Di-chlorido-{2-[(E)-phen-yl(pyridin-2-yl-κN)methyl-idene]-N-phenyl-hydra-zine-carboxamide-κ(2) N (2),O}copper(II).

The title compound, [CuCl2(C19H16N4O)], contains a Cu(II) atom N,N',O-chelated by a neutral N-phenyl-hy-dra-zine-car-box-amide ligand and additionally coordinated by two Cl atoms, resulting in a distorted square-pyramidal geometry. The ligating atoms in the basal square plane of the complex comprise the azomethine N, the pyridine N, the amide O and one of the Cl atoms, whereas the other Cl atom occupies an apical position. The apical Cl atoms in adjacent layers function as hydrogen-bond acceptors to both NH groups. Intermolecular C-H⋯Cl and C-H⋯O interactions are also observed.

Related literature

For the biological applications of hydrazinecarboxamide and its derivatives, see: Beraldo & Gambino (2004 ▶); Kasuga et al. (2006 ▶); Rivadeneira et al. (2009 ▶); Shalini et al. (2009 ▶); Rodriguez-Arguelles et al. (2010 ▶). For the synthesis of related compounds, see: Kurup et al. (2011 ▶). For related structures, see: Kunnath et al. (2012 ▶). For the calculation of the trigonality index, see: Addison et al. (1984 ▶). For the graph-set notation, see: Etter et al. (1990 ▶).

Experimental

Crystal data

[CuCl2(C19H16N4O)]

M = 450.81

Triclinic,

a = 9.4483 (5) Å

b = 9.8197 (3) Å

c = 11.5307 (4) Å

α = 104.067 (1)°

β = 103.026 (1)°

γ = 100.475 (1)°

V = 978.83 (7) Å3

Z = 2

Mo Kα radiation

μ = 1.41 mm−1

T = 293 K

0.35 × 0.32 × 0.30 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.614, T max = 0.649

7149 measured reflections

4411 independent reflections

3550 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.092

S = 1.01

4411 reflections

252 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.34 e Å−3

Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2/SAINT (Bruker, 2004 ▶); data reduction: SAINT/XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXL97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813026883/fj2644sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813026883/fj2644Isup2.hkl

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

[CuCl2(C19H16N4O)]	Z = 2
Mr = 450.81	F(000) = 458
Triclinic, P1	Dx = 1.530 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4483 (5) Å	Cell parameters from 3151 reflections
b = 9.8197 (3) Å	θ = 2.5–27.7°
c = 11.5307 (4) Å	µ = 1.41 mm−1
α = 104.067 (1)°	T = 293 K
β = 103.026 (1)°	Block, green
γ = 100.475 (1)°	0.35 × 0.32 × 0.30 mm
V = 978.83 (7) Å3

Bruker Kappa APEXII CCD diffractometer	4411 independent reflections
Radiation source: fine-focus sealed tube	3550 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 8.33 pixels mm-1	θmax = 27.5°, θmin = 3.3°
ω and φ scan	h = −9→12
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −12→12
Tmin = 0.614, Tmax = 0.649	l = −14→14
7149 measured reflections

