Dichlorido{N'-[1-(2-pyridin-2-yl)ethyl-idene]acetohydrazide-κN',O}copper(II).

In the title compound, [CuCl(2)(C(9)H(11)N(3)O)], the Cu(II) atom is in a distorted square-pyramidal CuCl(2)N(2)O coordination geometry. The tridentate acetohydrazide ligand chelates in a meridional fashion. The chloride ligand in the axial position forms a long Cu-Cl distance of 2.4892 (9) Å. In contrast, the Cu-Cl distance from the equatorial chloride ligand is much shorter [2.2110 (7) Å]. Inter-molecular N-H⋯Cl and C-H⋯Cl hydrogen bonds link the complexes into a three-dimensional network.

Related literature

For a related copper(II) complex with a similar tridentate ligand, see: Recio Despaigne et al. (2009 ▶).

Experimental

Crystal data

[CuCl2(C9H11N3O)]

M = 311.65

Monoclinic,

a = 6.6501 (15) Å

b = 15.680 (3) Å

c = 13.103 (2) Å

β = 118.769 (12)°

V = 1197.7 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.25 mm−1

T = 150 K

0.25 × 0.20 × 0.19 mm

Data collection

Bruker SMART APEXII diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T min = 0.603, T max = 0.674

16039 measured reflections

3081 independent reflections

2534 reflections with I > 2.0σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.075

S = 1.02

3081 reflections

147 parameters

H-atom parameters constrained

Δρmax = 0.51 e Å−3

Δρmin = −0.54 e Å−3

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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: DIAMOND (Brandenburg, 2006 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053195/pv2372sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053195/pv2372Isup2.hkl

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

[CuCl2(C9H11N3O)]	F(000) = 628
Mr = 311.65	Dx = 1.728 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6047 reflections
a = 6.6501 (15) Å	θ = 2.2–27.7°
b = 15.680 (3) Å	µ = 2.25 mm−1
c = 13.103 (2) Å	T = 150 K
β = 118.769 (12)°	Prism, green
V = 1197.7 (4) Å3	0.25 × 0.20 × 0.19 mm
Z = 4

Bruker SMART APEXII diffractometer	3081 independent reflections
Radiation source: fine-focus sealed tube	2534 reflections with I > 2.0σ(I)
graphite	Rint = 0.027
ω scans	θmax = 28.8°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −7→8
Tmin = 0.603, Tmax = 0.674	k = −21→21
16039 measured reflections	l = −17→17

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0302P)2 + 1.0145P] where P = (Fo2 + 2Fc2)/3
3081 reflections	(Δ/σ)max = 0.001
147 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.54 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	0.95537 (5)	0.835509 (17)	0.19694 (2)	0.03082 (9)
Cl1	0.77693 (11)	0.94146 (4)	0.23143 (6)	0.04312 (15)
Cl2	1.30421 (10)	0.81769 (4)	0.38962 (5)	0.04150 (15)
O1	1.0897 (3)	0.90737 (10)	0.11255 (15)	0.0412 (4)
N1	1.1191 (3)	0.77854 (12)	0.04581 (16)	0.0331 (4)
H1	1.1581	0.7462	0.0018	0.040*
N2	1.0103 (3)	0.74896 (11)	0.10466 (15)	0.0293 (4)
N3	0.7804 (3)	0.73440 (12)	0.21178 (16)	0.0324 (4)
C1	1.2447 (5)	0.90327 (18)	−0.0185 (2)	0.0453 (6)
H1A	1.3934	0.9294	0.0333	0.068*
H1B	1.1393	0.9470	−0.0699	0.068*
H1C	1.2651	0.8590	−0.0656	0.068*
C2	1.1484 (4)	0.86451 (15)	0.05182 (19)	0.0335 (5)
C3	0.9627 (5)	0.60109 (15)	0.0319 (2)	0.0457 (6)
H3A	1.0562	0.6197	−0.0033	0.069*
H3B	0.8111	0.5834	−0.0295	0.069*
H3C	1.0380	0.5529	0.0842	0.069*
C4	0.9369 (4)	0.67248 (13)	0.09883 (18)	0.0304 (4)
C5	0.8118 (4)	0.66154 (14)	0.16587 (19)	0.0309 (4)
C6	0.7298 (4)	0.58379 (16)	0.1791 (2)	0.0424 (6)
H6	0.7534	0.5334	0.1460	0.051*
C7	0.6118 (5)	0.58128 (19)	0.2426 (3)	0.0532 (7)
H7	0.5566	0.5286	0.2551	0.064*
C8	0.5757 (5)	0.6552 (2)	0.2867 (3)	0.0529 (7)
H8	0.4916	0.6546	0.3282	0.063*
C9	0.6626 (4)	0.73087 (18)	0.2702 (2)	0.0425 (6)
H9	0.6377	0.7820	0.3015	0.051*

