Aqua­tris(1H-benzimidazole-κN3)(dichloro­acetato-κO)copper(II) dichloro­acetate dihydrate

Li, Y.-F.; Jian, F.-F.

doi:10.1107/S1600536809038392

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page m1249

doi:10.1107/S1600536809038392

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Aquatris(1H-benzimidazole-κN³)(dichloroacetato-κO)copper(II) dichloroacetate dihydrate

Yu-Feng Li ^a and Fang-Fang Jian ^b ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, and ^bMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: ffjian2008@163.com

(Received 21 August 2009; accepted 22 September 2009; online 26 September 2009)

The title compound, [Cu(C₂HCl₂O₂)(C₇H₆N₂)₃(H₂O)]C₂HCl₂O₂·2H₂O, was prepared by reaction of copper(II) 2,2-dichloroacetic acid and benzimidazole in ethanol solution. The compound shows a regular trigonal–bipyramidal stereochemistry. The Cu^II centre possesses a five-coordinated environment, coordinated by three N atoms from the three benzimidazole ligands and two O atoms, one from the dichloroacetate ligand and the other from the coordinated water molecule. The molecular structure and packing are stabilized by O—H⋯O and N—H⋯O hydrogen bonds. The Cl atoms are disordered over two sites, with relative occupancies 0.67 (3) and 0.33 (3).

Related literature

For background to penta-coordinated copper complexes, see: Tyagi et al. (1984 ). For a related compound, see: Barszcz et al. (2004 ).

Experimental

Crystal data

[Cu(C₂HCl₂O₂)(C₇H₆N₂)₃(H₂O)]C₂HCl₂O₂·2H₂O
M_r = 727.86
Monoclinic, P 2₁ /n
a = 9.6027 (16) Å
b = 8.6957 (15) Å
c = 37.799 (6) Å
β = 93.945 (3)°
V = 3148.8 (9) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 293 K
0.23 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
19614 measured reflections
7576 independent reflections
5174 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.122
S = 1.04
7576 reflections
488 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.00 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1B⋯O3ⁱ	0.808 (18)	1.955 (18)	2.763 (3)	178 (4)
O1W—H1C⋯O2W	0.802 (18)	2.18 (2)	2.949 (3)	162 (3)
N2—H2⋯O2Wⁱⁱ	0.820 (17)	2.08 (2)	2.873 (3)	162 (3)
N4—H4⋯O3Wⁱⁱⁱ	0.856 (18)	2.00 (2)	2.842 (3)	166 (4)
N6—H6⋯O2^iv	0.836 (18)	1.991 (19)	2.826 (3)	176 (3)
O2W—H2B⋯O3W	0.835 (18)	2.01 (2)	2.832 (3)	168 (4)
O2W—H2C⋯O4^iv	0.810 (18)	2.080 (19)	2.886 (3)	172 (4)
O3W—H3B⋯O3	0.831 (17)	2.01 (2)	2.813 (4)	164 (3)
O3W—H3C⋯O4ⁱ	0.841 (17)	1.925 (18)	2.757 (3)	170 (4)
C15—H15A⋯O2	0.91 (3)	2.58 (3)	3.416 (4)	152 (3)
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x-1, y, z; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) x, y+1, z.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); 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 global, I. DOI: 10.1107/S1600536809038392/br2115sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809038392/br2115Isup2.hkl

checkCIF report

Comment top

The penta-coordinated copper complexes have been attracting great interest for their diverse stereo and physicochemical properties (Tyagi et al., 1984). Therefore the coordination chemistry of Cu(II) with ligands is of great interest. In this paper, we reported the synthesis and crystal structure of the title compound.

In the crystal structure of the title compound (Fig. 1), all the bond length and angle are in the normal range. (Barszcz et al., 2004). The title compound consists of discrete monovalent complex cations, dichloroacetic acid anion and solvent water molecules. The dichloroacetic ions appear to be loosely held in lattice holes by Coulombic forces and by weak hydrogen bonds to the solvent water molecules. The interionic hydrogen bonds play an important role in the crystal packing and the stability of the complex. The Cl1 and Cl2 atoms are disordered.