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) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0429P)2 + 0.3399P] where P = (Fo2 + 2Fc2)/3
4411 reflections	(Δ/σ)max = 0.001
252 parameters	Δρmax = 0.34 e Å−3
2 restraints	Δρmin = −0.40 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	0.56784 (3)	0.81865 (3)	0.45210 (3)	0.04217 (10)
Cl1	0.68970 (7)	0.63456 (5)	0.34892 (5)	0.04308 (14)
Cl2	0.54712 (10)	0.95006 (8)	0.32265 (7)	0.0657 (2)
O1	0.35179 (18)	0.68219 (17)	0.38879 (14)	0.0435 (4)
N1	0.7528 (2)	0.9491 (2)	0.5849 (2)	0.0474 (5)
N2	0.5556 (2)	0.74344 (17)	0.59382 (16)	0.0343 (4)
N3	0.4287 (2)	0.64128 (19)	0.57491 (17)	0.0385 (4)
H3'	0.418 (3)	0.593 (2)	0.625 (2)	0.048 (7)*
N4	0.2064 (2)	0.5040 (2)	0.43869 (19)	0.0459 (5)
C1	0.8558 (4)	1.0534 (3)	0.5712 (3)	0.0691 (9)
H1	0.8419	1.0733	0.4952	0.083*
C2	0.9811 (4)	1.1309 (4)	0.6673 (5)	0.0930 (12)
H2	1.0514	1.2026	0.6563	0.112*
C3	1.0019 (4)	1.1029 (4)	0.7775 (4)	0.0938 (12)
H3	1.0865	1.1555	0.8431	0.113*
C4	0.8967 (3)	0.9953 (3)	0.7934 (3)	0.0712 (8)
H4	0.9098	0.9743	0.8690	0.085*
C5	0.7732 (3)	0.9209 (2)	0.6946 (2)	0.0450 (5)
C6	0.6523 (2)	0.8054 (2)	0.7004 (2)	0.0358 (4)
C7	0.6428 (2)	0.7762 (2)	0.81791 (19)	0.0381 (5)
C8	0.6340 (3)	0.8871 (3)	0.9153 (2)	0.0500 (6)
H8	0.6375	0.9793	0.9066	0.060*
C9	0.6203 (3)	0.8607 (3)	1.0242 (2)	0.0596 (7)
H9	0.6128	0.9348	1.0884	0.071*
C10	0.6176 (3)	0.7256 (3)	1.0393 (2)	0.0587 (7)
H10	0.6090	0.7088	1.1137	0.070*
C11	0.6275 (3)	0.6155 (3)	0.9440 (2)	0.0564 (7)
H11	0.6263	0.5244	0.9544	0.068*
C12	0.6394 (3)	0.6395 (3)	0.8329 (2)	0.0458 (5)
H12	0.6450	0.5644	0.7684	0.055*
C13	0.3276 (2)	0.6125 (2)	0.46062 (19)	0.0364 (5)
C14	0.0774 (3)	0.4486 (3)	0.3355 (2)	0.0467 (5)
C15	−0.0277 (3)	0.3329 (3)	0.3403 (3)	0.0649 (8)
H15	−0.0097	0.2966	0.4081	0.078*
C16	−0.1589 (4)	0.2715 (4)	0.2447 (4)	0.0832 (10)
H16	−0.2297	0.1949	0.2488	0.100*
C17	−0.1846 (4)	0.3227 (5)	0.1446 (4)	0.0988 (13)
H17	−0.2719	0.2796	0.0793	0.119*
C18	−0.0819 (4)	0.4383 (5)	0.1398 (4)	0.0940 (12)
H18	−0.1011	0.4743	0.0719	0.113*
C19	0.0509 (3)	0.5020 (3)	0.2357 (3)	0.0664 (8)
H19	0.1206	0.5798	0.2319	0.080*
H4'	0.210 (3)	0.465 (3)	0.496 (2)	0.050 (8)*

