Chlorido[1-(pyridin-2-yl)ethanone oximato-κ2N,N′][1-(2-pyrid­yl)ethanone oxime-κ2N,N′]copper(II) trihydrate

Qiu, X.; Li, L.; Li, D.

doi:10.1107/S1600536811049129

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Pages m1810-m1811

https://doi.org/10.1107/S1600536811049129

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Chlorido[1-(pyridin-2-yl)ethanone oximato-κ²N,N′][1-(2-pyridyl)ethanone oxime-κ²N,N′]copper(II) trihydrate

Xiumin Qiu,^a Leilei Li ^a and Dacheng Li ^a ^*

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: lidacheng@lcu.edu.cn

(Received 6 November 2011; accepted 17 November 2011; online 23 November 2011)

In the title compound, [Cu(C₇H₇N₂O)Cl(C₇H₈N₂O)]·3H₂O, 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 intramolecular O—H⋯O hydrogen bond. In the crystal, molecules 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 molecular 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_r = 424.34
Triclinic, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.035
wR(F²) = 0.096
S = 1.00
3156 reflections
228 parameters
H-atom parameters constrained
Δρ_max = 0.41 e Å⁻³
Δρ_min = −0.30 e Å⁻³

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⋯O5^iv	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) x, y+1, z; (ii) -x+1, -y+1, -z+1; (iii) x+1, y+1, z; (iv) -x+1, -y+1, -z+2.

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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811049129/bx2382sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811049129/bx2382Isup2.hkl

checkCIF report

Comment top

There is currently a renewed interest in the coordination chemistry of oximes (Davidson et al., 2007; Pavlishchuk et al., 2003). The organic ligand is methyl 2-pyridyl ketone oxime, [(py)C(Me)NOH], which belongs to the family of 2-pyridyl oximes (Chaudhuri, 2003). 2-pyridyl oximes are a subclass of oximes whose anions are versatile ligands for a variety of research objectives and have been key ligands in several areas of molecular magnetism, including single-molecule and single-chain magnets (Clerac et al., 2002). We report here the synthesis and crystal structure of the title compound. In the title complex (Fig.1) the asymmetric unit consists of one metallic complex and three water molecules. The Cu center is five-coordinate by the N atoms from the methyl(2-pyridyl)ketooxime ligand and one chloride anions.The two methyl(2-pyridyl)ketooxime ligands are coordinated to copper to form two five-membered CuC₂N₂ rings. The copper atom adopts a distorted 4+1 square-pyramidal coordination mode with the distortion parameter being 0.192 (Addison et al., 1984) which is smaller than the values reported in the literature (Wu & Wu, 2008) and the angles around copper ion ranging from 78.86 (1)° for N1-Cu1-N2 to 168.50 (1)° for N1-Cu1-N4. There exists one deprotonated and one protonated oxime ligand with a strong intramolecular hydrogen bond between the OH group and the negatively charged oxygen of the other ligand (O1···O2 = 2.452 Å) which is shorter than the reported literature (Wu & Wu, 2008), (Table 2). The molecular conformation is stabilized by one intramolecular O—H···O and O—H···Cl hydrogen bonds interactions and the crystal structure is stabilized by six O—H···O hydrogen bonds interactions (Table 2, Fig.2).

Related literature top

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 top

A solution of CuCl₂ (0.0426g, 0.25mmol) in MeOH (10 ml) was added to a solution of (py)C(Me)NOH (0.068 g, 0.5 mmol) in MeOH (10 ml). The resulting dark green solution was stirred for about 6 h and was then allowed to slowly concentrate by solvent evaporation at room temperature. Dark green block crystals suitable for X-ray diffraction were obtained within two weeks. (56.7%, m.p. 310-315K). FTIR (KBr) v (cm^-l): 3424(O—H); 1597,(C=N); 2917, 1437, (C—H); 1157, 1177, 1260, (N—O).

