Dibromido{2-hydr-oxy-N'-[phen-yl(2-pyrid-yl)methyl-ene]benzohydrazide}copper(II).

In the title complex, [CuBr(2)(C(19)H(15)N(3)O(2))], the metal ion is coordinated by the N,N',O-tridentate 2-hydr-oxy-N'-[phen-yl(2-pyrid-yl)methyl-ene]benzohydrazide ligand and two bromide ions, resulting in a distorted CuN(2)OBr(2) square-based pyramidal coordination geometry with one bromide ion in the apical site. An intra-molecular N-H⋯O hydrogen bond occurs in the ligand. In the crystal, mol-ecules are connected by inter-molecular C-H⋯O, C-H⋯Br and O-H⋯Br inter-actions.

Related literature

For the crystal structures of metal complexes with 2-benzoyl­pyridine salicyloylhydrazone, see: Sur et al. (1993 ▶); Seth & Chakraborty (1984 ▶); Dan et al. (1989 ▶).

Experimental

Crystal data

[CuBr2(C19H15N3O2)]

M = 540.70

Monoclinic,

a = 8.0779 (11) Å

b = 16.302 (2) Å

c = 15.0376 (18) Å

β = 97.624 (2)°

V = 1962.8 (4) Å3

Z = 4

Mo Kα radiation

μ = 5.20 mm−1

T = 298 K

0.23 × 0.19 × 0.15 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.381, T max = 0.509

8676 measured reflections

3446 independent reflections

2426 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.082

S = 1.01

3446 reflections

244 parameters

H-atom parameters constrained

Δρmax = 0.94 e Å−3

Δρmin = −0.58 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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 I, global. DOI: 10.1107/S1600536809038070/hb5107sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038070/hb5107Isup2.hkl

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

[CuBr2(C19H15N3O2)]	F(000) = 1060
Mr = 540.70	Dx = 1.830 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2246 reflections
a = 8.0779 (11) Å	θ = 2.5–25.1°
b = 16.302 (2) Å	µ = 5.20 mm−1
c = 15.0376 (18) Å	T = 298 K
β = 97.624 (2)°	Block, dark green
V = 1962.8 (4) Å3	0.23 × 0.19 × 0.15 mm
Z = 4

Bruker SMART CCD diffractometer	3446 independent reflections
Radiation source: fine-focus sealed tube	2426 reflections with I > 2σ(I)
graphite	Rint = 0.034
ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→9
Tmin = 0.381, Tmax = 0.509	k = −17→19
8676 measured reflections	l = −17→11

