Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κ3O,N,N′]copper(II) tetra­hydrate

Zhao, K.; Yin, X.-H.; Hu, F.-L.; Lin, C.-W.; Zhang, S.-S.; Qing, R.-W.

doi:10.1107/S1600536807068110

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Pages m284-m285

doi:10.1107/S1600536807068110

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Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κ³O,N,N′]copper(II) tetrahydrate

Kai Zhao,^a,^b Xian-Hong Yin,^a ^* Fei-Long Hu,^a Cui-Wu Lin,^b Shang-Shang Zhang ^a and Ru-Wen Qing ^a

^aCollege of Chemistry and Ecological Engineering, Guangxi University for Nationalities, Nanning 530006, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, People's Republic of China
^*Correspondence e-mail: yxhphd@163.com

(Received 7 October 2007; accepted 21 December 2007; online 4 January 2008)

In the title complex, [Cu(C₁₁H₉ClN₃O₂)₂]·4H₂O, the Cu^II atom is in a distorted octahedral coordination environment, coordinated by four N atoms and two O atoms from two tridentate 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinate ligands. The molecules are linked via intermolecular O—H⋯O hydrogen bonds involving water molecules to form extended chains along [010], and there are short Cl⋯Cl contacts [3.153 (4) Å].

Related literature

For related literature, see: Aliev et al. (1988 ); Bhatia et al. (1981 ); Costamagna et al. (1992 ); Kai et al. (2007 ); Kuang et al. (1997 ); Ramazani et al. (2002 ); Xu et al. (2001 ); Yaghi & Li (1996 ); Yin et al. (2007 ); Zhao et al. (2007 ).

Experimental

Crystal data

[Cu(C₁₁H₉ClN₃O₂)₂]·4H₂O
M_r = 636.93
Triclinic, $[P \overline 1]$
a = 9.6578 (9) Å
b = 11.2637 (14) Å
c = 14.3127 (18) Å
α = 92.349 (2)°
β = 106.090 (2)°
γ = 114.065 (3)°
V = 1344.7 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.07 mm⁻¹
T = 298 (2) K
0.59 × 0.52 × 0.50 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.571, T_max = 0.617 (expected range = 0.543–0.586)
7014 measured reflections
4664 independent reflections
3789 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.101
S = 1.03
4664 reflections
352 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O6	0.85	1.96	2.804 (4)	170
O5—H5B⋯O4ⁱ	0.85	1.98	2.818 (4)	170
O6—H6A⋯O2	0.85	2.24	3.090 (5)	176
O6—H6B⋯O7ⁱⁱ	0.85	1.85	2.697 (4)	176
O8—H8A⋯O5	0.85	2.10	2.947 (5)	178
O8—H8B⋯O5ⁱⁱⁱ	0.85	1.98	2.825 (5)	179
Symmetry codes: (i) x+1, y+1, z; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y+1, -z.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807068110/rn2033sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068110/rn2033Isup2.hkl

checkCIF report

Comment top

Transition metal compounds containing pyrazolyl pyridine ligands have been of great interest for many years (Kuang et al., 1997; Ramazani et al., 2002). These compounds play an important role in the development of coordination chemistry related to catalysis and enzymatic reactions, magnetism and molecular architectures (Costamagna et al., 1992; Bhatia et al., 1981). Inorganic supramolecular chemistry, and in particular the construction of polymeric coordination networks, is an extremely topical area of research (Xu et al.., 2001; Yaghi et al.., 1996) and the construction of a wide variety of network topologies has been achieved through ligand design and the use of different counter-anions. Our work is aimed at obtaining multidimensional metal complexes. On the basis of the above-mentioned considerations, we designed and synthesized the flexible tridentate ligand 3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinic acid (CDPA) (Kai et al., 2007), which offers advantages over rigid ligands in that it can adopt a different coordination modes according to the geometric needs of the coordination environment of the transition metal. Recently we reported the crystal structures of bis(6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato)zinc(II)trihydrate (Yin et al., 2007). As a continuation of these investigations, we report in this paper the crystal structure of bis(6-(3-chloro-(3,5-dimethyl-1H-pyrazol-1-yl))picolinato) copper(II)tetra-hydrate, (I), Fig. 1.

The title complex, (I), is an asymmetric electronically neutral mononuclear compound with four uncoordinated water molecules (Fig. 1). The Cu^II atom is coordinated by four N atoms and two O atoms from two tridentate, 6-(3-chloro-(3,5-dimethyl-1H-pyrazol- 1-yl))picolinic acid (CDPA) ligands, respectively. that define a distorted octahedral environment for the copper atom. The Cu—O bond length is 2.073 (2)and 2.176 (2) Å, The Cu—N distances range from 1.969 (2) to 2.214 (2) Å, the C5—C6 and C9—C10 bond lengths are 1.388 (4) and 1.398 (5) Å; they are longer than the normal C=C bond length (1.38 Å) because they participate in the C—N conjugated system. There are many stacking interactions involving the CDPA ligand forming a supramolecular structure.