	U11	U22	U33	U12	U13	U23
Cu1	0.03910 (16)	0.02660 (14)	0.03380 (15)	0.00029 (11)	0.02316 (12)	−0.00381 (11)
Cl1	0.0510 (4)	0.0394 (3)	0.0457 (3)	0.0123 (3)	0.0286 (3)	−0.0023 (2)
Cl2	0.0372 (3)	0.0551 (4)	0.0348 (3)	−0.0009 (3)	0.0194 (2)	0.0016 (3)
O1	0.0604 (11)	0.0295 (8)	0.0477 (10)	−0.0026 (7)	0.0372 (9)	−0.0024 (7)
N1	0.0447 (11)	0.0317 (9)	0.0341 (10)	0.0001 (8)	0.0280 (9)	−0.0009 (8)
N2	0.0362 (9)	0.0288 (9)	0.0295 (9)	0.0012 (7)	0.0211 (8)	−0.0011 (7)
N3	0.0328 (9)	0.0363 (10)	0.0328 (9)	−0.0008 (8)	0.0196 (8)	−0.0005 (8)
C1	0.0559 (16)	0.0463 (14)	0.0428 (13)	−0.0087 (12)	0.0310 (12)	0.0032 (11)
C2	0.0381 (12)	0.0335 (11)	0.0308 (11)	−0.0005 (9)	0.0180 (9)	0.0019 (9)
C3	0.0772 (19)	0.0281 (11)	0.0453 (14)	−0.0010 (12)	0.0402 (14)	−0.0053 (10)
C4	0.0382 (11)	0.0272 (10)	0.0275 (10)	0.0020 (9)	0.0173 (9)	0.0001 (8)
C5	0.0311 (10)	0.0319 (11)	0.0285 (10)	−0.0003 (9)	0.0134 (8)	0.0004 (9)
C6	0.0414 (13)	0.0364 (13)	0.0509 (14)	−0.0033 (10)	0.0234 (11)	0.0045 (11)
C7	0.0456 (15)	0.0498 (16)	0.0685 (19)	−0.0052 (12)	0.0309 (14)	0.0175 (14)
C8	0.0440 (15)	0.067 (2)	0.0615 (18)	0.0006 (13)	0.0366 (14)	0.0145 (15)
C9	0.0393 (13)	0.0541 (16)	0.0443 (14)	0.0026 (11)	0.0282 (11)	0.0022 (12)