Structure description top

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).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Part of the crystal structure with hydrogen bonds shown as dashed lines.

Chlorido[1-(pyridin-2-yl)ethanone oximato-κ²N,N'][1-(2-pyridyl)ethanone oxime-κ²N,N']copper(II) trihydrate top

Crystal data top

[Cu(C₇H₇N₂O)Cl(C₇H₈N₂O)]·3H₂O	Z = 2
M_r = 424.34	F(000) = 438
Triclinic, P1	D_x = 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

Data collection top

Siemens SMART 1000 CCD diffractometer	3156 independent reflections
Radiation source: fine-focus sealed tube	2493 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
phi and ω scans	θ_max = 25.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.575, T_max = 0.733	k = −7→12
4646 measured reflections	l = −14→11

Refinement top

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(F_o²) + (0.0446P)² + 0.7087P] where P = (F_o² + 2F_c²)/3
3156 reflections	(Δ/σ)_max = 0.022
228 parameters	Δρ_max = 0.41 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Cu(C₇H₇N₂O)Cl(C₇H₈N₂O)]·3H₂O	γ = 103.972 (1)°
M_r = 424.34	V = 908.29 (17) Å³
Triclinic, P1	Z = 2
a = 8.3980 (9) Å	Mo Kα radiation
b = 10.2559 (11) Å	µ = 1.38 mm⁻¹
c = 12.1121 (13) Å	T = 298 K
α = 114.199 (2)°	0.45 × 0.41 × 0.24 mm
β = 93.462 (1)°

Data collection top

Siemens SMART 1000 CCD diffractometer	3156 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2493 reflections with I > 2σ(I)
T_min = 0.575, T_max = 0.733	R_int = 0.018
4646 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.00	Δρ_max = 0.41 e Å⁻³
3156 reflections	Δρ_min = −0.30 e Å⁻³
228 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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···O5^iv	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) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y+1, z; (iv) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₇N₂O)Cl(C₇H₈N₂O)]·3H₂O
M_r	424.34
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	8.3980 (9), 10.2559 (11), 12.1121 (13)
α, β, γ (°)	114.199 (2), 93.462 (1), 103.972 (1)
V (Å³)	908.29 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.38
Crystal size (mm)	0.45 × 0.41 × 0.24

Data collection
Diffractometer	Siemens SMART 1000 CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.575, 0.733
No. of measured, independent and observed [I > 2σ(I)] reflections	4646, 3156, 2493
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.096, 1.00
No. of reflections	3156
No. of parameters	228
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.41, −0.30

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

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

N1—Cu1—N3	92.87 (11)	N1—Cu1—N2	78.86 (11)
N1—Cu1—N4	168.50 (11)	N3—Cu1—N2	157.52 (11)
N3—Cu1—N4	78.92 (10)	N4—Cu1—N2	105.76 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5D···Cl1	0.85	2.40	3.244 (3)	173.6
O5—H5C···O3ⁱ	0.85	2.01	2.857 (5)	173.3
O4—H4D···Cl1ⁱⁱ	0.85	2.44	3.275 (3)	167.5
O4—H4C···O1ⁱⁱ	0.85	2.60	3.165 (4)	125.5
O4—H4C···O1ⁱⁱⁱ	0.85	2.23	3.063 (4)	167.1
O3—H3D···O5^iv	0.85	1.94	2.785 (4)	172.6
O3—H3C···O4ⁱⁱ	0.85	1.96	2.802 (4)	172.0
O1—H1···O2	0.82	1.67	2.452 (4)	159.7

Symmetry codes: (i) x, y+1, z; (ii) −x+1, −y+1, −z+1; (iii) x+1, y+1, z; (iv) −x+1, −y+1, −z+2.

Acknowledgements

This work was supported by the National Natural Science Foundation of PR China (Project Nos. 20971063, 21041002) and Shandong Province Higher School Science and Technology Plan Projects (project No. J10LB61).

References

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