In the crystal structure, all oxygen atoms, except O1 and O3, bound to the metal center, contribute to the formation of intermolecular hydrogen bonds involving the solvate water molecules (Zhao et al., 2007), and there are short Cl···Cl contacts (Cl2—Cl2= 3.153 Å), their distances are much shorter than the van der Waal distance(Aliev et al., 1988). (Fig.2. for symmetry codes see Table 2). A great number of H-bonds and short Cl···Cl contacts join the complex to form a three-dimensional supramolecular network structure along b axis.

Related literature top

For related literature, see: Aliev et al. (1988); Bhatia et al. (1981); Costamagna et al. (1992); Kai et al. (2007); Kuang et al. (1997); Ramazani et al. (2002); Xu et al. (2001); Yaghi & Li (1996); Yin et al. (2007); Zhao et al. (2007).

Experimental top

6-(3-chloro-(3,5-dimethyl-1H-pyrazol-1-yl))picolinic acid, and CuSO₄. 6H₂O were available commercially and were used without further purification. Equimolar 6-(3-chloro-(3,5-dimethyl-1H-pyrazol-1-yl))picolinic acid (1 mmol, 217 mg) was dissolved in anhydrous alcohol (15 ml). The mixture was stirred to give a clear solution, To this solution was added CuSO₄.6H₂O (0.5 mmol, 119 mg) in anhydrous alcohol (10 ml). After keeping the resulting solution in air to evaporate about half of the solvents, blue blocks of the title compound were formed. The crystals were isolated, washed with alcohol three times and dried in a vacuum desiccator using silica gel (Yield 72%). Elemental analysis: found: C, 53.708; H, 4.20; N, 17.04;; calc. for C₂₂H₂0_CuCl_N6_O4: C, 53.78; H, 4.10; N, 17.10.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SMART (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top

	Fig. 1. The structure of the title compound (I) showing 50% probability displacement ellipsoids and the atom-numbering scheme, H atoms have been omitted for clarity
	Fig. 2. Crystal packing of (I) showing the hydrogen bonded interactions as dashed lines, H atoms have been omitted for clarity.

Bis[3-chloro-6-(3,5-dimethyl-1H-pyrazol-1-yl)picolinato-κ³O,N,N']copper(II) tetrahydrate top

Crystal data top

[Cu(C₁₁H₉ClN₃O₂)₂]·4H₂O	Z = 2
M_r = 636.93	F(000) = 654
Triclinic, P1	D_x = 1.573 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.6578 (9) Å	Cell parameters from 3642 reflections
b = 11.2637 (14) Å	θ = 2.4–27.8°
c = 14.3127 (18) Å	µ = 1.07 mm⁻¹
α = 92.349 (2)°	T = 298 K
β = 106.090 (2)°	Block, blue
γ = 114.065 (3)°	0.59 × 0.52 × 0.50 mm
V = 1344.7 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	4664 independent reflections
Radiation source: fine-focus sealed tube	3789 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.571, T_max = 0.617	k = −7→13
7014 measured reflections	l = −16→17