Related literature top

For background to penta-coordinated copper complexes, see: Tyagi et al. (1984). For a related compound, see: Barszcz et al. (2004).

Experimental top

Solid copper(II) 2,2-dicholoracetate, C₄H₂Cl₄Cu₁O₄ 0.32 g (1 mmol) and benzimidazole 0.35 g (3 mmol) were added in 50 ml anhydrous alcohol under stirring. The mixture was refluxed for 5 h. The blue solution was filtered and the filtrate was left to stand undisturbed. Upon slow evaporation at room temperature, a blue crystalline solid appeared three days later and was separated by filtration. Determined by X-ray crystallography.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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 and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level.

Aquatris(1H-benzimidazole-κN³)(dichloroacetato- κO)copper(II) dichloroacetate dihydrate top

Crystal data top

[Cu(C₂HCl₂O₂)(C₇H₆N₂)₃(H₂O)]C₂HCl₂O₂·2H₂O	F(000) = 1484
M_r = 727.86	D_x = 1.535 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2360 reflections
a = 9.6027 (16) Å	θ = 2.3–28.2°
b = 8.6957 (15) Å	µ = 1.09 mm⁻¹
c = 37.799 (6) Å	T = 293 K
β = 93.945 (3)°	Block, blue
V = 3148.8 (9) Å³	0.23 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	5174 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 28.2°, θ_min = 2.2°
ϕ and ω scans	h = −12→10
19614 measured reflections	k = −11→11
7576 independent reflections	l = −34→50

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0529P)² + 1.2061P] where P = (F_o² + 2F_c²)/3
7576 reflections	(Δ/σ)_max = 0.001
488 parameters	Δρ_max = 1.00 e Å⁻³
10 restraints	Δρ_min = −0.59 e Å⁻³