	U11	U22	U33	U12	U13	U23
Cu1	0.05420 (19)	0.03721 (16)	0.04289 (17)	0.00880 (12)	0.02232 (13)	0.01988 (12)
Cl1	0.0519 (3)	0.0338 (3)	0.0490 (3)	0.0081 (2)	0.0230 (3)	0.0161 (2)
Cl2	0.0992 (6)	0.0637 (4)	0.0735 (4)	0.0432 (4)	0.0528 (4)	0.0476 (4)
O1	0.0447 (9)	0.0477 (9)	0.0384 (8)	0.0059 (7)	0.0103 (7)	0.0190 (7)
N1	0.0500 (12)	0.0343 (9)	0.0629 (13)	0.0037 (9)	0.0314 (10)	0.0142 (9)
N2	0.0371 (10)	0.0284 (8)	0.0358 (9)	0.0010 (7)	0.0125 (8)	0.0099 (7)
N3	0.0438 (11)	0.0336 (9)	0.0337 (9)	−0.0034 (8)	0.0093 (8)	0.0135 (7)
N4	0.0431 (11)	0.0439 (11)	0.0445 (11)	−0.0019 (9)	0.0069 (9)	0.0167 (9)
C1	0.069 (2)	0.0500 (15)	0.102 (2)	0.0047 (14)	0.0523 (19)	0.0291 (15)
C2	0.057 (2)	0.063 (2)	0.156 (4)	−0.0107 (16)	0.044 (2)	0.033 (2)
C3	0.0433 (18)	0.080 (2)	0.129 (3)	−0.0197 (16)	0.004 (2)	0.024 (2)
C4	0.0431 (16)	0.0650 (18)	0.087 (2)	−0.0045 (13)	0.0021 (15)	0.0175 (16)
C5	0.0352 (12)	0.0374 (11)	0.0601 (15)	0.0044 (9)	0.0168 (11)	0.0107 (10)
C6	0.0362 (11)	0.0304 (10)	0.0405 (11)	0.0067 (8)	0.0133 (9)	0.0089 (8)
C7	0.0337 (11)	0.0398 (11)	0.0348 (11)	0.0055 (9)	0.0043 (9)	0.0081 (9)
C8	0.0583 (16)	0.0470 (13)	0.0391 (12)	0.0146 (12)	0.0068 (11)	0.0080 (10)
C9	0.0671 (19)	0.0687 (18)	0.0319 (12)	0.0138 (14)	0.0067 (12)	0.0041 (11)
C10	0.0535 (16)	0.081 (2)	0.0347 (12)	0.0047 (14)	0.0041 (11)	0.0220 (13)
C11	0.0546 (16)	0.0560 (15)	0.0559 (15)	0.0024 (12)	0.0057 (12)	0.0291 (13)
C12	0.0495 (14)	0.0413 (12)	0.0434 (12)	0.0069 (10)	0.0105 (11)	0.0124 (10)
C13	0.0398 (12)	0.0319 (10)	0.0367 (11)	0.0070 (9)	0.0122 (9)	0.0089 (8)
C14	0.0369 (13)	0.0430 (12)	0.0529 (14)	0.0084 (10)	0.0097 (11)	0.0049 (10)
C15	0.0482 (16)	0.0527 (15)	0.080 (2)	−0.0010 (13)	0.0132 (14)	0.0086 (14)
C16	0.0487 (18)	0.070 (2)	0.099 (3)	−0.0065 (15)	0.0032 (18)	−0.0016 (19)
C17	0.051 (2)	0.099 (3)	0.099 (3)	0.0014 (19)	−0.0168 (19)	−0.008 (2)
C18	0.072 (2)	0.114 (3)	0.077 (2)	0.022 (2)	−0.0126 (19)	0.026 (2)
C19	0.0487 (16)	0.0738 (19)	0.0654 (18)	0.0083 (14)	−0.0001 (13)	0.0205 (15)