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0396P)2] where P = (Fo2 + 2Fc2)/3
3446 reflections	(Δ/σ)max = 0.001
244 parameters	Δρmax = 0.94 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	0.63317 (6)	0.70295 (3)	0.15437 (3)	0.03541 (16)
Br1	0.63665 (6)	0.81344 (2)	0.05459 (3)	0.04420 (15)
Br2	0.92790 (7)	0.70189 (3)	0.24686 (4)	0.06244 (18)
N1	0.5874 (4)	0.53300 (18)	0.1785 (2)	0.0390 (9)
H1	0.5667	0.4870	0.2027	0.047*
N2	0.5516 (4)	0.60651 (17)	0.2140 (2)	0.0349 (8)
N3	0.5009 (4)	0.75634 (19)	0.2434 (2)	0.0347 (8)
O1	0.6872 (4)	0.60672 (14)	0.07174 (18)	0.0389 (7)
O2	0.5854 (4)	0.37576 (16)	0.1626 (2)	0.0585 (10)
H2	0.5800	0.3273	0.1765	0.088*
C1	0.6586 (5)	0.5380 (2)	0.1020 (3)	0.0337 (10)
C2	0.7003 (5)	0.4611 (2)	0.0589 (3)	0.0341 (10)
C3	0.6649 (5)	0.3826 (2)	0.0886 (3)	0.0392 (11)
C4	0.7099 (6)	0.3140 (2)	0.0427 (3)	0.0481 (12)
H4	0.6868	0.2618	0.0625	0.058*
C5	0.7887 (6)	0.3237 (3)	−0.0321 (3)	0.0523 (13)
H5	0.8161	0.2774	−0.0631	0.063*
C6	0.8283 (6)	0.3997 (3)	−0.0622 (3)	0.0530 (13)
H6	0.8842	0.4053	−0.1121	0.064*
C7	0.7826 (6)	0.4679 (2)	−0.0164 (3)	0.0453 (12)
H7	0.8076	0.5198	−0.0365	0.054*
C8	0.4677 (5)	0.6152 (2)	0.2817 (3)	0.0347 (10)
C9	0.4411 (5)	0.7033 (2)	0.3016 (3)	0.0330 (10)
C10	0.3652 (5)	0.7305 (2)	0.3723 (3)	0.0382 (11)
H10	0.3305	0.6934	0.4131	0.046*
C11	0.3407 (6)	0.8137 (2)	0.3823 (3)	0.0464 (12)
H11	0.2869	0.8332	0.4290	0.056*
C12	0.3965 (6)	0.8670 (2)	0.3226 (3)	0.0474 (12)
H12	0.3790	0.9232	0.3275	0.057*
C13	0.4786 (6)	0.8367 (2)	0.2553 (3)	0.0441 (12)
H13	0.5204	0.8735	0.2166	0.053*
C14	0.4049 (5)	0.5474 (2)	0.3330 (3)	0.0323 (10)
C15	0.2398 (5)	0.5486 (2)	0.3512 (3)	0.0410 (11)
H15	0.1692	0.5914	0.3300	0.049*
C16	0.1819 (6)	0.4863 (2)	0.4004 (3)	0.0466 (12)
H16	0.0725	0.4878	0.4133	0.056*
C17	0.2839 (6)	0.4219 (3)	0.4306 (3)	0.0530 (13)
H17	0.2435	0.3798	0.4634	0.064*
C18	0.4474 (6)	0.4201 (3)	0.4120 (3)	0.0520 (13)
H18	0.5165	0.3763	0.4319	0.062*
C19	0.5076 (5)	0.4825 (2)	0.3643 (3)	0.0428 (11)
H19	0.6180	0.4814	0.3529	0.051*

