Bis(μ-3-chloro­benzene-1,2-dicarboxyl­ato-κ2O2:O2)bis­[diaqua­(5,5′-dimethyl-2,2′-bipyridine-κ2N,N′)copper(II)]

Li, F.-A.; Xu, F.; Hu, X.-M.

doi:10.1107/S1600536811035112

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page m1366

https://doi.org/10.1107/S1600536811035112

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Bis(μ-3-chlorobenzene-1,2-dicarboxylato-κ²O²:O²)bis[diaqua(5,5′-dimethyl-2,2′-bipyridine-κ²N,N′)copper(II)]

Fu-An Li,^a ^* Fu Xu ^a and Xiao-Ming Hu ^a

^aCollege of Chemistry and Chemical Engineering, Pingdingshan University, Pingdingshan 467000, Henan, People's Republic of China
^*Correspondence e-mail: lifuanpds@163.com

(Received 16 August 2011; accepted 27 August 2011; online 14 September 2011)

In the centrosymmetric binuclear title compound, [Cu₂(C₈H₃ClO₄)₂(C₁₂H₁₂N₂)₂(H₂O)₄], the Cu^II ion is six-coordinated by two N atoms from a 5,5′-dimethyl-2,2′-bipyridine ligand, two bridging O atoms from two 3-chlorobenzene-1,2-dicarboxylate ligands and two water molecules in a distorted octahedral geometry. The binuclear complex molecules are linked together by intermolecular O—H⋯O hydrogen bonds into a layer parallel to (100). The layers are connected by C—H⋯Cl hydrogen bonds. Intramolecular O—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distance = 3.5958 (16) Å] are also present.

Related literature

For background to polynuclear coordination compounds containing benzenecarboxylate ligands, see: Baca et al. (2005 ); Ma et al. (2004 ); Thirumurugan & Rao (2005 ); Zang et al. (2010 ). For O—H⋯O and C—H⋯Cl hydrogen bonds, see: Desiraju (2004 ); Song & Iyoda (2009 ); Wang et al. (2011 ).

Experimental

Crystal data

[Cu₂(C₈H₃ClO₄)₂(C₁₂H₁₂N₂)₂(H₂O)₄]
M_r = 964.72
Monoclinic, P 2₁ /c
a = 11.6908 (7) Å
b = 11.8643 (6) Å
c = 17.2869 (13) Å
β = 124.806 (5)°
V = 1968.8 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 296 K
0.21 × 0.20 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.774, T_max = 0.792
7602 measured reflections
3450 independent reflections
2845 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.07
3450 reflections
273 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O3	0.85	1.79	2.622 (3)	164
O1W—H1WB⋯O4ⁱ	0.85	1.82	2.655 (3)	167
O2W—H2WA⋯O1	0.85	2.17	2.731 (3)	124
O2W—H2WB⋯O4ⁱ	0.85	2.06	2.786 (3)	143
C6—H6⋯Cl1ⁱⁱ	0.93	2.82	3.609 (4)	144
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536811035112/hy2462sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035112/hy2462Isup2.hkl

checkCIF report

Comment top

It is common knowledge that the coordination geometry of metal ion and the shape and bonding mode of ligand are generally the primary considerations in metal-mediated self-assembly reactions. Relatively small changes in the bridging ligand can give rise to large variation in the overall structure of the assembly. Recently, some polynuclear coordination compounds containing benzenecarboxylate ligands and O—H···O and C—H···Cl hydrogen bonds (Desiraju, 2004; Song & Iyoda, 2009; Wang et al., 2011) have been reported (Baca et al., 2005; Ma et al., 2004; Thirumurugan & Rao, 2005; Zang et al., 2010). To better understand the influence of benzenecarboxylate ligands and hydrogen-bonding interactions on the resultant structures, we have begun working on the architectures of polynuclear structures from 3-chlorobenzene-1,2-dioic acid. As part of our ongoing investigation, the title compound has been prepared and its structure was determined.

