Chlorido[1-(pyridin-2-yl)ethanone oximato-κN,N'][1-(2-pyrid-yl)ethanone oxime-κN,N']copper(II) trihydrate.

In the title compound, [Cu(C(7)H(7)N(2)O)Cl(C(7)H(8)N(2)O)]·3H(2)O, the metal ion is five-coordinated by the N atoms from the 1-(pyridin-2-yl)ethanone oximate and 1-(pyridin-2-yl)ethanone oxime ligands and by the chloride anion in a distorted square-pyramidal geometry. The distortion parameter is 0.192. The two organic ligands are linked by an intra-molecular O-H⋯O hydrogen bond. In the crystal, mol-ecules are linked by O-H⋯O and O-H⋯Cl hydrogen bonds. The title compound is the hydrated form of a previously reported structure [Wu & Wu (2008 ▶). Acta Cryst. E64, m828]. There are only slight variations in the mol-ecular geometries of the two compounds.

Related literature

For uses of oximes, see: Chaudhuri (2003 ▶). For theoretical research, see: Pavlishchuk et al. (2003 ▶). For related structure, see: Zuo et al. (2007 ▶); Wu & Wu (2008 ▶). For the properties of related complexes, see: Davidson et al. (2007 ▶); Clerac et al. (2002 ▶). For the distortion parameter, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[Cu(C7H7N2O)Cl(C7H8N2O)]·3H2O

M = 424.34

Triclinic,

a = 8.3980 (9) Å

b = 10.2559 (11) Å

c = 12.1121 (13) Å

α = 114.199 (2)°

β = 93.462 (1)°

γ = 103.972 (1)°

V = 908.29 (17) Å3

Z = 2

Mo Kα radiation

μ = 1.38 mm−1

T = 298 K

0.45 × 0.41 × 0.24 mm

Data collection

Siemens SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.575, T max = 0.733

4646 measured reflections

3156 independent reflections

2493 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.096

S = 1.00

3156 reflections

228 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.30 e Å−3

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); 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 datablock(s) I, global. DOI: 10.1107/S1600536811049129/bx2382sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049129/bx2382Isup2.hkl

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

[Cu(C7H7N2O)Cl(C7H8N2O)]·3H2O	Z = 2
Mr = 424.34	F(000) = 438
Triclinic, P1	Dx = 1.552 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3980 (9) Å	Cell parameters from 2075 reflections
b = 10.2559 (11) Å	θ = 2.5–26.8°
c = 12.1121 (13) Å	µ = 1.38 mm−1
α = 114.199 (2)°	T = 298 K
β = 93.462 (1)°	Block, dark-green
γ = 103.972 (1)°	0.45 × 0.41 × 0.24 mm
V = 908.29 (17) Å3

Siemens SMART 1000 CCD diffractometer	3156 independent reflections
Radiation source: fine-focus sealed tube	2493 reflections with I > 2σ(I)
graphite	Rint = 0.018
phi and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.575, Tmax = 0.733	k = −7→12
4646 measured reflections	l = −14→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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0446P)2 + 0.7087P] where P = (Fo2 + 2Fc2)/3
3156 reflections	(Δ/σ)max = 0.022
228 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