	U11	U22	U33	U12	U13	U23
Cu1	0.0471 (3)	0.0269 (3)	0.0353 (3)	0.0016 (2)	0.0168 (3)	0.0001 (2)
Br1	0.0552 (3)	0.0367 (2)	0.0453 (3)	0.0031 (2)	0.0238 (2)	0.0088 (2)
Br2	0.0575 (3)	0.0528 (3)	0.0716 (4)	0.0197 (2)	−0.0113 (3)	−0.0204 (3)
N1	0.057 (2)	0.0228 (17)	0.042 (2)	0.0029 (15)	0.0223 (19)	−0.0013 (15)
N2	0.048 (2)	0.0262 (18)	0.033 (2)	0.0023 (15)	0.0149 (18)	−0.0039 (15)
N3	0.041 (2)	0.0322 (19)	0.033 (2)	0.0046 (15)	0.0129 (17)	0.0022 (15)
O1	0.060 (2)	0.0265 (15)	0.0343 (18)	−0.0017 (13)	0.0203 (15)	−0.0002 (12)
O2	0.086 (3)	0.0286 (16)	0.068 (2)	−0.0033 (15)	0.038 (2)	0.0041 (15)
C1	0.038 (3)	0.034 (2)	0.031 (3)	0.0028 (18)	0.010 (2)	0.0000 (19)
C2	0.039 (3)	0.025 (2)	0.038 (3)	−0.0001 (17)	0.007 (2)	−0.0042 (18)
C3	0.042 (3)	0.031 (2)	0.046 (3)	−0.0022 (19)	0.009 (2)	−0.004 (2)
C4	0.053 (3)	0.026 (2)	0.066 (3)	−0.001 (2)	0.008 (3)	−0.004 (2)
C5	0.069 (4)	0.038 (3)	0.049 (3)	0.010 (2)	0.007 (3)	−0.014 (2)
C6	0.075 (4)	0.045 (3)	0.043 (3)	0.008 (2)	0.021 (3)	−0.009 (2)
C7	0.062 (3)	0.033 (2)	0.044 (3)	0.001 (2)	0.016 (3)	0.004 (2)
C8	0.034 (2)	0.034 (2)	0.036 (3)	−0.0020 (18)	0.005 (2)	−0.0017 (19)
C9	0.038 (3)	0.032 (2)	0.030 (2)	0.0024 (18)	0.009 (2)	0.0025 (18)
C10	0.049 (3)	0.036 (2)	0.033 (3)	−0.0011 (19)	0.016 (2)	−0.0008 (19)
C11	0.058 (3)	0.046 (3)	0.039 (3)	0.006 (2)	0.020 (2)	−0.006 (2)
C12	0.073 (4)	0.031 (2)	0.040 (3)	0.008 (2)	0.016 (3)	−0.002 (2)
C13	0.065 (3)	0.028 (2)	0.042 (3)	0.007 (2)	0.016 (3)	0.003 (2)
C14	0.040 (3)	0.030 (2)	0.029 (2)	0.0015 (18)	0.009 (2)	0.0044 (18)
C15	0.040 (3)	0.034 (2)	0.050 (3)	0.0055 (19)	0.009 (2)	0.001 (2)
C16	0.041 (3)	0.042 (3)	0.060 (3)	−0.009 (2)	0.020 (3)	−0.003 (2)
C17	0.071 (4)	0.039 (3)	0.052 (3)	−0.011 (2)	0.019 (3)	0.009 (2)
C18	0.066 (3)	0.037 (3)	0.054 (3)	0.011 (2)	0.014 (3)	0.015 (2)
C19	0.041 (3)	0.045 (3)	0.045 (3)	0.005 (2)	0.012 (2)	0.006 (2)