The title compound is a binuclear complex (Fig. 1). The Cu^II atom is coordinated by two N atoms from a 5,5'-dimethyl-2,2'-bipyridine ligand, two O atoms from two 3-chlorobenzene-1,2-dicarboxylate ligands and two O atoms from two coordinated water molecules, forming a distorted octahedral geometry. As shown in Fig. 2, each complex molecule is connected to four neighboring molecules through O—H···O hydrogen bonds (Table 1), resulting in a two-dimensional supramolecular structure parallel to (1 0 0). Adjacent layers are associated together by C—H···Cl hydrogen bonds, forming a three-dimensional supramolecular structure (Fig. 3).

Related literature top

For background to polynuclear coordination compounds containing benzenecarboxylate ligands, see: Baca et al. (2005); Ma et al. (2004); Thirumurugan & Rao (2005); Zang et al. (2010). For O—H···O and C—H···Cl hydrogen bonds, see: Desiraju (2004); Song et al. (2009); Wang et al. (2011).

Experimental top

A mixture of CuSO₄.5H₂O (7.5 mg, 0.03 mmol), 3-chlorobenzene-1,2-dioic acid (6 mg, 0.03 mmol), 5,5'-dimethyl-2,2'-bipyridine (5.5 mg, 0.03 mmol) and NaOH (2.4 mg, 0.06 mmol) in 10 ml of H₂O was sealed in a stainless-steel reactor with a Teflon liner and heated at 393 K for 72 h. A quantity of green single crystals was obtained after the solution was cooled to room temperature at a rate of 10 K h^-1.

Structure description top

For background to polynuclear coordination compounds containing benzenecarboxylate ligands, see: Baca et al. (2005); Ma et al. (2004); Thirumurugan & Rao (2005); Zang et al. (2010). For O—H···O and C—H···Cl hydrogen bonds, see: Desiraju (2004); Song et al. (2009); Wang et al. (2011).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are omitted for clarity. [Symmetry code: (i) -x, 2-y, 1-z.]
	Fig. 2. A view of the supramolecular layer in the title compound. Dotted lines represent hydrogen bonds.
	Fig. 3. The three-dimensional supramolecular structure in the title compound. Dashed lines indicate hydrogen bonds.

Bis(µ-3-chlorobenzene-1,2-dicarboxylato- κ²O²:O²)bis[diaqua(5,5'-dimethyl-2,2'-bipyridine- κ²N,N')copper(II)] top

Crystal data top

[Cu₂(C₈H₃ClO₄)₂(C₁₂H₁₂N₂)₂(H₂O)₄]	F(000) = 988
M_r = 964.72	D_x = 1.627 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2332 reflections
a = 11.6908 (7) Å	θ = 3.0–29.3°
b = 11.8643 (6) Å	µ = 1.29 mm⁻¹
c = 17.2869 (13) Å	T = 296 K
β = 124.806 (5)°	Block, green
V = 1968.8 (2) Å³	0.21 × 0.20 × 0.19 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3450 independent reflections
Radiation source: fine-focus sealed tube	2845 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
φ and ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→12
T_min = 0.774, T_max = 0.792	k = −13→14
7602 measured reflections	l = −19→20

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0451P)²] where P = (F_o² + 2F_c²)/3
3450 reflections	(Δ/σ)_max = 0.001
273 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Cu₂(C₈H₃ClO₄)₂(C₁₂H₁₂N₂)₂(H₂O)₄]	V = 1968.8 (2) Å³
M_r = 964.72	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.6908 (7) Å	µ = 1.29 mm⁻¹
b = 11.8643 (6) Å	T = 296 K
c = 17.2869 (13) Å	0.21 × 0.20 × 0.19 mm
β = 124.806 (5)°

Data collection top

Bruker APEXII CCD diffractometer	3450 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2845 reflections with I > 2σ(I)
T_min = 0.774, T_max = 0.792	R_int = 0.030
7602 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.07	Δρ_max = 0.34 e Å⁻³
3450 reflections	Δρ_min = −0.29 e Å⁻³
273 parameters