Crystal data top

[Cu(C₂HCl₂O₂)(C₇H₆N₂)₃(H₂O)]C₂HCl₂O₂·2H₂O	V = 3148.8 (9) Å³
M_r = 727.86	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6027 (16) Å	µ = 1.09 mm⁻¹
b = 8.6957 (15) Å	T = 293 K
c = 37.799 (6) Å	0.23 × 0.20 × 0.18 mm
β = 93.945 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	5174 reflections with I > 2σ(I)
19614 measured reflections	R_int = 0.036
7576 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	10 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 1.00 e Å⁻³
7576 reflections	Δρ_min = −0.59 e Å⁻³
488 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	Occ. (<1)
Cu1	0.55853 (3)	0.58911 (4)	0.621230 (8)	0.03147 (11)
Cl1A	0.8686 (6)	0.1449 (6)	0.63210 (11)	0.0763 (11)	0.67 (3)
Cl2A	0.9346 (9)	0.2214 (14)	0.56111 (10)	0.087 (2)	0.67 (3)
Cl1B	0.8843 (14)	0.1269 (15)	0.6237 (7)	0.107 (4)	0.33 (3)
Cl2B	0.9719 (14)	0.298 (3)	0.5610 (2)	0.096 (3)	0.33 (3)
O1	0.7499 (2)	0.5103 (2)	0.61458 (6)	0.0418 (5)
O2	0.6514 (2)	0.3248 (2)	0.58070 (6)	0.0461 (5)
O1W	0.6458 (2)	0.7384 (3)	0.66834 (6)	0.0456 (5)
H1B	0.619 (3)	0.741 (4)	0.6881 (6)	0.055*
H1C	0.729 (2)	0.749 (4)	0.6710 (9)	0.055*
N1	0.3528 (2)	0.6367 (3)	0.62332 (6)	0.0353 (5)
N2	0.1489 (3)	0.6637 (3)	0.64701 (7)	0.0439 (6)
H2	0.096 (3)	0.671 (4)	0.6629 (7)	0.044 (9)*
N3	0.5337 (2)	0.4060 (3)	0.65180 (6)	0.0352 (5)
N4	0.5672 (3)	0.2358 (3)	0.69497 (7)	0.0430 (6)
H4	0.603 (3)	0.193 (4)	0.7139 (7)	0.066 (12)*
N5	0.5864 (2)	0.7632 (3)	0.58822 (6)	0.0319 (5)
N6	0.6065 (3)	1.0057 (3)	0.57153 (7)	0.0407 (6)
H6	0.619 (4)	1.100 (2)	0.5752 (9)	0.058 (11)*
C1	0.2615 (3)	0.6892 (4)	0.55998 (9)	0.0503 (8)
H1A	0.353 (4)	0.666 (4)	0.5496 (9)	0.060*
C2	0.1406 (4)	0.7264 (6)	0.53993 (11)	0.0736 (13)
H2A	0.145 (4)	0.736 (5)	0.5136 (11)	0.088*
C3	0.0141 (4)	0.7475 (6)	0.55558 (13)	0.0830 (14)
H3A	−0.060 (3)	0.783 (5)	0.5426 (10)	0.100*
C4	0.0025 (4)	0.7312 (5)	0.59114 (12)	0.0609 (10)
H4A	−0.085 (4)	0.737 (4)	0.6013 (10)	0.073*
C5	0.1233 (3)	0.6914 (3)	0.61125 (9)	0.0409 (7)
C6	0.2516 (3)	0.6730 (3)	0.59624 (8)	0.0364 (6)
C7	0.2861 (3)	0.6327 (4)	0.65275 (9)	0.0430 (7)
H6A	0.330 (3)	0.608 (4)	0.6749 (9)	0.052*
C8	0.3385 (3)	0.2603 (4)	0.61785 (8)	0.0408 (7)
H8A	0.323 (3)	0.327 (4)	0.6009 (9)	0.049*
C9	0.2590 (3)	0.1300 (4)	0.61945 (10)	0.0486 (8)
H9A	0.188 (4)	0.110 (4)	0.6006 (9)	0.058*
C10	0.2782 (4)	0.0263 (4)	0.64766 (10)	0.0515 (9)
H10A	0.219 (4)	−0.060 (4)	0.6483 (9)	0.062*
C11	0.3790 (4)	0.0449 (4)	0.67445 (9)	0.0459 (8)
H11A	0.397 (3)	−0.027 (4)	0.6935 (9)	0.055*