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0452P)² + 1.138P] where P = (F_o² + 2F_c²)/3
4664 reflections	(Δ/σ)_max < 0.001
352 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Cu(C₁₁H₉ClN₃O₂)₂]·4H₂O	γ = 114.065 (3)°
M_r = 636.93	V = 1344.7 (3) Å³
Triclinic, P1	Z = 2
a = 9.6578 (9) Å	Mo Kα radiation
b = 11.2637 (14) Å	µ = 1.07 mm⁻¹
c = 14.3127 (18) Å	T = 298 K
α = 92.349 (2)°	0.59 × 0.52 × 0.50 mm
β = 106.090 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4664 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3789 reflections with I > 2σ(I)
T_min = 0.571, T_max = 0.617	R_int = 0.016
7014 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	Δρ_max = 0.38 e Å⁻³
4664 reflections	Δρ_min = −0.48 e Å⁻³
352 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Cu1	0.26465 (4)	0.01979 (4)	0.24804 (3)	0.03700 (13)
Cl1	0.05694 (11)	0.41095 (9)	0.17347 (7)	0.0574 (2)
Cl2	0.08351 (12)	−0.43064 (9)	0.42400 (7)	0.0646 (3)
N1	0.2134 (3)	0.1366 (2)	0.16023 (16)	0.0305 (5)
N2	0.2500 (3)	0.0211 (2)	0.04162 (17)	0.0352 (5)
N3	0.2667 (3)	−0.0574 (2)	0.11161 (18)	0.0395 (6)
N4	0.3193 (3)	−0.0982 (2)	0.33689 (16)	0.0324 (5)
N5	0.5845 (3)	0.0389 (2)	0.36071 (17)	0.0347 (5)
N6	0.5287 (3)	0.1231 (2)	0.31390 (18)	0.0376 (6)
O1	0.2253 (3)	0.1378 (2)	0.34278 (16)	0.0530 (6)
O2	0.1882 (3)	0.3198 (3)	0.35335 (17)	0.0664 (7)
O3	0.0307 (3)	−0.1408 (3)	0.22898 (19)	0.0631 (7)
O4	−0.0869 (3)	−0.2981 (3)	0.3052 (2)	0.0967 (12)
O5	0.6077 (3)	0.6078 (3)	0.1622 (2)	0.0812 (9)
H5A	0.5484	0.5881	0.1987	0.097*
H5B	0.7046	0.6379	0.1991	0.097*
O6	0.4476 (4)	0.5544 (4)	0.3027 (2)	0.1041 (11)
H6A	0.3801	0.4903	0.3196	0.125*
H6B	0.5371	0.5849	0.3487	0.125*
O7	0.2625 (4)	0.3401 (4)	0.5565 (2)	0.1128 (14)
H7D	0.2174	0.3287	0.4946	0.135*
H7E	0.1920	0.3234	0.5851	0.135*
O8	0.5577 (6)	0.3762 (5)	0.0299 (3)	0.151 (2)
H8A	0.5727	0.4423	0.0690	0.182*
H8B	0.5076	0.3798	−0.0282	0.182*
C1	0.1974 (4)	0.2295 (3)	0.3083 (2)	0.0409 (7)
C2	0.1742 (3)	0.2257 (3)	0.1976 (2)	0.0324 (6)
C3	0.1224 (3)	0.3012 (3)	0.1356 (2)	0.0381 (7)
C4	0.1170 (4)	0.2856 (3)	0.0382 (2)	0.0479 (8)
H4	0.0841	0.3371	−0.0034	0.057*
C5	0.1595 (4)	0.1955 (3)	0.0018 (2)	0.0453 (8)
H5	0.1559	0.1847	−0.0637	0.054*
C6	0.2079 (3)	0.1210 (3)	0.0667 (2)	0.0331 (6)
C7	0.2632 (5)	0.0403 (4)	−0.1324 (3)	0.0605 (10)
H7A	0.1546	0.0238	−0.1664	0.091*
H7B	0.3021	0.0037	−0.1754	0.091*
H7C	0.3289	0.1338	−0.1134	0.091*
C8	0.2695 (4)	−0.0226 (3)	−0.0424 (2)	0.0421 (7)
C9	0.2988 (4)	−0.1298 (3)	−0.0245 (3)	0.0484 (8)
H9	0.3181	−0.1806	−0.0676	0.058*
C10	0.2944 (4)	−0.1488 (3)	0.0707 (3)	0.0444 (8)
C11	0.3113 (5)	−0.2561 (4)	0.1247 (3)	0.0666 (11)
H11A	0.4186	−0.2238	0.1694	0.100*
H11B	0.2892	−0.3304	0.0780	0.100*
H11C	0.2370	−0.2828	0.1611	0.100*
C12	0.0307 (4)	−0.2160 (3)	0.2893 (2)	0.0481 (8)
C13	0.1965 (3)	−0.2044 (3)	0.3486 (2)	0.0359 (7)
C14	0.2302 (4)	−0.2895 (3)	0.4077 (2)	0.0405 (7)
C15	0.3880 (4)	−0.2626 (3)	0.4558 (2)	0.0466 (8)
H15	0.4108	−0.3189	0.4966	0.056*
C16	0.5106 (4)	−0.1545 (3)	0.4443 (2)	0.0446 (8)
H16	0.6169	−0.1354	0.4771	0.054*
C17	0.4708 (3)	−0.0740 (3)	0.3816 (2)	0.0331 (6)
C18	0.6426 (4)	0.3362 (3)	0.2609 (3)	0.0595 (10)
H18A	0.5317	0.3178	0.2349	0.089*
H18B	0.6886	0.3486	0.2085	0.089*
H18C	0.6986	0.4149	0.3101	0.089*