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

	x	y	z	U_iso*/U_eq
Cu1	0.00030 (3)	0.85763 (3)	0.53560 (2)	0.02829 (13)
O1	0.2700 (2)	0.90830 (15)	0.72939 (15)	0.0422 (5)
O2	0.11583 (17)	0.99350 (14)	0.59290 (12)	0.0273 (4)
O3	0.0506 (2)	1.03936 (16)	0.73724 (14)	0.0417 (5)
O4	0.0696 (2)	1.19348 (17)	0.81467 (15)	0.0481 (6)
O1W	−0.08536 (18)	0.88808 (15)	0.60396 (13)	0.0323 (4)
H1WA	−0.0475	0.9459	0.6386	0.048*
H1WB	−0.0733	0.8317	0.6382	0.048*
O2W	0.1570 (2)	0.69797 (18)	0.67213 (17)	0.0595 (7)
H2WA	0.2298	0.7286	0.7187	0.089*
H2WB	0.1093	0.6695	0.6903	0.089*
N1	0.0910 (2)	0.80054 (17)	0.47615 (15)	0.0283 (5)
N2	−0.1213 (2)	0.72318 (17)	0.47124 (15)	0.0291 (5)
C1	0.2153 (3)	0.9926 (2)	0.68096 (18)	0.0275 (6)
C2	0.1059 (3)	1.1301 (2)	0.77408 (19)	0.0294 (6)
C3	0.2744 (3)	1.1063 (2)	0.72625 (18)	0.0262 (6)
C4	0.2292 (3)	1.1679 (2)	0.77316 (19)	0.0313 (7)
C5	0.2972 (3)	1.2677 (2)	0.8182 (2)	0.0442 (8)
H5	0.2670	1.3091	0.8490	0.053*
C6	0.4079 (4)	1.3067 (3)	0.8183 (2)	0.0535 (9)
H6	0.4529	1.3728	0.8501	0.064*
C7	0.4520 (3)	1.2485 (3)	0.7716 (2)	0.0438 (8)
H7	0.5257	1.2751	0.7704	0.053*
C8	0.3848 (3)	1.1490 (2)	0.7262 (2)	0.0332 (7)
C9	0.1929 (3)	0.8511 (2)	0.47533 (19)	0.0329 (7)
H9	0.2267	0.9196	0.5066	0.040*
C10	0.2500 (3)	0.8080 (3)	0.4313 (2)	0.0430 (8)
C11	0.3573 (4)	0.8730 (3)	0.4275 (3)	0.0691 (11)
H11A	0.3784	0.9420	0.4621	0.104*
H11B	0.3214	0.8898	0.3631	0.104*
H11C	0.4405	0.8287	0.4548	0.104*
C12	0.2011 (3)	0.7028 (3)	0.3883 (2)	0.0457 (8)
H12	0.2390	0.6687	0.3593	0.055*
C13	0.0978 (3)	0.6501 (2)	0.3887 (2)	0.0432 (8)
H13	0.0651	0.5803	0.3599	0.052*
C14	0.0421 (3)	0.7003 (2)	0.43179 (18)	0.0290 (6)
C15	−0.0748 (3)	0.6550 (2)	0.43229 (19)	0.0317 (7)
C16	−0.1362 (3)	0.5512 (2)	0.3958 (2)	0.0435 (8)
H16	−0.1047	0.5051	0.3682	0.052*
C17	−0.2437 (3)	0.5169 (2)	0.4008 (2)	0.0482 (9)
H17	−0.2842	0.4467	0.3772	0.058*
C18	−0.2924 (3)	0.5854 (2)	0.4403 (2)	0.0398 (7)
C19	−0.4090 (3)	0.5521 (3)	0.4481 (3)	0.0620 (10)
H19A	−0.4961	0.5765	0.3929	0.093*
H19B	−0.3959	0.5867	0.5028	0.093*
H19C	−0.4099	0.4716	0.4536	0.093*
C20	−0.2279 (3)	0.6894 (2)	0.4739 (2)	0.0353 (7)
H20	−0.2605	0.7379	0.4995	0.042*
Cl1	0.44008 (8)	1.07793 (7)	0.66549 (6)	0.0534 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0343 (2)	0.0238 (2)	0.0340 (2)	−0.00589 (14)	0.02376 (18)	−0.00736 (15)