Cu1—N2	1.9672 (16)	C6—C7	1.470 (3)
Cu1—N1	2.016 (2)	C7—C12	1.390 (3)
Cu1—O1	2.0865 (16)	C7—C8	1.391 (3)
Cu1—Cl2	2.1973 (6)	C8—C9	1.370 (4)
Cu1—Cl1	2.5175 (6)	C8—H8	0.9300
O1—C13	1.229 (3)	C9—C10	1.376 (4)
N1—C5	1.339 (3)	C9—H9	0.9300
N1—C1	1.344 (3)	C10—C11	1.375 (4)
N2—C6	1.282 (3)	C10—H10	0.9300
N2—N3	1.352 (2)	C11—C12	1.383 (3)
N3—C13	1.372 (3)	C11—H11	0.9300
N3—H3'	0.846 (16)	C12—H12	0.9300
N4—C13	1.343 (3)	C14—C19	1.369 (4)
N4—C14	1.410 (3)	C14—C15	1.388 (4)
N4—H4'	0.833 (16)	C15—C16	1.380 (4)
C1—C2	1.371 (5)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.358 (5)
C2—C3	1.344 (6)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.374 (6)
C3—C4	1.389 (4)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.393 (4)
C4—C5	1.371 (4)	C18—H18	0.9300
C4—H4	0.9300	C19—H19	0.9300
C5—C6	1.483 (3)
N2—Cu1—N1	78.70 (7)	C7—C6—C5	122.45 (19)
N2—Cu1—O1	77.84 (6)	C12—C7—C8	119.4 (2)
N1—Cu1—O1	154.03 (7)	C12—C7—C6	121.4 (2)
N2—Cu1—Cl2	162.21 (6)	C8—C7—C6	119.2 (2)
N1—Cu1—Cl2	99.08 (6)	C9—C8—C7	120.0 (2)
O1—Cu1—Cl2	99.86 (5)	C9—C8—H8	120.0
N2—Cu1—Cl1	96.69 (5)	C7—C8—H8	120.0
N1—Cu1—Cl1	97.98 (6)	C8—C9—C10	120.7 (2)
O1—Cu1—Cl1	95.64 (5)	C8—C9—H9	119.6
Cl2—Cu1—Cl1	101.09 (2)	C10—C9—H9	119.6
C13—O1—Cu1	112.00 (14)	C11—C10—C9	119.7 (2)
C5—N1—C1	119.2 (3)	C11—C10—H10	120.1
C5—N1—Cu1	114.21 (15)	C9—C10—H10	120.1
C1—N1—Cu1	126.5 (2)	C10—C11—C12	120.5 (2)
C6—N2—N3	123.84 (17)	C10—C11—H11	119.8
C6—N2—Cu1	120.05 (14)	C12—C11—H11	119.8
N3—N2—Cu1	115.29 (13)	C11—C12—C7	119.7 (2)
N2—N3—C13	113.53 (17)	C11—C12—H12	120.1
N2—N3—H3'	122.5 (18)	C7—C12—H12	120.1
C13—N3—H3'	123.5 (18)	O1—C13—N4	125.9 (2)
C13—N4—C14	129.7 (2)	O1—C13—N3	120.75 (19)
C13—N4—H4'	113.5 (19)	N4—C13—N3	113.39 (19)
C14—N4—H4'	116.8 (19)	C19—C14—C15	119.9 (3)
N1—C1—C2	121.2 (3)	C19—C14—N4	124.6 (2)
N1—C1—H1	119.4	C15—C14—N4	115.5 (2)
C2—C1—H1	119.4	C16—C15—C14	120.2 (3)
C3—C2—C1	119.8 (3)	C16—C15—H15	119.9
C3—C2—H2	120.1	C14—C15—H15	119.9
C1—C2—H2	120.1	C17—C16—C15	120.1 (3)
C2—C3—C4	119.9 (3)	C17—C16—H16	120.0
C2—C3—H3	120.1	C15—C16—H16	120.0
C4—C3—H3	120.1	C16—C17—C18	120.1 (3)
C5—C4—C3	118.2 (3)	C16—C17—H17	120.0
C5—C4—H4	120.9	C18—C17—H17	120.0
C3—C4—H4	120.9	C17—C18—C19	120.6 (4)
N1—C5—C4	121.8 (2)	C17—C18—H18	119.7