Cu1—N2	1.966 (3)	C6—H6	0.9300
Cu1—N3	2.018 (3)	C7—H7	0.9300
Cu1—O1	2.083 (2)	C8—C14	1.474 (5)
Cu1—Br1	2.3469 (6)	C8—C9	1.490 (5)
Cu1—Br2	2.5931 (8)	C9—C10	1.370 (5)
N1—C1	1.355 (5)	C10—C11	1.381 (5)
N1—N2	1.358 (4)	C10—H10	0.9300
N1—H1	0.8600	C11—C12	1.369 (6)
N2—C8	1.304 (5)	C11—H11	0.9300
N3—C13	1.338 (5)	C12—C13	1.373 (5)
N3—C9	1.363 (5)	C12—H12	0.9300
O1—C1	1.242 (4)	C13—H13	0.9300
O2—C3	1.361 (5)	C14—C19	1.388 (5)
O2—H2	0.8200	C14—C15	1.397 (5)
C1—C2	1.471 (5)	C15—C16	1.375 (5)
C2—C7	1.393 (5)	C15—H15	0.9300
C2—C3	1.396 (5)	C16—C17	1.374 (6)
C3—C4	1.388 (5)	C16—H16	0.9300
C4—C5	1.373 (6)	C17—C18	1.386 (6)
C4—H4	0.9300	C17—H17	0.9300
C5—C6	1.373 (6)	C18—C19	1.371 (5)
C5—H5	0.9300	C18—H18	0.9300
C6—C7	1.383 (5)	C19—H19	0.9300
N2—Cu1—N3	78.67 (12)	C6—C7—C2	121.9 (4)
N2—Cu1—O1	77.25 (11)	C6—C7—H7	119.0
N3—Cu1—O1	153.13 (12)	C2—C7—H7	119.0
N2—Cu1—Br1	159.76 (10)	N2—C8—C14	125.3 (3)
N3—Cu1—Br1	98.37 (9)	N2—C8—C9	111.4 (3)
O1—Cu1—Br1	100.10 (7)	C14—C8—C9	123.3 (3)
N2—Cu1—Br2	95.15 (10)	N3—C9—C10	121.8 (3)
N3—Cu1—Br2	100.15 (10)	N3—C9—C8	114.2 (3)
O1—Cu1—Br2	93.71 (8)	C10—C9—C8	124.0 (3)
Br1—Cu1—Br2	105.07 (2)	C9—C10—C11	119.2 (4)
C1—N1—N2	114.6 (3)	C9—C10—H10	120.4
C1—N1—H1	122.7	C11—C10—H10	120.4
N2—N1—H1	122.7	C12—C11—C10	119.2 (4)
C8—N2—N1	124.2 (3)	C12—C11—H11	120.4
C8—N2—Cu1	120.7 (2)	C10—C11—H11	120.4
N1—N2—Cu1	115.1 (2)	C11—C12—C13	119.2 (4)
C13—N3—C9	118.0 (3)	C11—C12—H12	120.4
C13—N3—Cu1	127.2 (3)	C13—C12—H12	120.4
C9—N3—Cu1	114.6 (2)	N3—C13—C12	122.6 (4)
C1—O1—Cu1	113.3 (2)	N3—C13—H13	118.7
C3—O2—H2	109.5	C12—C13—H13	118.7
O1—C1—N1	119.1 (3)	C19—C14—C15	119.2 (3)
O1—C1—C2	122.9 (4)	C19—C14—C8	121.1 (4)
N1—C1—C2	118.0 (3)	C15—C14—C8	119.7 (3)
C7—C2—C3	118.3 (4)	C16—C15—C14	119.8 (4)
C7—C2—C1	116.9 (3)	C16—C15—H15	120.1
C3—C2—C1	124.9 (4)	C14—C15—H15	120.1
O2—C3—C4	121.6 (4)	C17—C16—C15	120.7 (4)
O2—C3—C2	118.4 (3)	C17—C16—H16	119.7
C4—C3—C2	120.0 (4)	C15—C16—H16	119.7
C5—C4—C3	119.7 (4)	C16—C17—C18	119.7 (4)
C5—C4—H4	120.1	C16—C17—H17	120.1
C3—C4—H4	120.1	C18—C17—H17	120.1
C4—C5—C6	121.9 (4)	C19—C18—C17	120.2 (4)
C4—C5—H5	119.1	C19—C18—H18	119.9
C6—C5—H5	119.1	C17—C18—H18	119.9
C5—C6—C7	118.2 (4)	C18—C19—C14	120.4 (4)
C5—C6—H6	120.9	C18—C19—H19	119.8
C7—C6—H6	120.9	C14—C19—H19	119.8