	x	y	z	Uiso*/Ueq
Cu1	0.08870 (5)	0.44895 (4)	0.68063 (3)	0.03697 (15)
Cl1	0.35260 (11)	0.46847 (10)	0.79450 (8)	0.0481 (2)
N1	0.0912 (4)	0.2780 (3)	0.5265 (2)	0.0418 (7)
N2	0.1968 (3)	0.5577 (3)	0.5806 (2)	0.0364 (6)
N3	−0.0916 (3)	0.3230 (3)	0.7265 (3)	0.0403 (7)
N4	0.0355 (3)	0.6084 (3)	0.8295 (2)	0.0355 (6)
O1	0.0222 (3)	0.1363 (2)	0.5044 (2)	0.0568 (7)
H1	−0.0247	0.1338	0.5613	0.085*
O2	−0.1472 (3)	0.1713 (3)	0.6666 (2)	0.0555 (7)
O3	0.4005 (4)	0.0145 (3)	0.8601 (3)	0.0820 (10)
H3C	0.3588	0.0494	0.8165	0.098*
H3D	0.4073	0.0722	0.9355	0.098*
O4	0.7339 (4)	0.8940 (3)	0.3036 (3)	0.0840 (10)
H4C	0.8180	0.9495	0.3605	0.101*
H4D	0.7251	0.8032	0.2868	0.101*
O5	0.5675 (4)	0.8149 (3)	0.8877 (3)	0.0795 (9)
H5C	0.5105	0.8684	0.8772	0.095*
H5D	0.5043	0.7260	0.8616	0.095*
C1	0.1862 (6)	0.1812 (4)	0.3309 (3)	0.0639 (11)
H1A	0.2069	0.1028	0.3481	0.096*
H1B	0.2772	0.2196	0.2977	0.096*
H1C	0.0847	0.1424	0.2722	0.096*
C2	0.1705 (4)	0.3039 (4)	0.4468 (3)	0.0421 (8)
C3	0.2392 (4)	0.4625 (4)	0.4784 (3)	0.0373 (7)
C4	0.3404 (4)	0.5153 (4)	0.4109 (3)	0.0474 (9)
H4	0.3695	0.4487	0.3416	0.057*
C5	0.3981 (5)	0.6664 (5)	0.4465 (3)	0.0534 (10)
H5	0.4678	0.7030	0.4024	0.064*
C6	0.3516 (5)	0.7628 (4)	0.5479 (3)	0.0506 (9)
H6	0.3880	0.8655	0.5732	0.061*
C7	0.2498 (4)	0.7036 (4)	0.6111 (3)	0.0439 (8)
H7	0.2163	0.7687	0.6786	0.053*
C8	−0.3054 (5)	0.3094 (4)	0.8534 (4)	0.0558 (10)
H8A	−0.3315	0.2037	0.8035	0.084*
H8B	−0.4012	0.3419	0.8436	0.084*
H8C	−0.2750	0.3313	0.9382	0.084*
C9	−0.1636 (4)	0.3891 (4)	0.8147 (3)	0.0397 (8)
C10	−0.0901 (4)	0.5520 (4)	0.8775 (3)	0.0375 (7)
C11	−0.1392 (5)	0.6427 (4)	0.9816 (3)	0.0502 (9)
H11	−0.2280	0.6026	1.0116	0.060*
C12	−0.0552 (5)	0.7932 (4)	1.0402 (4)	0.0577 (10)
H12	−0.0871	0.8559	1.1100	0.069*
C13	0.0756 (5)	0.8495 (4)	0.9948 (3)	0.0505 (9)
H13	0.1353	0.9503	1.0339	0.061*
C14	0.1169 (4)	0.7534 (4)	0.8898 (3)	0.0436 (8)
H14	0.2063	0.7920	0.8595	0.052*