C19	0.6568 (4)	0.2227 (3)	0.3066 (2)	0.0407 (7)
C20	0.7943 (4)	0.2036 (3)	0.3471 (2)	0.0456 (8)
H20	0.8981	0.2598	0.3502	0.055*
C21	0.7478 (3)	0.0879 (3)	0.3812 (2)	0.0398 (7)
C22	0.8476 (4)	0.0199 (4)	0.4272 (3)	0.0674 (11)
H22A	0.9540	0.0668	0.4241	0.101*
H22B	0.8008	−0.0689	0.3919	0.101*
H22C	0.8519	0.0181	0.4949	0.101*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0349 (2)	0.0417 (2)	0.0385 (2)	0.01931 (17)	0.01275 (16)	0.01578 (16)
Cl1	0.0640 (5)	0.0492 (5)	0.0682 (6)	0.0368 (4)	0.0159 (5)	0.0117 (4)
Cl2	0.0792 (7)	0.0425 (5)	0.0685 (6)	0.0132 (4)	0.0369 (5)	0.0254 (4)
N1	0.0250 (11)	0.0347 (13)	0.0303 (12)	0.0120 (10)	0.0074 (10)	0.0088 (10)
N2	0.0373 (13)	0.0372 (14)	0.0299 (13)	0.0158 (11)	0.0096 (11)	0.0087 (10)
N3	0.0433 (14)	0.0409 (14)	0.0388 (14)	0.0223 (12)	0.0131 (12)	0.0136 (11)
N4	0.0308 (12)	0.0356 (13)	0.0313 (12)	0.0144 (11)	0.0101 (10)	0.0109 (10)
N5	0.0297 (12)	0.0386 (14)	0.0354 (13)	0.0172 (11)	0.0058 (10)	0.0105 (11)
N6	0.0317 (13)	0.0386 (14)	0.0432 (14)	0.0171 (11)	0.0093 (11)	0.0151 (11)
O1	0.0644 (15)	0.0755 (17)	0.0426 (13)	0.0471 (14)	0.0236 (11)	0.0286 (12)
O2	0.094 (2)	0.087 (2)	0.0413 (14)	0.0615 (17)	0.0213 (14)	0.0092 (13)
O3	0.0385 (12)	0.0869 (19)	0.0636 (16)	0.0240 (13)	0.0163 (11)	0.0444 (15)
O4	0.0394 (15)	0.117 (3)	0.111 (3)	0.0099 (16)	0.0215 (15)	0.069 (2)
O5	0.0692 (18)	0.104 (2)	0.0615 (17)	0.0372 (17)	0.0076 (15)	0.0196 (16)
O6	0.0652 (19)	0.133 (3)	0.080 (2)	0.019 (2)	0.0139 (17)	−0.007 (2)
O7	0.072 (2)	0.211 (4)	0.0474 (17)	0.059 (2)	0.0128 (15)	0.008 (2)
O8	0.246 (6)	0.188 (5)	0.074 (2)	0.163 (4)	0.027 (3)	0.014 (3)
C1	0.0380 (16)	0.054 (2)	0.0366 (16)	0.0244 (15)	0.0141 (14)	0.0125 (15)
C2	0.0257 (14)	0.0333 (15)	0.0353 (15)	0.0110 (12)	0.0085 (12)	0.0059 (12)
C3	0.0320 (15)	0.0339 (16)	0.0462 (18)	0.0147 (13)	0.0083 (13)	0.0091 (13)
C4	0.053 (2)	0.049 (2)	0.0448 (19)	0.0280 (17)	0.0092 (16)	0.0218 (16)
C5	0.0541 (19)	0.052 (2)	0.0303 (16)	0.0250 (16)	0.0103 (14)	0.0120 (14)
C6	0.0276 (14)	0.0341 (15)	0.0316 (15)	0.0103 (12)	0.0052 (12)	0.0074 (12)
C7	0.077 (3)	0.069 (3)	0.043 (2)	0.034 (2)	0.0275 (19)	0.0136 (18)
C8	0.0354 (16)	0.0464 (19)	0.0366 (17)	0.0109 (14)	0.0112 (13)	0.0033 (14)
C9	0.0469 (19)	0.0461 (19)	0.053 (2)	0.0185 (16)	0.0208 (16)	−0.0001 (16)
C10	0.0394 (17)	0.0386 (18)	0.057 (2)	0.0178 (14)	0.0177 (15)	0.0094 (15)
C11	0.084 (3)	0.053 (2)	0.086 (3)	0.043 (2)	0.041 (2)	0.025 (2)
C12	0.0336 (17)	0.055 (2)	0.0461 (19)	0.0095 (16)	0.0134 (14)	0.0179 (16)
C13	0.0392 (16)	0.0363 (16)	0.0313 (15)	0.0129 (13)	0.0152 (13)	0.0094 (12)
C14	0.0547 (19)	0.0350 (16)	0.0340 (16)	0.0164 (15)	0.0216 (15)	0.0121 (13)
C15	0.066 (2)	0.0470 (19)	0.0388 (17)	0.0337 (17)	0.0184 (16)	0.0209 (15)
C16	0.0451 (18)	0.054 (2)	0.0394 (17)	0.0282 (16)	0.0082 (14)	0.0178 (15)
C17	0.0323 (15)	0.0373 (16)	0.0302 (14)	0.0164 (13)	0.0087 (12)	0.0078 (12)
C18	0.057 (2)	0.047 (2)	0.076 (3)	0.0202 (17)	0.025 (2)	0.0254 (19)
C19	0.0402 (17)	0.0364 (17)	0.0423 (17)	0.0142 (14)	0.0122 (14)	0.0088 (14)
C20	0.0285 (15)	0.0469 (19)	0.054 (2)	0.0098 (14)	0.0124 (14)	0.0057 (15)
C21	0.0283 (15)	0.0466 (18)	0.0399 (17)	0.0165 (14)	0.0047 (13)	0.0035 (14)
C22	0.0401 (19)	0.086 (3)	0.088 (3)	0.039 (2)	0.0181 (19)	0.035 (2)