C12	0.4602 (3)	0.1785 (3)	0.67299 (7)	0.0347 (6)
C13	0.4394 (3)	0.2852 (3)	0.64544 (7)	0.0330 (6)
C14	0.6067 (3)	0.3692 (4)	0.68129 (8)	0.0413 (7)
H14A	0.685 (3)	0.428 (4)	0.6910 (8)	0.050*
C15	0.6404 (4)	0.6474 (4)	0.52901 (8)	0.0463 (8)
H15A	0.634 (3)	0.546 (4)	0.5351 (9)	0.056*
C16	0.6743 (4)	0.6869 (5)	0.49547 (9)	0.0633 (10)
H16A	0.690 (4)	0.609 (5)	0.4791 (11)	0.076*
C17	0.6901 (4)	0.8402 (5)	0.48565 (9)	0.0620 (10)
H17A	0.717 (4)	0.858 (4)	0.4628 (10)	0.074*
C18	0.6700 (4)	0.9586 (5)	0.50846 (9)	0.0509 (9)
H18A	0.683 (4)	1.060 (4)	0.5054 (9)	0.061*
C19	0.6356 (3)	0.9184 (3)	0.54269 (7)	0.0361 (6)
C20	0.6221 (3)	0.7658 (3)	0.55289 (7)	0.0310 (6)
C21	0.5786 (3)	0.9084 (4)	0.59758 (8)	0.0376 (6)
H21A	0.559 (3)	0.941 (4)	0.6204 (8)	0.045*
C22	0.7507 (3)	0.3848 (3)	0.59806 (8)	0.0397 (7)
C23	0.8912 (4)	0.3007 (4)	0.60214 (9)	0.0517 (8)
H23	0.963 (4)	0.356 (4)	0.6143 (9)	0.062*
Cl3	1.08746 (13)	0.35382 (14)	0.69629 (3)	0.0815 (3)
Cl4	1.26119 (11)	0.22307 (19)	0.75391 (3)	0.0951 (4)
O3	0.9457 (3)	0.2538 (3)	0.76400 (7)	0.0684 (8)
O4	0.9295 (3)	0.0293 (3)	0.73571 (7)	0.0609 (7)
C24	0.9847 (3)	0.1547 (4)	0.74289 (8)	0.0446 (7)
C25	1.1158 (3)	0.1918 (4)	0.72357 (9)	0.0481 (8)
H25	1.136 (4)	0.111 (4)	0.7106 (9)	0.058*
O2W	0.9420 (3)	0.7505 (3)	0.69464 (6)	0.0511 (6)
H2B	0.924 (4)	0.685 (3)	0.7097 (8)	0.061*
H2C	0.946 (4)	0.830 (3)	0.7056 (9)	0.061*
O3W	0.8433 (2)	0.5492 (3)	0.74611 (6)	0.0478 (5)
H3B	0.878 (4)	0.467 (3)	0.7505 (10)	0.057*
H3C	0.762 (2)	0.530 (4)	0.7494 (10)	0.057*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03492 (19)	0.02875 (19)	0.03115 (18)	−0.00259 (14)	0.00518 (13)	0.00311 (14)
Cl1A	0.085 (2)	0.070 (2)	0.071 (3)	0.0185 (14)	−0.0159 (12)	0.0213 (11)
Cl2A	0.073 (2)	0.126 (4)	0.0618 (12)	0.044 (2)	0.0070 (12)	−0.0200 (18)
Cl1B	0.057 (4)	0.039 (3)	0.217 (10)	−0.003 (3)	−0.046 (5)	0.023 (5)
Cl2B	0.078 (4)	0.136 (9)	0.075 (3)	0.024 (5)	0.022 (3)	−0.024 (4)
O1	0.0390 (11)	0.0322 (11)	0.0552 (13)	−0.0025 (9)	0.0103 (9)	−0.0024 (10)
O2	0.0464 (12)	0.0340 (12)	0.0569 (13)	0.0046 (10)	−0.0030 (11)	−0.0003 (10)
O1W	0.0436 (12)	0.0581 (14)	0.0352 (11)	−0.0098 (11)	0.0024 (10)	−0.0060 (11)
N1	0.0392 (13)	0.0310 (13)	0.0363 (13)	−0.0004 (10)	0.0078 (10)	0.0054 (10)
N2	0.0443 (15)	0.0372 (15)	0.0529 (17)	−0.0025 (12)	0.0223 (13)	0.0032 (13)
N3	0.0381 (13)	0.0335 (13)	0.0338 (12)	−0.0063 (11)	−0.0001 (10)	0.0037 (10)
N4	0.0485 (15)	0.0453 (16)	0.0346 (14)	0.0015 (12)	−0.0015 (12)	0.0098 (12)
