.5115 (3)	0.0665 (11)
H13A	−0.1945	0.2805	0.4456	0.080*
C11	−0.2471 (4)	0.5005 (4)	0.6306 (3)	0.0442 (8)
C4	−0.2312 (5)	1.0593 (4)	1.1908 (3)	0.0501 (9)
C12	−0.2778 (5)	0.4198 (4)	0.5330 (3)	0.0595 (10)
H12A	−0.3695	0.4240	0.4822	0.071*
C6	−0.1546 (4)	0.8990 (3)	1.0669 (3)	0.0396 (7)
C14	−0.0388 (5)	0.3255 (5)	0.5852 (3)	0.0641 (11)
H14A	0.0322	0.2676	0.5694	0.077*
O5	0.2998 (3)	0.6509 (2)	1.06249 (19)	0.0480 (6)
N3	0.5109 (3)	0.6665 (3)	1.1985 (2)	0.0469 (7)
C17	0.3796 (4)	0.7041 (4)	1.1530 (3)	0.0456 (8)
H17A	0.3414	0.7742	1.1886	0.055*
C16	0.6002 (5)	0.7336 (5)	1.3018 (3)	0.0617 (11)
H16A	0.5433	0.8023	1.3272	0.093*
H16B	0.7090	0.7806	1.2907	0.093*
H16C	0.6073	0.6622	1.3557	0.093*
C1	0.2101 (6)	1.0583 (5)	1.4017 (3)	0.0672 (11)
H1A	0.3178	1.0496	1.4351	0.101*
H1B	0.1304	1.0154	1.4472	0.101*
H1C	0.2066	1.1573	1.3941	0.101*
C18	0.5749 (5)	0.5542 (5)	1.1512 (4)	0.0654 (11)
H18A	0.4883	0.4937	1.1028	0.098*
H18B	0.6171	0.4988	1.2089	0.098*
H18C	0.6616	0.5955	1.1104	0.098*

	U11	U22	U33	U12	U13	U23
Cu1	0.0362 (2)	0.0507 (3)	0.0374 (2)	0.01501 (18)	−0.00696 (16)	−0.00787 (17)
Br1	0.0733 (3)	0.1088 (4)	0.0734 (3)	0.0549 (3)	−0.0096 (2)	−0.0330 (3)
O2	0.0385 (13)	0.0546 (14)	0.0435 (12)	0.0180 (11)	−0.0066 (10)	−0.0112 (10)
O3	0.0419 (13)	0.0591 (15)	0.0408 (12)	0.0209 (11)	−0.0079 (10)	−0.0123 (10)
N1	0.0389 (15)	0.0411 (15)	0.0336 (13)	0.0104 (12)	−0.0023 (11)	−0.0008 (11)
C8	0.0374 (17)	0.046 (2)	0.0449 (18)	0.0123 (15)	−0.0077 (14)	−0.0012 (15)
N2	0.0387 (15)	0.0393 (15)	0.0375 (14)	0.0080 (12)	−0.0067 (11)	−0.0072 (11)
O4	0.0599 (16)	0.0672 (18)	0.0486 (15)	0.0250 (14)	−0.0163 (12)	−0.0091 (12)
O1	0.0450 (14)	0.0676 (17)	0.0441 (13)	0.0160 (12)	−0.0094 (11)	−0.0157 (12)
C7	0.0384 (17)	0.0368 (17)	0.0360 (16)	0.0086 (14)	0.0018 (13)	−0.0004 (13)
C5	0.0402 (19)	0.059 (2)	0.0440 (19)	0.0185 (16)	−0.0023 (15)	−0.0039 (16)
C2	0.0405 (18)	0.048 (2)	0.0374 (17)	0.0088 (15)	−0.0014 (14)	−0.0027 (14)
C15	0.043 (2)	0.061 (2)	0.047 (2)	0.0170 (17)	−0.0022 (15)	−0.0081 (16)
C9	0.0331 (16)	0.0435 (19)	0.0334 (16)	0.0037 (14)	−0.0015 (13)	0.0015 (13)
C10	0.0389 (18)	0.0436 (19)	0.0354 (16)	0.0040 (15)	0.0006 (13)	−0.0007 (14)
C3	0.050 (2)	0.049 (2)	0.0398 (18)	0.0120 (16)	0.0042 (15)	−0.0070 (15)
C13	0.071 (3)	0.083 (3)	0.045 (2)	0.020 (2)	−0.0027 (19)	−0.022 (2)
C11	0.046 (2)	0.046 (2)	0.0379 (17)	0.0096 (16)	−0.0007 (15)	0.0021 (14)
C4	0.048 (2)	0.054 (2)	0.051 (2)	0.0195 (17)	0.0041 (16)	−0.0053 (16)
C12	0.062 (3)	0.069 (3)	0.040 (2)	0.009 (2)	−0.0111 (17)	−0.0053 (18)
C6	0.0348 (17)	0.0389 (18)	0.0440 (18)	0.0088 (14)	0.0004 (13)	−0.0017 (14)
C14	0.063 (3)	0.076 (3)	0.056 (2)	0.024 (2)	0.0040 (19)	−0.019 (2)
O5	0.0379 (13)	0.0562 (15)	0.0488 (13)	0.0164 (11)	−0.0074 (10)	−0.0079 (11)
N3	0.0310 (14)	0.0506 (18)	0.0537 (17)	0.0044 (12)	−0.0062 (12)	−0.0006 (13)
C17	0.0346 (18)	0.049 (2)	0.050 (2)	0.0069 (15)	−0.0017 (15)	0.0024 (16)
C16	0.047 (2)	0.070 (3)	0.060 (2)	0.0083 (19)	−0.0155 (18)	−0.0032 (19)
C1	0.061 (3)	0.077 (3)	0.055 (2)	0.010 (2)	−0.014 (2)	−0.022 (2)
C18	0.045 (2)	0.076 (3)	0.077 (3)	0.026 (2)	−0.003 (2)	−0.005 (2)