Cu1—N2	1.9653 (18)	C1—H1C	0.9800
Cu1—N3	2.0305 (19)	C3—C4	1.482 (3)
Cu1—O1	2.0592 (17)	C3—H3A	0.9800
Cu1—Cl1	2.2110 (7)	C3—H3B	0.9800
Cu1—Cl2	2.4892 (9)	C3—H3C	0.9800
O1—C2	1.240 (3)	C4—C5	1.482 (3)
N1—C2	1.359 (3)	C5—C6	1.380 (3)
N1—N2	1.367 (3)	C6—C7	1.392 (4)
N1—H1	0.8900	C6—H6	0.9500
N2—C4	1.283 (3)	C7—C8	1.367 (4)
N3—C9	1.334 (3)	C7—H7	0.9500
N3—C5	1.353 (3)	C8—C9	1.381 (4)
C1—C2	1.483 (3)	C8—H8	0.9500
C1—H1A	0.9800	C9—H9	0.9500
C1—H1B	0.9800
N2—Cu1—N3	78.73 (8)	O1—C2—C1	122.7 (2)
N2—Cu1—O1	77.90 (7)	N1—C2—C1	117.6 (2)
N3—Cu1—O1	153.54 (7)	C4—C3—H3A	109.5
N2—Cu1—Cl1	157.16 (6)	C4—C3—H3B	109.5
N3—Cu1—Cl1	100.28 (6)	H3A—C3—H3B	109.5
O1—Cu1—Cl1	96.47 (5)	C4—C3—H3C	109.5
N2—Cu1—Cl2	100.84 (6)	H3A—C3—H3C	109.5
N3—Cu1—Cl2	96.46 (6)	H3B—C3—H3C	109.5
O1—Cu1—Cl2	99.95 (6)	N2—C4—C3	126.3 (2)
Cl1—Cu1—Cl2	101.94 (3)	N2—C4—C5	112.26 (19)
C2—O1—Cu1	113.58 (15)	C3—C4—C5	121.4 (2)
C2—N1—N2	113.82 (18)	N3—C5—C6	122.3 (2)
C2—N1—H1	121.4	N3—C5—C4	114.61 (19)
N2—N1—H1	124.6	C6—C5—C4	123.0 (2)
C4—N2—N1	124.94 (19)	C5—C6—C7	118.1 (3)
C4—N2—Cu1	120.27 (15)	C5—C6—H6	121.0
N1—N2—Cu1	114.72 (14)	C7—C6—H6	121.0
C9—N3—C5	118.6 (2)	C8—C7—C6	119.5 (3)
C9—N3—Cu1	127.53 (18)	C8—C7—H7	120.2
C5—N3—Cu1	113.48 (15)	C6—C7—H7	120.2
C2—C1—H1A	109.5	C7—C8—C9	119.4 (3)
C2—C1—H1B	109.5	C7—C8—H8	120.3
H1A—C1—H1B	109.5	C9—C8—H8	120.3
C2—C1—H1C	109.5	N3—C9—C8	122.0 (3)
H1A—C1—H1C	109.5	N3—C9—H9	119.0
H1B—C1—H1C	109.5	C8—C9—H9	119.0
O1—C2—N1	119.6 (2)
N2—Cu1—O1—C2	−3.14 (17)	Cu1—O1—C2—C1	178.65 (18)
N3—Cu1—O1—C2	−31.6 (3)	N2—N1—C2—O1	4.0 (3)
Cl1—Cu1—O1—C2	−160.69 (16)	N2—N1—C2—C1	−174.3 (2)
Cl2—Cu1—O1—C2	95.94 (17)	N1—N2—C4—C3	2.5 (4)
C2—N1—N2—C4	170.3 (2)	Cu1—N2—C4—C3	179.18 (19)
C2—N1—N2—Cu1	−6.6 (2)	N1—N2—C4—C5	−175.88 (19)
N3—Cu1—N2—C4	−4.33 (17)	Cu1—N2—C4—C5	0.8 (3)
O1—Cu1—N2—C4	−171.84 (19)	C9—N3—C5—C6	−1.2 (3)
Cl1—Cu1—N2—C4	−94.1 (2)	Cu1—N3—C5—C6	172.25 (18)
Cl2—Cu1—N2—C4	90.18 (17)	C9—N3—C5—C4	177.8 (2)
N3—Cu1—N2—N1	172.68 (16)	Cu1—N3—C5—C4	−8.8 (2)
O1—Cu1—N2—N1	5.18 (14)	N2—C4—C5—N3	5.4 (3)
Cl1—Cu1—N2—N1	82.9 (2)	C3—C4—C5—N3	−173.0 (2)
Cl2—Cu1—N2—N1	−92.80 (14)	N2—C4—C5—C6	−175.6 (2)
N2—Cu1—N3—C9	179.8 (2)	C3—C4—C5—C6	5.9 (4)
O1—Cu1—N3—C9	−151.88 (19)	N3—C5—C6—C7	−0.2 (4)
Cl1—Cu1—N3—C9	−23.5 (2)	C4—C5—C6—C7	−179.1 (2)
Cl2—Cu1—N3—C9	80.0 (2)	C5—C6—C7—C8	1.7 (4)
N2—Cu1—N3—C5	7.08 (15)	C6—C7—C8—C9	−1.8 (4)
O1—Cu1—N3—C5	35.4 (3)	C5—N3—C9—C8	1.1 (4)
Cl1—Cu1—N3—C5	163.84 (14)	Cu1—N3—C9—C8	−171.3 (2)
Cl2—Cu1—N3—C5	−92.74 (15)	C7—C8—C9—N3	0.4 (4)
Cu1—O1—C2—N1	0.5 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2i	0.89	2.34	3.226 (2)	170
C1—H1A···Cl1ii	0.98	2.63	3.529 (3)	153
C3—H3A···N1	0.98	2.56	2.945 (3)	104
C3—H3A···Cl2i	0.98	2.81	3.785 (3)	176
C3—H3C···Cl1iii	0.98	2.75	3.703 (3)	165
C7—H7···Cl1iv	0.95	2.68	3.529 (3)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2i	0.89	2.34	3.226 (2)	170
C1—H1A⋯Cl1ii	0.98	2.63	3.529 (3)	153
C3—H3A⋯Cl2i	0.98	2.81	3.785 (3)	176
C3—H3C⋯Cl1iii	0.98	2.75	3.703 (3)	165
C7—H7⋯Cl1iv	0.95	2.68	3.529 (3)	149

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