N5	0.0365 (12)	0.0289 (13)	0.0308 (12)	−0.0034 (10)	0.0065 (10)	0.0005 (10)
N6	0.0528 (16)	0.0266 (14)	0.0429 (14)	−0.0026 (12)	0.0058 (12)	0.0014 (12)
C1	0.0384 (17)	0.069 (2)	0.0433 (18)	−0.0134 (17)	0.0011 (14)	0.0042 (17)
C2	0.048 (2)	0.117 (4)	0.054 (2)	−0.020 (2)	−0.0085 (18)	0.020 (2)
C3	0.043 (2)	0.117 (4)	0.086 (3)	−0.012 (2)	−0.017 (2)	0.027 (3)
C4	0.0322 (18)	0.064 (2)	0.087 (3)	−0.0074 (16)	0.0059 (18)	0.013 (2)
C5	0.0346 (16)	0.0293 (16)	0.060 (2)	−0.0075 (13)	0.0093 (14)	0.0026 (14)
C6	0.0340 (15)	0.0343 (16)	0.0415 (16)	−0.0073 (12)	0.0054 (12)	0.0032 (13)
C7	0.0467 (18)	0.0417 (18)	0.0420 (17)	−0.0009 (14)	0.0138 (14)	0.0073 (14)
C8	0.0416 (17)	0.0400 (18)	0.0405 (17)	−0.0003 (14)	0.0002 (14)	−0.0006 (14)
C9	0.0414 (18)	0.048 (2)	0.057 (2)	−0.0067 (15)	0.0028 (15)	−0.0142 (16)
C10	0.052 (2)	0.0336 (18)	0.072 (2)	−0.0095 (15)	0.0215 (18)	−0.0107 (17)
C11	0.058 (2)	0.0296 (16)	0.053 (2)	0.0030 (15)	0.0230 (17)	0.0041 (14)
C12	0.0381 (15)	0.0333 (16)	0.0334 (15)	0.0015 (12)	0.0087 (12)	0.0015 (12)
C13	0.0348 (15)	0.0303 (15)	0.0345 (15)	−0.0005 (12)	0.0050 (12)	0.0019 (12)
C14	0.0432 (17)	0.0438 (19)	0.0360 (16)	−0.0045 (14)	−0.0034 (13)	0.0069 (13)
C15	0.059 (2)	0.0405 (18)	0.0392 (17)	0.0015 (16)	0.0032 (15)	−0.0056 (15)
C16	0.084 (3)	0.071 (3)	0.0350 (18)	0.008 (2)	0.0089 (18)	−0.0110 (18)
C17	0.076 (3)	0.082 (3)	0.0288 (17)	0.002 (2)	0.0124 (17)	0.0102 (18)
C18	0.057 (2)	0.053 (2)	0.0421 (18)	−0.0073 (17)	0.0058 (16)	0.0177 (17)
C19	0.0340 (14)	0.0395 (17)	0.0348 (15)	−0.0016 (13)	0.0032 (12)	0.0042 (13)
C20	0.0293 (13)	0.0349 (16)	0.0290 (13)	0.0001 (11)	0.0026 (11)	0.0011 (11)
C21	0.0438 (16)	0.0368 (16)	0.0331 (15)	0.0012 (13)	0.0092 (13)	0.0016 (13)
C22	0.0435 (17)	0.0339 (18)	0.0427 (17)	0.0025 (13)	0.0090 (14)	0.0057 (13)
C23	0.0475 (19)	0.052 (2)	0.055 (2)	0.0138 (16)	−0.0009 (16)	−0.0027 (17)
Cl3	0.1008 (8)	0.0806 (7)	0.0658 (6)	−0.0078 (6)	0.0254 (6)	0.0240 (6)
Cl4	0.0566 (6)	0.1605 (13)	0.0683 (7)	0.0004 (7)	0.0034 (5)	−0.0003 (7)
O3	0.0913 (19)	0.0503 (15)	0.0697 (16)	−0.0018 (13)	0.0500 (15)	−0.0059 (13)
O4	0.0587 (15)	0.0485 (15)	0.0781 (17)	−0.0107 (12)	0.0229 (13)	−0.0105 (13)
C24	0.0498 (18)	0.0414 (19)	0.0445 (18)	0.0068 (15)	0.0166 (15)	0.0040 (15)
C25	0.0519 (19)	0.049 (2)	0.0458 (18)	−0.0027 (16)	0.0185 (15)	−0.0044 (15)
O2W	0.0505 (13)	0.0561 (16)	0.0482 (14)	−0.0009 (12)	0.0135 (11)	−0.0052 (11)
O3W	0.0425 (13)	0.0501 (14)	0.0508 (13)	0.0010 (11)	0.0027 (11)	−0.0071 (11)