C1—N1—N2—C8	172.6 (4)	C3—C4—C5—C6	1.5 (8)
C1—N1—N2—Cu1	−6.5 (4)	C4—C5—C6—C7	−1.7 (8)
N3—Cu1—N2—C8	−4.6 (3)	C5—C6—C7—C2	0.7 (7)
O1—Cu1—N2—C8	−172.6 (3)	C3—C2—C7—C6	0.5 (7)
Br1—Cu1—N2—C8	−88.0 (4)	C1—C2—C7—C6	179.9 (4)
Br2—Cu1—N2—C8	94.8 (3)	N1—N2—C8—C14	2.8 (6)
N3—Cu1—N2—N1	174.6 (3)	Cu1—N2—C8—C14	−178.1 (3)
O1—Cu1—N2—N1	6.6 (3)	N1—N2—C8—C9	−176.9 (4)
Br1—Cu1—N2—N1	91.2 (4)	Cu1—N2—C8—C9	2.2 (5)
Br2—Cu1—N2—N1	−86.1 (3)	C13—N3—C9—C10	−2.2 (6)
N2—Cu1—N3—C13	−179.8 (4)	Cu1—N3—C9—C10	172.6 (3)
O1—Cu1—N3—C13	−153.1 (3)	C13—N3—C9—C8	178.5 (4)
Br1—Cu1—N3—C13	−20.1 (4)	Cu1—N3—C9—C8	−6.8 (4)
Br2—Cu1—N3—C13	87.0 (3)	N2—C8—C9—N3	3.1 (5)
N2—Cu1—N3—C9	6.0 (3)	C14—C8—C9—N3	−176.6 (4)
O1—Cu1—N3—C9	32.7 (5)	N2—C8—C9—C10	−176.2 (4)
Br1—Cu1—N3—C9	165.7 (3)	C14—C8—C9—C10	4.1 (7)
Br2—Cu1—N3—C9	−87.2 (3)	N3—C9—C10—C11	3.4 (7)
N2—Cu1—O1—C1	−6.0 (3)	C8—C9—C10—C11	−177.3 (4)
N3—Cu1—O1—C1	−32.8 (5)	C9—C10—C11—C12	−1.6 (7)
Br1—Cu1—O1—C1	−165.6 (3)	C10—C11—C12—C13	−1.4 (7)
Br2—Cu1—O1—C1	88.4 (3)	C9—N3—C13—C12	−0.9 (6)
Cu1—O1—C1—N1	4.5 (5)	Cu1—N3—C13—C12	−174.9 (3)
Cu1—O1—C1—C2	−174.8 (3)	C11—C12—C13—N3	2.7 (7)
N2—N1—C1—O1	1.1 (6)	N2—C8—C14—C19	48.2 (6)
N2—N1—C1—C2	−179.6 (3)	C9—C8—C14—C19	−132.1 (4)
O1—C1—C2—C7	3.1 (6)	N2—C8—C14—C15	−132.3 (4)
N1—C1—C2—C7	−176.1 (4)	C9—C8—C14—C15	47.4 (6)
O1—C1—C2—C3	−177.5 (4)	C19—C14—C15—C16	0.7 (6)
N1—C1—C2—C3	3.2 (6)	C8—C14—C15—C16	−178.8 (4)
C7—C2—C3—O2	179.6 (4)	C14—C15—C16—C17	−1.2 (7)
C1—C2—C3—O2	0.3 (6)	C15—C16—C17—C18	0.5 (7)
C7—C2—C3—C4	−0.7 (7)	C16—C17—C18—C19	0.6 (7)
C1—C2—C3—C4	180.0 (4)	C17—C18—C19—C14	−1.1 (7)
O2—C3—C4—C5	179.5 (4)	C15—C14—C19—C18	0.4 (7)
C2—C3—C4—C5	−0.2 (7)	C8—C14—C19—C18	179.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.86	1.92	2.574 (4)	131
O2—H2···Br2i	0.82	2.35	3.153 (3)	166
C11—H11···O1ii	0.93	2.58	3.503 (5)	170
C10—H10···Br1ii	0.93	2.81	3.575 (4)	141
C15—H15···Br2iii	0.93	2.82	3.742 (4)	171

Table 1

Selected bond lengths (Å)

Cu1—N2	1.966 (3)
Cu1—N3	2.018 (3)
Cu1—O1	2.083 (2)
Cu1—Br1	2.3469 (6)
Cu1—Br2	2.5931 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.86	1.92	2.574 (4)	131
O2—H2⋯Br2i	0.82	2.35	3.153 (3)	166
C11—H11⋯O1ii	0.93	2.58	3.503 (5)	170
C10—H10⋯Br1ii	0.93	2.81	3.575 (4)	141
C15—H15⋯Br2iii	0.93	2.82	3.742 (4)	171

Symmetry codes: (i) ; (ii) ; (iii) .