Geometric parameters (Å, º) top

Cu1—N1	1.969 (2)	C3—C4	1.382 (4)
Cu1—N4	2.000 (2)	C4—C5	1.373 (5)
Cu1—O1	2.073 (2)	C4—H4	0.9300
Cu1—N3	2.113 (3)	C5—C6	1.388 (4)
Cu1—O3	2.176 (2)	C5—H5	0.9300
Cu1—N6	2.214 (2)	C7—C8	1.495 (4)
Cl1—C3	1.730 (3)	C7—H7A	0.9600
Cl2—C14	1.722 (3)	C7—H7B	0.9600
N1—C6	1.327 (4)	C7—H7C	0.9600
N1—C2	1.347 (4)	C8—C9	1.366 (5)
N2—C8	1.370 (4)	C9—C10	1.398 (5)
N2—N3	1.382 (3)	C9—H9	0.9300
N2—C6	1.408 (4)	C10—C11	1.500 (4)
N3—C10	1.318 (4)	C11—H11A	0.9600
N4—C17	1.329 (3)	C11—H11B	0.9600
N4—C13	1.354 (3)	C11—H11C	0.9600
N5—C21	1.378 (4)	C12—C13	1.538 (4)
N5—N6	1.381 (3)	C13—C14	1.382 (4)
N5—C17	1.409 (4)	C14—C15	1.383 (4)
N6—C19	1.323 (4)	C15—C16	1.364 (4)
O1—C1	1.256 (4)	C15—H15	0.9300
O2—C1	1.229 (4)	C16—C17	1.392 (4)
O3—C12	1.235 (4)	C16—H16	0.9300
O4—C12	1.225 (4)	C18—C19	1.497 (4)
O5—H5A	0.8500	C18—H18A	0.9600
O5—H5B	0.8500	C18—H18B	0.9600
O6—H6A	0.8501	C18—H18C	0.9600
O6—H6B	0.8500	C19—C20	1.400 (4)
O7—H7D	0.8499	C20—C21	1.353 (4)
O7—H7E	0.8501	C20—H20	0.9300
O8—H8A	0.8501	C21—C22	1.497 (4)
O8—H8B	0.8500	C22—H22A	0.9600
C1—C2	1.534 (4)	C22—H22B	0.9600
C2—C3	1.386 (4)	C22—H22C	0.9600