	U11	U22	U33	U12	U13	U23
Cu1	0.0435 (3)	0.0338 (2)	0.0336 (2)	0.01245 (17)	0.01058 (18)	0.01352 (17)
Cl1	0.0494 (5)	0.0579 (6)	0.0446 (5)	0.0244 (4)	0.0113 (4)	0.0246 (4)
N1	0.0512 (18)	0.0330 (15)	0.0382 (16)	0.0145 (13)	0.0054 (14)	0.0118 (12)
N2	0.0428 (16)	0.0390 (15)	0.0312 (14)	0.0154 (12)	0.0093 (12)	0.0170 (12)
N3	0.0412 (16)	0.0367 (15)	0.0424 (16)	0.0098 (12)	0.0051 (13)	0.0180 (13)
N4	0.0402 (16)	0.0366 (15)	0.0340 (14)	0.0148 (12)	0.0107 (12)	0.0170 (12)
O1	0.0778 (19)	0.0337 (13)	0.0522 (15)	0.0157 (12)	0.0182 (14)	0.0119 (12)
O2	0.0658 (17)	0.0346 (13)	0.0603 (16)	0.0062 (12)	0.0103 (14)	0.0201 (12)
O3	0.113 (3)	0.0569 (18)	0.070 (2)	0.0055 (17)	0.0038 (19)	0.0344 (16)
O4	0.097 (3)	0.0676 (19)	0.074 (2)	0.0333 (18)	−0.0174 (18)	0.0177 (17)
O5	0.075 (2)	0.073 (2)	0.087 (2)	0.0174 (17)	0.0154 (18)	0.0332 (18)
C1	0.088 (3)	0.052 (2)	0.043 (2)	0.030 (2)	0.020 (2)	0.0075 (18)
C2	0.049 (2)	0.046 (2)	0.0309 (17)	0.0222 (16)	0.0064 (16)	0.0121 (15)
C3	0.0375 (19)	0.052 (2)	0.0283 (16)	0.0204 (15)	0.0055 (14)	0.0187 (15)
C4	0.051 (2)	0.064 (2)	0.0372 (19)	0.0252 (19)	0.0133 (17)	0.0253 (18)
C5	0.054 (2)	0.076 (3)	0.048 (2)	0.023 (2)	0.0184 (19)	0.042 (2)
C6	0.060 (2)	0.051 (2)	0.046 (2)	0.0140 (18)	0.0075 (18)	0.0272 (18)
C7	0.053 (2)	0.046 (2)	0.0337 (18)	0.0160 (17)	0.0093 (16)	0.0178 (16)
C8	0.044 (2)	0.068 (3)	0.067 (3)	0.0134 (19)	0.0167 (19)	0.041 (2)
C9	0.0348 (18)	0.050 (2)	0.0443 (19)	0.0130 (15)	0.0057 (15)	0.0302 (17)
C10	0.0376 (19)	0.0488 (19)	0.0365 (18)	0.0196 (15)	0.0086 (15)	0.0245 (16)
C11	0.051 (2)	0.065 (2)	0.049 (2)	0.0258 (19)	0.0245 (18)	0.0308 (19)
C12	0.071 (3)	0.058 (2)	0.047 (2)	0.032 (2)	0.027 (2)	0.0164 (19)
C13	0.065 (3)	0.043 (2)	0.044 (2)	0.0227 (18)	0.0137 (19)	0.0157 (17)
C14	0.049 (2)	0.0412 (19)	0.0411 (19)	0.0136 (16)	0.0113 (16)	0.0175 (16)