Geometric parameters (Å, º) top

Cu1—N3	1.991 (2)	C5—C6	1.400 (4)
Cu1—N5	1.992 (2)	C7—H6A	0.94 (3)
Cu1—O1	1.993 (2)	C8—C9	1.370 (4)
Cu1—N1	2.025 (2)	C8—C13	1.391 (4)
Cu1—O1W	2.314 (2)	C8—H8A	0.87 (3)
Cl1A—C23	1.789 (6)	C9—C10	1.399 (5)
Cl2A—C23	1.773 (5)	C9—H9A	0.97 (4)
Cl1B—C23	1.720 (11)	C10—C11	1.361 (5)
Cl2B—C23	1.784 (9)	C10—H10A	0.94 (4)
O1—C22	1.257 (3)	C11—C12	1.403 (4)
O2—C22	1.235 (4)	C11—H11A	0.96 (3)
O1W—H1B	0.808 (18)	C12—C13	1.399 (4)
O1W—H1C	0.803 (18)	C14—H14A	0.96 (3)
N1—C7	1.322 (4)	C15—C16	1.374 (5)
N1—C6	1.398 (4)	C15—C20	1.388 (4)
N2—C7	1.347 (4)	C15—H15A	0.91 (3)
N2—C5	1.378 (4)	C16—C17	1.395 (6)
N2—H2	0.820 (17)	C16—H16A	0.94 (4)
N3—C14	1.315 (4)	C17—C18	1.365 (6)
N3—C13	1.397 (4)	C17—H17A	0.93 (4)
N4—C14	1.336 (4)	C18—C19	1.401 (4)
N4—C12	1.370 (4)	C18—H18A	0.90 (4)
N4—H4	0.856 (18)	C19—C20	1.391 (4)
N5—C21	1.315 (4)	C21—H21A	0.94 (3)
N5—C20	1.401 (3)	C22—C23	1.533 (4)
N6—C21	1.339 (4)	C23—H23	0.93 (4)
N6—C19	1.373 (4)	Cl3—C25	1.756 (4)
N6—H6	0.835 (18)	Cl4—C25	1.766 (4)
C1—C2	1.380 (5)	O3—C24	1.249 (4)
C1—C6	1.388 (4)	O4—C24	1.235 (4)
C1—H1A	1.01 (3)	C24—C25	1.532 (4)
C2—C3	1.400 (6)	C25—H25	0.88 (3)
C2—H2A	1.00 (4)	O2W—H2B	0.835 (18)
C3—C4	1.364 (6)	O2W—H2C	0.809 (18)
C3—H3A	0.891 (19)	O3W—H3B	0.802 (18)
C4—C5	1.387 (5)	O3W—H3C	0.814 (18)
C4—H4A	0.95 (4)