N1—Cu1—N4	179.30 (9)	H7A—C7—H7B	109.5
N1—Cu1—O1	79.35 (9)	C8—C7—H7C	109.5
N4—Cu1—O1	101.05 (9)	H7A—C7—H7C	109.5
N1—Cu1—N3	77.32 (9)	H7B—C7—H7C	109.5
N4—Cu1—N3	102.32 (9)	C9—C8—N2	106.0 (3)
O1—Cu1—N3	156.38 (9)	C9—C8—C7	128.8 (3)
N1—Cu1—O3	103.12 (9)	N2—C8—C7	125.2 (3)
N4—Cu1—O3	77.47 (9)	C8—C9—C10	107.2 (3)
O1—Cu1—O3	90.45 (11)	C8—C9—H9	126.4
N3—Cu1—O3	91.28 (10)	C10—C9—H9	126.4
N1—Cu1—N6	103.57 (9)	N3—C10—C9	110.2 (3)
N4—Cu1—N6	75.84 (9)	N3—C10—C11	120.7 (3)
O1—Cu1—N6	94.00 (10)	C9—C10—C11	129.0 (3)
N3—Cu1—N6	94.97 (10)	C10—C11—H11A	109.5
O3—Cu1—N6	153.30 (9)	C10—C11—H11B	109.5
C6—N1—C2	122.1 (2)	H11A—C11—H11B	109.5
C6—N1—Cu1	120.64 (19)	C10—C11—H11C	109.5
C2—N1—Cu1	117.06 (18)	H11A—C11—H11C	109.5
C8—N2—N3	110.4 (2)	H11B—C11—H11C	109.5
C8—N2—C6	133.3 (2)	O4—C12—O3	126.5 (3)
N3—N2—C6	116.2 (2)	O4—C12—C13	118.1 (3)
C10—N3—N2	106.1 (2)	O3—C12—C13	115.4 (3)
C10—N3—Cu1	141.9 (2)	N4—C13—C14	119.0 (3)
N2—N3—Cu1	111.56 (18)	N4—C13—C12	113.3 (2)
C17—N4—C13	121.4 (2)	C14—C13—C12	127.6 (3)
C17—N4—Cu1	120.97 (18)	C13—C14—C15	119.5 (3)
C13—N4—Cu1	117.61 (18)	C13—C14—Cl2	122.9 (2)
C21—N5—N6	110.6 (2)	C15—C14—Cl2	117.6 (2)
C21—N5—C17	132.6 (2)	C16—C15—C14	120.9 (3)
N6—N5—C17	116.7 (2)	C16—C15—H15	119.6
C19—N6—N5	105.3 (2)	C14—C15—H15	119.6
C19—N6—Cu1	142.4 (2)	C15—C16—C17	117.6 (3)
N5—N6—Cu1	109.55 (16)	C15—C16—H16	121.2
C1—O1—Cu1	115.75 (19)	C17—C16—H16	121.2
C12—O3—Cu1	114.4 (2)	N4—C17—C16	121.6 (3)
H5A—O5—H5B	108.1	N4—C17—N5	114.6 (2)
H6A—O6—H6B	108.5	C16—C17—N5	123.8 (3)
H7D—O7—H7E	108.8	C19—C18—H18A	109.5
H8A—O8—H8B	108.4	C19—C18—H18B	109.5
O2—C1—O1	127.3 (3)	H18A—C18—H18B	109.5
O2—C1—C2	118.0 (3)	C19—C18—H18C	109.5
O1—C1—C2	114.7 (3)	H18A—C18—H18C	109.5
N1—C2—C3	118.9 (3)	H18B—C18—H18C	109.5
N1—C2—C1	112.4 (2)	N6—C19—C20	110.7 (3)
C3—C2—C1	128.7 (3)	N6—C19—C18	120.5 (3)
C4—C3—C2	119.1 (3)	C20—C19—C18	128.8 (3)
C4—C3—Cl1	117.9 (2)	C21—C20—C19	107.2 (3)
C2—C3—Cl1	122.9 (2)	C21—C20—H20	126.4
C5—C4—C3	121.1 (3)	C19—C20—H20	126.4
C5—C4—H4	119.4	C20—C21—N5	106.1 (3)
C3—C4—H4	119.4	C20—C21—C22	128.5 (3)
C4—C5—C6	117.3 (3)	N5—C21—C22	125.4 (3)
C4—C5—H5	121.3	C21—C22—H22A	109.5
C6—C5—H5	121.3	C21—C22—H22B	109.5
N1—C6—C5	121.3 (3)	H22A—C22—H22B	109.5
N1—C6—N2	113.4 (2)	C21—C22—H22C	109.5
C5—C6—N2	125.2 (3)	H22A—C22—H22C	109.5
C8—C7—H7A	109.5	H22B—C22—H22C	109.5
C8—C7—H7B	109.5