Cu1—N1	1.975 (3)	C1—H1C	0.9600
Cu1—N3	2.004 (3)	C2—C3	1.462 (5)
Cu1—N4	2.038 (2)	C3—C4	1.382 (5)
Cu1—N2	2.071 (3)	C4—C5	1.374 (5)
Cu1—Cl1	2.4584 (10)	C4—H4	0.9300
N1—C2	1.284 (4)	C5—C6	1.374 (5)
N1—O1	1.333 (3)	C5—H5	0.9300
N2—C7	1.333 (4)	C6—C7	1.377 (5)
N2—C3	1.357 (4)	C6—H6	0.9300
N3—C9	1.284 (4)	C7—H7	0.9300
N3—O2	1.359 (3)	C8—C9	1.490 (5)
N4—C14	1.331 (4)	C8—H8A	0.9600
N4—C10	1.357 (4)	C8—H8B	0.9600
O1—H1	0.8200	C8—H8C	0.9600
O3—H3C	0.8500	C9—C10	1.467 (5)
O3—H3D	0.8499	C10—C11	1.382 (5)
O4—H4C	0.8500	C11—C12	1.379 (5)
O4—H4D	0.8499	C11—H11	0.9300
O5—H5C	0.8501	C12—C13	1.367 (5)
O5—H5D	0.8500	C12—H12	0.9300
C1—C2	1.492 (4)	C13—C14	1.379 (5)
C1—H1A	0.9600	C13—H13	0.9300
C1—H1B	0.9600	C14—H14	0.9300
N1—Cu1—N3	92.87 (11)	C4—C3—C2	123.6 (3)
N1—Cu1—N4	168.50 (11)	C5—C4—C3	119.8 (3)
N3—Cu1—N4	78.92 (10)	C5—C4—H4	120.1
N1—Cu1—N2	78.86 (11)	C3—C4—H4	120.1
N3—Cu1—N2	157.52 (11)	C4—C5—C6	119.3 (3)
N4—Cu1—N2	105.76 (10)	C4—C5—H5	120.4
N1—Cu1—Cl1	96.51 (9)	C6—C5—H5	120.4
N3—Cu1—Cl1	105.86 (8)	C5—C6—C7	118.3 (3)
N4—Cu1—Cl1	93.50 (8)	C5—C6—H6	120.8
N2—Cu1—Cl1	95.89 (8)	C7—C6—H6	120.8
C2—N1—O1	118.3 (3)	N2—C7—C6	123.4 (3)
C2—N1—Cu1	118.7 (2)	N2—C7—H7	118.3
O1—N1—Cu1	122.9 (2)	C6—C7—H7	118.3
C7—N2—C3	118.0 (3)	C9—C8—H8A	109.5
C7—N2—Cu1	129.7 (2)	C9—C8—H8B	109.5
C3—N2—Cu1	111.4 (2)	H8A—C8—H8B	109.5
C9—N3—O2	117.7 (3)	C9—C8—H8C	109.5
C9—N3—Cu1	118.3 (2)	H8A—C8—H8C	109.5
O2—N3—Cu1	123.9 (2)	H8B—C8—H8C	109.5
C14—N4—C10	117.7 (3)	N3—C9—C10	113.8 (3)
C14—N4—Cu1	128.6 (2)	N3—C9—C8	123.8 (3)
C10—N4—Cu1	113.4 (2)	C10—C9—C8	122.3 (3)
N1—O1—H1	109.5	N4—C10—C11	121.6 (3)
H3C—O3—H3D	108.6	N4—C10—C9	115.3 (3)
H4C—O4—H4D	108.7	C11—C10—C9	123.0 (3)
H5C—O5—H5D	108.6	C12—C11—C10	119.3 (3)
C2—C1—H1A	109.5	C12—C11—H11	120.4
C2—C1—H1B	109.5	C10—C11—H11	120.4
H1A—C1—H1B	109.5	C13—C12—C11	119.3 (3)
C2—C1—H1C	109.5	C13—C12—H12	120.3
H1A—C1—H1C	109.5	C11—C12—H12	120.3
H1B—C1—H1C	109.5	C12—C13—C14	118.5 (3)
N1—C2—C3	114.2 (3)	C12—C13—H13	120.7
N1—C2—C1	122.3 (3)	C14—C13—H13	120.7
C3—C2—C1	123.5 (3)	N4—C14—C13	123.5 (3)
N2—C3—C4	121.1 (3)	N4—C14—H14	118.2
N2—C3—C2	115.3 (3)	C13—C14—H14	118.2
N3—Cu1—N1—C2	167.8 (3)	Cu1—N1—C2—C1	176.8 (3)
N4—Cu1—N1—C2	123.8 (5)	C7—N2—C3—C4	2.8 (5)
N2—Cu1—N1—C2	8.9 (3)	Cu1—N2—C3—C4	−167.7 (3)
Cl1—Cu1—N1—C2	−85.9 (3)	C7—N2—C3—C2	−177.2 (3)
N3—Cu1—N1—O1	−16.2 (3)	Cu1—N2—C3—C2	12.3 (3)
N4—Cu1—N1—O1	−60.2 (7)	N1—C2—C3—N2	−5.6 (4)
N2—Cu1—N1—O1	−175.1 (3)	C1—C2—C3—N2	172.9 (3)
Cl1—Cu1—N1—O1	90.2 (3)	N1—C2—C3—C4	174.4 (3)
N1—Cu1—N2—C7	179.7 (3)	C1—C2—C3—C4	−7.2 (5)
N3—Cu1—N2—C7	109.7 (4)	N2—C3—C4—C5	−0.8 (5)
N4—Cu1—N2—C7	10.5 (3)	C2—C3—C4—C5	179.3 (3)
Cl1—Cu1—N2—C7	−84.8 (3)	C3—C4—C5—C6	−1.1 (6)
N1—Cu1—N2—C3	−11.2 (2)	C4—C5—C6—C7	0.8 (6)
N3—Cu1—N2—C3	−81.2 (3)	C3—N2—C7—C6	−3.2 (5)
N4—Cu1—N2—C3	179.6 (2)	Cu1—N2—C7—C6	165.3 (3)
Cl1—Cu1—N2—C3	84.3 (2)	C5—C6—C7—N2	1.5 (6)
N1—Cu1—N3—C9	−167.7 (3)	O2—N3—C9—C10	177.3 (3)
N4—Cu1—N3—C9	4.2 (2)	Cu1—N3—C9—C10	−5.3 (4)
N2—Cu1—N3—C9	−100.3 (3)	O2—N3—C9—C8	−0.9 (5)
Cl1—Cu1—N3—C9	94.7 (2)	Cu1—N3—C9—C8	176.5 (3)
N1—Cu1—N3—O2	9.6 (3)	C14—N4—C10—C11	3.7 (5)
N4—Cu1—N3—O2	−178.5 (3)	Cu1—N4—C10—C11	177.5 (3)
N2—Cu1—N3—O2	76.9 (4)	C14—N4—C10—C9	−173.8 (3)
Cl1—Cu1—N3—O2	−88.0 (2)	Cu1—N4—C10—C9	0.0 (3)
N1—Cu1—N4—C14	−144.0 (5)	N3—C9—C10—N4	3.4 (4)
N3—Cu1—N4—C14	171.0 (3)	C8—C9—C10—N4	−178.4 (3)
N2—Cu1—N4—C14	−31.6 (3)	N3—C9—C10—C11	−174.1 (3)
Cl1—Cu1—N4—C14	65.5 (3)	C8—C9—C10—C11	4.1 (5)
N1—Cu1—N4—C10	43.0 (6)	N4—C10—C11—C12	−2.2 (5)
N3—Cu1—N4—C10	−2.0 (2)	C9—C10—C11—C12	175.2 (3)
N2—Cu1—N4—C10	155.4 (2)	C10—C11—C12—C13	−0.4 (6)
Cl1—Cu1—N4—C10	−107.5 (2)	C11—C12—C13—C14	1.3 (6)
O1—N1—C2—C3	179.1 (3)	C10—N4—C14—C13	−2.8 (5)
Cu1—N1—C2—C3	−4.7 (4)	Cu1—N4—C14—C13	−175.6 (3)
O1—N1—C2—C1	0.6 (5)	C12—C13—C14—N4	0.4 (6)