N3—Cu1—N5	176.38 (9)	C10—C11—C12	116.0 (3)
N3—Cu1—O1	86.92 (9)	C10—C11—H11A	124 (2)
N5—Cu1—O1	91.01 (9)	C12—C11—H11A	120 (2)
N3—Cu1—N1	89.13 (9)	N4—C12—C13	105.8 (2)
N5—Cu1—N1	92.43 (9)	N4—C12—C11	132.3 (3)
O1—Cu1—N1	170.17 (9)	C13—C12—C11	121.8 (3)
N3—Cu1—O1W	93.07 (9)	C8—C13—N3	131.0 (3)
N5—Cu1—O1W	89.91 (9)	C8—C13—C12	120.8 (3)
O1—Cu1—O1W	90.11 (9)	N3—C13—C12	108.2 (2)
N1—Cu1—O1W	99.09 (9)	N3—C14—N4	113.0 (3)
C22—O1—Cu1	113.46 (19)	N3—C14—H14A	123 (2)
Cu1—O1W—H1B	127 (3)	N4—C14—H14A	123.4 (19)
Cu1—O1W—H1C	118 (3)	C16—C15—C20	117.6 (3)
H1B—O1W—H1C	105 (4)	C16—C15—H15A	120 (2)
C7—N1—C6	105.6 (2)	C20—C15—H15A	122 (2)
C7—N1—Cu1	123.9 (2)	C15—C16—C17	121.4 (4)
C6—N1—Cu1	130.43 (18)	C15—C16—H16A	119 (2)
C7—N2—C5	107.4 (3)	C17—C16—H16A	119 (2)
C7—N2—H2	123 (2)	C18—C17—C16	122.0 (3)
C5—N2—H2	129 (2)	C18—C17—H17A	121 (3)
C14—N3—C13	105.3 (2)	C16—C17—H17A	117 (2)
C14—N3—Cu1	127.5 (2)	C17—C18—C19	116.6 (3)
C13—N3—Cu1	127.11 (19)	C17—C18—H18A	129 (2)
C14—N4—C12	107.6 (3)	C19—C18—H18A	114 (2)
C14—N4—H4	127 (3)	N6—C19—C20	106.2 (2)
C12—N4—H4	126 (3)	N6—C19—C18	132.0 (3)
C21—N5—C20	105.3 (2)	C20—C19—C18	121.8 (3)
C21—N5—Cu1	123.29 (19)	C15—C20—C19	120.6 (3)
C20—N5—Cu1	131.40 (18)	C15—C20—N5	131.1 (3)
C21—N6—C19	107.3 (3)	C19—C20—N5	108.2 (2)
C21—N6—H6	122 (2)	N5—C21—N6	113.0 (3)
C19—N6—H6	129 (2)	N5—C21—H21A	124 (2)
C2—C1—C6	117.0 (3)	N6—C21—H21A	123 (2)
C2—C1—H1A	123.8 (19)	O2—C22—O1	126.9 (3)
C6—C1—H1A	119.0 (19)	O2—C22—C23	119.6 (3)
C1—C2—C3	121.4 (4)	O1—C22—C23	113.5 (3)
C1—C2—H2A	118 (2)	C22—C23—Cl1B	113.9 (7)
C3—C2—H2A	120 (2)	C22—C23—Cl2A	110.8 (3)
C4—C3—C2	122.3 (4)	Cl1B—C23—Cl2A	95.2 (7)
C4—C3—H3A	117 (3)	C22—C23—Cl2B	110.6 (4)
C2—C3—H3A	120 (3)	Cl1B—C23—Cl2B	115.6 (5)
C3—C4—C5	116.4 (3)	Cl2A—C23—Cl2B	24.5 (5)
C3—C4—H4A	122 (2)	C22—C23—Cl1A	106.3 (3)
C5—C4—H4A	121 (2)	Cl1B—C23—Cl1A	12.7 (10)
N2—C5—C4	131.9 (3)	Cl2A—C23—Cl1A	107.8 (4)
N2—C5—C6	105.9 (3)	Cl2B—C23—Cl1A	128.3 (8)
C4—C5—C6	122.2 (3)	C22—C23—H23	115 (2)
C1—C6—N1	130.9 (3)	Cl1B—C23—H23	106 (2)
C1—C6—C5	120.7 (3)	Cl2A—C23—H23	115 (2)
N1—C6—C5	108.4 (2)	Cl2B—C23—H23	95 (2)
N1—C7—N2	112.6 (3)	Cl1A—C23—H23	101 (2)
N1—C7—H6A	123 (2)	O4—C24—O3	127.3 (3)
N2—C7—H6A	124 (2)	O4—C24—C25	115.8 (3)
C9—C8—C13	117.2 (3)	O3—C24—C25	116.9 (3)
C9—C8—H8A	121 (2)	C24—C25—Cl3	110.5 (2)
C13—C8—H8A	122 (2)	C24—C25—Cl4	111.2 (2)
C8—C9—C10	121.5 (3)	Cl3—C25—Cl4	109.9 (2)
C8—C9—H9A	119 (2)	C24—C25—H25	108 (2)
C10—C9—H9A	120 (2)	Cl3—C25—H25	110 (2)
C11—C10—C9	122.7 (3)	Cl4—C25—H25	107 (2)
C11—C10—H10A	118 (2)	H2B—O2W—H2C	104 (4)
C9—C10—H10A	119 (2)	H3B—O3W—H3C	100 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1B···O3ⁱ	0.81 (2)	1.96 (2)	2.763 (3)	178 (4)
O1W—H1C···O2W	0.80 (2)	2.18 (2)	2.949 (3)	162 (3)
N2—H2···O2Wⁱⁱ	0.82 (2)	2.08 (2)	2.873 (3)	162 (3)
N4—H4···O3Wⁱⁱⁱ	0.86 (2)	2.00 (2)	2.842 (3)	166 (4)
N6—H6···O2^iv	0.84 (2)	1.99 (2)	2.826 (3)	176 (3)
O2W—H2B···O3W	0.84 (2)	2.01 (2)	2.832 (3)	168 (4)
O2W—H2C···O4^iv	0.81 (2)	2.08 (2)	2.886 (3)	172 (4)
O3W—H3B···O3	0.83 (2)	2.01 (2)	2.813 (4)	164 (3)
O3W—H3C···O4ⁱ	0.84 (2)	1.93 (2)	2.757 (3)	170 (4)
C15—H15A···O2	0.91 (3)	2.58 (3)	3.416 (4)	152 (3)