O1—Cu1—N1—C6	−178.1 (2)	N1—C2—C3—Cl1	175.8 (2)
N3—Cu1—N1—C6	−1.8 (2)	C1—C2—C3—Cl1	−5.3 (4)
O3—Cu1—N1—C6	−90.2 (2)	C2—C3—C4—C5	1.1 (5)
N6—Cu1—N1—C6	90.3 (2)	Cl1—C3—C4—C5	−176.7 (3)
O1—Cu1—N1—C2	−2.46 (19)	C3—C4—C5—C6	0.0 (5)
N3—Cu1—N1—C2	173.8 (2)	C2—N1—C6—C5	−0.7 (4)
O3—Cu1—N1—C2	85.5 (2)	Cu1—N1—C6—C5	174.8 (2)
N6—Cu1—N1—C2	−94.04 (19)	C2—N1—C6—N2	−178.7 (2)
C8—N2—N3—C10	−0.6 (3)	Cu1—N1—C6—N2	−3.3 (3)
C6—N2—N3—C10	175.6 (2)	C4—C5—C6—N1	−0.2 (4)
C8—N2—N3—Cu1	173.32 (18)	C4—C5—C6—N2	177.6 (3)
C6—N2—N3—Cu1	−10.5 (3)	C8—N2—C6—N1	−175.6 (3)
N1—Cu1—N3—C10	177.1 (4)	N3—N2—C6—N1	9.3 (3)
N4—Cu1—N3—C10	−2.3 (4)	C8—N2—C6—C5	6.4 (5)
O1—Cu1—N3—C10	−173.8 (3)	N3—N2—C6—C5	−168.7 (3)
O3—Cu1—N3—C10	−79.8 (3)	N3—N2—C8—C9	−0.1 (3)
N6—Cu1—N3—C10	74.3 (3)	C6—N2—C8—C9	−175.3 (3)
N1—Cu1—N3—N2	6.59 (17)	N3—N2—C8—C7	−178.5 (3)
N4—Cu1—N3—N2	−172.80 (17)	C6—N2—C8—C7	6.2 (5)
O1—Cu1—N3—N2	15.7 (4)	N2—C8—C9—C10	0.6 (3)
O3—Cu1—N3—N2	109.75 (18)	C7—C8—C9—C10	179.0 (3)
N6—Cu1—N3—N2	−96.23 (18)	N2—N3—C10—C9	1.0 (3)
O1—Cu1—N4—C17	−98.3 (2)	Cu1—N3—C10—C9	−169.8 (3)
N3—Cu1—N4—C17	85.1 (2)	N2—N3—C10—C11	−177.1 (3)
O3—Cu1—N4—C17	173.7 (2)	Cu1—N3—C10—C11	12.1 (5)
N6—Cu1—N4—C17	−7.0 (2)	C8—C9—C10—N3	−1.1 (4)
O1—Cu1—N4—C13	82.6 (2)	C8—C9—C10—C11	176.9 (3)
N3—Cu1—N4—C13	−94.0 (2)	Cu1—O3—C12—O4	166.2 (4)
O3—Cu1—N4—C13	−5.4 (2)	Cu1—O3—C12—C13	−14.6 (4)
N6—Cu1—N4—C13	173.9 (2)	C17—N4—C13—C14	−0.6 (4)
C21—N5—N6—C19	−0.4 (3)	Cu1—N4—C13—C14	178.5 (2)
C17—N5—N6—C19	177.3 (3)	C17—N4—C13—C12	−179.0 (3)
C21—N5—N6—Cu1	165.40 (19)	Cu1—N4—C13—C12	0.1 (3)
C17—N5—N6—Cu1	−16.9 (3)	O4—C12—C13—N4	−170.4 (3)
N1—Cu1—N6—C19	−10.0 (4)	O3—C12—C13—N4	10.2 (4)
N4—Cu1—N6—C19	169.6 (4)	O4—C12—C13—C14	11.3 (6)
O1—Cu1—N6—C19	−90.0 (4)	O3—C12—C13—C14	−168.1 (3)
N3—Cu1—N6—C19	68.2 (4)	N4—C13—C14—C15	2.0 (4)
O3—Cu1—N6—C19	171.0 (3)	C12—C13—C14—C15	−179.9 (3)
N1—Cu1—N6—N5	−167.16 (17)	N4—C13—C14—Cl2	−177.5 (2)
N4—Cu1—N6—N5	12.44 (17)	C12—C13—C14—Cl2	0.7 (5)
O1—Cu1—N6—N5	112.84 (18)	C13—C14—C15—C16	−1.2 (5)
N3—Cu1—N6—N5	−89.03 (18)	Cl2—C14—C15—C16	178.2 (3)
O3—Cu1—N6—N5	13.8 (3)	C14—C15—C16—C17	−0.8 (5)
N1—Cu1—O1—C1	−3.6 (2)	C13—N4—C17—C16	−1.5 (4)
N4—Cu1—O1—C1	175.8 (2)	Cu1—N4—C17—C16	179.4 (2)
N3—Cu1—O1—C1	−12.7 (4)	C13—N4—C17—N5	179.0 (2)
O3—Cu1—O1—C1	−106.9 (2)	Cu1—N4—C17—N5	−0.1 (3)
N6—Cu1—O1—C1	99.4 (2)	C15—C16—C17—N4	2.2 (5)
N1—Cu1—O3—C12	−168.9 (3)	C15—C16—C17—N5	−178.4 (3)
N4—Cu1—O3—C12	11.5 (3)	C21—N5—C17—N4	−170.6 (3)
O1—Cu1—O3—C12	−89.7 (3)	N6—N5—C17—N4	12.3 (4)
N3—Cu1—O3—C12	113.9 (3)	C21—N5—C17—C16	9.9 (5)
N6—Cu1—O3—C12	10.1 (4)	N6—N5—C17—C16	−167.1 (3)
Cu1—O1—C1—O2	−171.3 (3)	N5—N6—C19—C20	0.5 (3)
Cu1—O1—C1—C2	8.2 (3)	Cu1—N6—C19—C20	−157.2 (3)
C6—N1—C2—C3	1.7 (4)	N5—N6—C19—C18	−178.7 (3)
Cu1—N1—C2—C3	−173.9 (2)	Cu1—N6—C19—C18	23.6 (5)
C6—N1—C2—C1	−177.4 (2)	N6—C19—C20—C21	−0.4 (4)
Cu1—N1—C2—C1	7.0 (3)	C18—C19—C20—C21	178.7 (3)
O2—C1—C2—N1	169.5 (3)	C19—C20—C21—N5	0.2 (4)
O1—C1—C2—N1	−10.0 (4)	C19—C20—C21—C22	177.2 (4)
O2—C1—C2—C3	−9.5 (5)	N6—N5—C21—C20	0.1 (3)
O1—C1—C2—C3	171.0 (3)	C17—N5—C21—C20	−177.1 (3)
N1—C2—C3—C4	−1.9 (4)	N6—N5—C21—C22	−177.0 (3)
C1—C2—C3—C4	177.0 (3)	C17—N5—C21—C22	5.8 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6	0.85	1.96	2.804 (4)	170
O5—H5B···O4ⁱ	0.85	1.98	2.818 (4)	170
O6—H6A···O2	0.85	2.24	3.090 (5)	176
O6—H6B···O7ⁱⁱ	0.85	1.85	2.697 (4)	176
O8—H8A···O5	0.85	2.10	2.947 (5)	178
O8—H8B···O5ⁱⁱⁱ	0.85	1.98	2.825 (5)	179