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5D···Cl1	0.85	2.40	3.244 (3)	174.
O5—H5C···O3i	0.85	2.01	2.857 (5)	173.
O4—H4D···Cl1ii	0.85	2.44	3.275 (3)	168.
O4—H4C···O1ii	0.85	2.60	3.165 (4)	126.
O4—H4C···O1iii	0.85	2.23	3.063 (4)	167.
O3—H3D···O5iv	0.85	1.94	2.785 (4)	173.
O3—H3C···O4ii	0.85	1.96	2.802 (4)	172.
O1—H1···O2	0.82	1.67	2.452 (4)	160.

Table 1

Selected geometric parameters (Å, °)

Cu1—N1	1.975 (3)
Cu1—N3	2.004 (3)
Cu1—N4	2.038 (2)
Cu1—N2	2.071 (3)
Cu1—Cl1	2.4584 (10)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5D⋯Cl1	0.85	2.40	3.244 (3)	174
O5—H5C⋯O3i	0.85	2.01	2.857 (5)	173
O4—H4D⋯Cl1ii	0.85	2.44	3.275 (3)	168
O4—H4C⋯O1ii	0.85	2.60	3.165 (4)	126
O4—H4C⋯O1iii	0.85	2.23	3.063 (4)	167
O3—H3D⋯O5iv	0.85	1.94	2.785 (4)	173
O3—H3C⋯O4ii	0.85	1.96	2.802 (4)	172
O1—H1⋯O2	0.82	1.67	2.452 (4)	160

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