Cu1—O2	1.874 (2)	C9—C10	1.470 (4)
Cu1—N1	1.907 (3)	C10—C11	1.399 (4)
Cu1—O3	1.936 (2)	C3—C4	1.398 (5)
Cu1—O5	1.948 (2)	C3—H3A	0.9300
Br1—C4	1.899 (4)	C13—C14	1.364 (6)
O2—C7	1.294 (4)	C13—C12	1.365 (6)
O3—C9	1.282 (4)	C13—H13A	0.9300
N1—C8	1.281 (4)	C11—C12	1.385 (5)
N1—N2	1.386 (3)	C12—H12A	0.9300
C8—C6	1.429 (4)	C14—H14A	0.9300
C8—H8A	0.9300	O5—C17	1.262 (4)
N2—C9	1.326 (4)	N3—C17	1.284 (4)
O4—C11	1.359 (4)	N3—C18	1.446 (5)
O4—H4A	0.8200	N3—C16	1.454 (5)
O1—C2	1.369 (4)	C17—H17A	0.9300
O1—C1	1.414 (4)	C16—H16A	0.9600
C7—C6	1.418 (4)	C16—H16B	0.9600
C7—C2	1.426 (4)	C16—H16C	0.9600
C5—C4	1.345 (5)	C1—H1A	0.9600
C5—C6	1.412 (5)	C1—H1B	0.9600
C5—H5A	0.9300	C1—H1C	0.9600
C2—C3	1.358 (5)	C18—H18A	0.9600
C15—C14	1.367 (5)	C18—H18B	0.9600
C15—C10	1.382 (5)	C18—H18C	0.9600
C15—H15A	0.9300
O2—Cu1—N1	93.33 (10)	O4—C11—C12	117.5 (3)
O2—Cu1—O3	174.87 (9)	O4—C11—C10	122.6 (3)
N1—Cu1—O3	81.62 (10)	C12—C11—C10	119.8 (3)
O2—Cu1—O5	91.67 (10)	C5—C4—C3	122.0 (3)
N1—Cu1—O5	172.69 (11)	C5—C4—Br1	119.4 (3)
O3—Cu1—O5	93.28 (9)	C3—C4—Br1	118.7 (3)
C7—O2—Cu1	127.5 (2)	C13—C12—C11	120.0 (4)
C9—O3—Cu1	110.17 (19)	C13—C12—H12A	120.0
C8—N1—N2	118.0 (3)	C11—C12—H12A	120.0
C8—N1—Cu1	127.4 (2)	C5—C6—C7	119.7 (3)
N2—N1—Cu1	114.56 (19)	C5—C6—C8	117.7 (3)
N1—C8—C6	124.1 (3)	C7—C6—C8	122.6 (3)
N1—C8—H8A	118.0	C13—C14—C15	119.5 (4)
C6—C8—H8A	118.0	C13—C14—H14A	120.2
C9—N2—N1	109.4 (2)	C15—C14—H14A	120.2
C11—O4—H4A	109.5	C17—O5—Cu1	122.1 (2)
C2—O1—C1	118.4 (3)	C17—N3—C18	121.9 (3)
O2—C7—C6	124.4 (3)	C17—N3—C16	121.1 (3)
O2—C7—C2	118.6 (3)	C18—N3—C16	117.0 (3)
C6—C7—C2	117.0 (3)	O5—C17—N3	123.4 (3)
C4—C5—C6	120.2 (3)	O5—C17—H17A	118.3
C4—C5—H5A	119.9	N3—C17—H17A	118.3
C6—C5—H5A	119.9	N3—C16—H16A	109.5
C3—C2—O1	124.7 (3)	N3—C16—H16B	109.5
C3—C2—C7	122.2 (3)	H16A—C16—H16B	109.5
O1—C2—C7	113.1 (3)	N3—C16—H16C	109.5
C14—C15—C10	121.6 (3)	H16A—C16—H16C	109.5
C14—C15—H15A	119.2	H16B—C16—H16C	109.5
C10—C15—H15A	119.2	O1—C1—H1A	109.5
O3—C9—N2	123.8 (3)	O1—C1—H1B	109.5
O3—C9—C10	119.6 (3)	H1A—C1—H1B	109.5
N2—C9—C10	116.5 (3)	O1—C1—H1C	109.5
C15—C10—C11	118.0 (3)	H1A—C1—H1C	109.5
C15—C10—C9	119.2 (3)	H1B—C1—H1C	109.5
C11—C10—C9	122.8 (3)	N3—C18—H18A	109.5
C2—C3—C4	118.9 (3)	N3—C18—H18B	109.5
C2—C3—H3A	120.6	H18A—C18—H18B	109.5
C4—C3—H3A	120.6	N3—C18—H18C	109.5
C14—C13—C12	120.9 (4)	H18A—C18—H18C	109.5
C14—C13—H13A	119.6	H18B—C18—H18C	109.5
C12—C13—H13A	119.6

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4A···N2	0.82	1.84	2.566 (3)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H4A⋯N2	0.82	1.84	2.566 (3)	146