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₁H₉ClN₃O₂)₂]·4H₂O
M_r	636.93
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.6578 (9), 11.2637 (14), 14.3127 (18)
α, β, γ (°)	92.349 (2), 106.090 (2), 114.065 (3)
V (Å³)	1344.7 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.07
Crystal size (mm)	0.59 × 0.52 × 0.50

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.571, 0.617
No. of measured, independent and observed [I > 2σ(I)] reflections	7014, 4664, 3789
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.101, 1.03
No. of reflections	4664
No. of parameters	352
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.48

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O6	0.85	1.96	2.804 (4)	169.7
O5—H5B···O4ⁱ	0.85	1.98	2.818 (4)	169.5
O6—H6A···O2	0.85	2.24	3.090 (5)	175.7
O6—H6B···O7ⁱⁱ	0.85	1.85	2.697 (4)	175.9
O8—H8A···O5	0.85	2.10	2.947 (5)	178.4
O8—H8B···O5ⁱⁱⁱ	0.85	1.98	2.825 (5)	178.8

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

Acknowledgements

The authors thank the National Natural Science Foundation of China (grant No. 20761002). This research was sponsored by the Talent Highland research program of Guangxi University (grant No. 205121), the Science Foundation of the State Ethnic Affairs Commission (grant No. 07GX05), the Development Foundation Guangxi Research Institute of Chemical Industry, and the Science Foundation of Guangxi University for Nationalities (grant Nos. 0409032, 0409012 and 0509ZD047).

References

Aliev, Z. G., Atovmyan, L. O. & Saratovskikh, E. A. (1988). lzv. Akad. Nauk. SSSR Khim. pp. 2495–2501. Google Scholar
Bhatia, S. C., Bindlish, J. M., Saini, A. R. & Jain, P. C. (1981). J. Chem. Soc. Dalton Trans. pp. 1773–1779. CSD CrossRef Web of Science Google Scholar
Costamagna, J., Vargas, J., Latorre, R. & Alvarado, A. (1992). Coord. Chem. Rev. 119, 67–88. CrossRef CAS Web of Science Google Scholar
Kai, Z., Yin, X.-H., Zhang, S.-S., Zhuang, Y. & Hu, F.-L. (2007). Acta Cryst. E63, o4801. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kuang, S. M., Zhang, Z. Z. & Wang, Q. G. (1997). J. Chem. Soc. Dalton Trans. pp. 4477–4478. Web of Science CSD CrossRef Google Scholar
Ramazani, A., Morsali, A. & Jamali, F. (2002). Z. Kristallogr. New Cryst. Struct. 217, 228–229. CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Xu, A.-W., Su, C.-Y., Zhang, Z.-F., Cai, Y.-P. & Chen, C.-L. (2001). New J. Chem. 25, 479–482. Web of Science CSD CrossRef CAS Google Scholar
Yaghi, O. M. & Li, H. (1996). J. Am. Chem. Soc. 118, 295–296. CSD CrossRef CAS Web of Science Google Scholar
Yin, X.-H., Zhao, K., Feng, Y. & Zhu, J. (2007). Acta Cryst. E63, m2926. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhao, K., Yin, X.-H., Feng, Y. & Zhu, J. (2007). Acta Cryst. E63, m3023. Web of Science CSD CrossRef IUCr Journals Google Scholar

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