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−1, y, z; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₂HCl₂O₂)(C₇H₆N₂)₃(H₂O)]C₂HCl₂O₂·2H₂O
M_r	727.86
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.6027 (16), 8.6957 (15), 37.799 (6)
β (°)	93.945 (3)
V (Å³)	3148.8 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.23 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	19614, 7576, 5174
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.122, 1.04
No. of reflections	7576
No. of parameters	488
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.00, −0.59

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1B···O3ⁱ	0.808 (18)	1.955 (18)	2.763 (3)	178 (4)
O1W—H1C···O2W	0.802 (18)	2.18 (2)	2.949 (3)	162 (3)
N2—H2···O2Wⁱⁱ	0.820 (17)	2.08 (2)	2.873 (3)	162 (3)
N4—H4···O3Wⁱⁱⁱ	0.856 (18)	2.00 (2)	2.842 (3)	166 (4)
N6—H6···O2^iv	0.836 (18)	1.991 (19)	2.826 (3)	176 (3)
O2W—H2B···O3W	0.835 (18)	2.01 (2)	2.832 (3)	168 (4)
O2W—H2C···O4^iv	0.810 (18)	2.080 (19)	2.886 (3)	172 (4)
O3W—H3B···O3	0.831 (17)	2.01 (2)	2.813 (4)	164 (3)
O3W—H3C···O4ⁱ	0.841 (17)	1.925 (18)	2.757 (3)	170 (4)
C15—H15A···O2	0.91 (3)	2.58 (3)	3.416 (4)	152 (3)

Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x−1, y, z; (iii) −x+3/2, y−1/2, −z+3/2; (iv) x, y+1, z.

Acknowledgements

The authors thank the Science Foundation of Weifang University (grant No. 2009Z24). Thanks are also extended to Hai-Xing Liu for help with preparing the CIF.

References

Barszcz, B., Glowiak, T., Jezierska, J. & Tomkiewicz, A. (2004). Polyhedron, 23, 1308–1316. Web of Science CSD CrossRef Google Scholar
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tyagi, S., Hathaway, B., Kremer, S., Stratemeier, H. & Reinen, D. (1984). J. Chem. Soc. Dalton Trans. pp. 2087–2091. CSD CrossRef Web of Science Google Scholar

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