N1—C5—C6	114.9 (2)	C19—C18—H18	119.7
C4—C5—C6	123.3 (2)	C14—C19—C18	119.1 (3)
N2—C6—C7	125.61 (19)	C14—C19—H19	120.4
N2—C6—C5	111.80 (19)	C18—C19—H19	120.4
N2—Cu1—O1—C13	−6.89 (15)	N3—N2—C6—C5	−175.36 (19)
N1—Cu1—O1—C13	−32.7 (3)	Cu1—N2—C6—C5	−6.2 (2)
Cl2—Cu1—O1—C13	−168.91 (14)	N1—C5—C6—N2	6.1 (3)
Cl1—Cu1—O1—C13	88.77 (15)	C4—C5—C6—N2	−174.4 (2)
N2—Cu1—N1—C5	0.20 (16)	N1—C5—C6—C7	−169.7 (2)
O1—Cu1—N1—C5	25.9 (3)	C4—C5—C6—C7	9.7 (4)
Cl2—Cu1—N1—C5	162.26 (16)	N2—C6—C7—C12	61.0 (3)
Cl1—Cu1—N1—C5	−95.08 (16)	C5—C6—C7—C12	−123.7 (2)
N2—Cu1—N1—C1	177.3 (2)	N2—C6—C7—C8	−117.7 (3)
O1—Cu1—N1—C1	−157.0 (2)	C5—C6—C7—C8	57.6 (3)
Cl2—Cu1—N1—C1	−20.6 (2)	C12—C7—C8—C9	−0.8 (4)
Cl1—Cu1—N1—C1	82.0 (2)	C6—C7—C8—C9	177.9 (2)
N1—Cu1—N2—C6	3.66 (16)	C7—C8—C9—C10	1.1 (4)
O1—Cu1—N2—C6	−165.14 (18)	C8—C9—C10—C11	−0.5 (4)
Cl2—Cu1—N2—C6	−80.8 (3)	C9—C10—C11—C12	−0.4 (4)
Cl1—Cu1—N2—C6	100.51 (16)	C10—C11—C12—C7	0.7 (4)
N1—Cu1—N2—N3	173.68 (16)	C8—C7—C12—C11	−0.1 (4)
O1—Cu1—N2—N3	4.88 (14)	C6—C7—C12—C11	−178.8 (2)
Cl2—Cu1—N2—N3	89.2 (2)	Cu1—O1—C13—N4	−171.66 (19)
Cl1—Cu1—N2—N3	−89.48 (14)	Cu1—O1—C13—N3	8.0 (3)
C6—N2—N3—C13	167.1 (2)	C14—N4—C13—O1	−3.4 (4)
Cu1—N2—N3—C13	−2.5 (2)	C14—N4—C13—N3	176.9 (2)
C5—N1—C1—C2	0.1 (4)	N2—N3—C13—O1	−4.0 (3)
Cu1—N1—C1—C2	−176.9 (2)	N2—N3—C13—N4	175.67 (19)
N1—C1—C2—C3	−0.1 (6)	C13—N4—C14—C19	−1.9 (4)
C1—C2—C3—C4	0.2 (6)	C13—N4—C14—C15	178.9 (3)
C2—C3—C4—C5	−0.3 (6)	C19—C14—C15—C16	0.0 (5)
C1—N1—C5—C4	−0.2 (4)	N4—C14—C15—C16	179.3 (3)
Cu1—N1—C5—C4	177.2 (2)	C14—C15—C16—C17	1.0 (5)
C1—N1—C5—C6	179.3 (2)	C15—C16—C17—C18	−1.7 (6)
Cu1—N1—C5—C6	−3.4 (3)	C16—C17—C18—C19	1.4 (7)
C3—C4—C5—N1	0.3 (5)	C15—C14—C19—C18	−0.3 (5)
C3—C4—C5—C6	−179.1 (3)	N4—C14—C19—C18	−179.5 (3)
N3—N2—C6—C7	0.4 (3)	C17—C18—C19—C14	−0.4 (6)
Cu1—N2—C6—C7	169.48 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3′···Cl1i	0.85 (2)	2.40 (2)	3.1397 (18)	147 (2)
N4—H4′···Cl1i	0.83 (2)	2.35 (2)	3.136 (2)	159 (2)
C2—H2···Cl1ii	0.93	2.69	3.589 (4)	163
C19—H19···O1	0.93	2.36	2.953 (4)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3′⋯Cl1i	0.85 (2)	2.40 (2)	3.1397 (18)	147 (2)
N4—H4′⋯Cl1i	0.83 (2)	2.35 (2)	3.136 (2)	159 (2)
C2—H2⋯Cl1ii	0.93	2.69	3.589 (4)	163
C19—H19⋯O1	0.93	2.36	2.953 (4)	121

Symmetry codes: (i) ; (ii) .