O1	0.0441 (12)	0.0252 (10)	0.0467 (13)	0.0041 (10)	0.0196 (10)	0.0063 (10)
O2	0.0310 (10)	0.0261 (9)	0.0260 (10)	−0.0061 (8)	0.0170 (9)	−0.0060 (9)
O3	0.0569 (13)	0.0368 (11)	0.0489 (13)	−0.0175 (10)	0.0405 (11)	−0.0177 (10)
O4	0.0625 (14)	0.0416 (12)	0.0574 (15)	0.0008 (11)	0.0444 (13)	−0.0117 (11)
O1W	0.0441 (11)	0.0252 (9)	0.0366 (11)	−0.0045 (9)	0.0284 (10)	−0.0031 (9)
O2W	0.0635 (15)	0.0554 (14)	0.0714 (17)	−0.0126 (12)	0.0455 (14)	−0.0206 (13)
N1	0.0357 (13)	0.0248 (12)	0.0271 (12)	0.0010 (10)	0.0194 (11)	−0.0024 (10)
N2	0.0336 (13)	0.0242 (11)	0.0271 (12)	−0.0014 (10)	0.0159 (11)	0.0003 (10)
C1	0.0281 (14)	0.0294 (14)	0.0321 (16)	−0.0001 (12)	0.0213 (13)	−0.0032 (13)
C2	0.0386 (16)	0.0265 (14)	0.0246 (14)	0.0025 (13)	0.0190 (13)	0.0014 (12)
C3	0.0278 (14)	0.0233 (13)	0.0202 (13)	−0.0004 (12)	0.0094 (12)	0.0033 (12)
C4	0.0399 (16)	0.0258 (13)	0.0260 (15)	−0.0024 (13)	0.0175 (13)	−0.0008 (13)
C5	0.062 (2)	0.0355 (16)	0.0428 (19)	−0.0137 (16)	0.0344 (17)	−0.0129 (15)
C6	0.073 (2)	0.0365 (17)	0.056 (2)	−0.0237 (17)	0.040 (2)	−0.0156 (17)
C7	0.0390 (16)	0.0455 (18)	0.0418 (19)	−0.0152 (15)	0.0200 (15)	−0.0018 (16)
C8	0.0296 (15)	0.0365 (15)	0.0323 (16)	0.0012 (13)	0.0170 (13)	0.0029 (14)
C9	0.0379 (16)	0.0341 (15)	0.0286 (15)	0.0016 (13)	0.0200 (14)	−0.0002 (13)
C10	0.0429 (18)	0.057 (2)	0.0355 (17)	0.0078 (16)	0.0265 (15)	0.0077 (16)
C11	0.066 (2)	0.099 (3)	0.069 (3)	−0.013 (2)	0.055 (2)	−0.007 (2)
C12	0.056 (2)	0.056 (2)	0.0368 (18)	0.0155 (17)	0.0341 (17)	0.0012 (16)
C13	0.061 (2)	0.0343 (16)	0.0388 (18)	0.0077 (15)	0.0313 (17)	−0.0042 (15)
C14	0.0376 (16)	0.0250 (14)	0.0227 (14)	0.0053 (12)	0.0162 (13)	0.0025 (12)
C15	0.0393 (17)	0.0251 (14)	0.0233 (14)	0.0022 (13)	0.0134 (13)	0.0021 (12)
C16	0.057 (2)	0.0276 (15)	0.0389 (18)	−0.0044 (15)	0.0233 (16)	−0.0087 (14)
C17	0.050 (2)	0.0288 (15)	0.0441 (19)	−0.0129 (15)	0.0141 (16)	−0.0029 (15)
C18	0.0358 (16)	0.0363 (16)	0.0326 (16)	−0.0078 (14)	0.0109 (14)	0.0044 (15)
C19	0.050 (2)	0.058 (2)	0.067 (2)	−0.0219 (18)	0.0273 (19)	−0.002 (2)
C20	0.0314 (15)	0.0360 (15)	0.0314 (16)	−0.0018 (13)	0.0138 (13)	0.0011 (14)
Cl1	0.0504 (5)	0.0573 (5)	0.0724 (6)	−0.0032 (4)	0.0468 (5)	−0.0078 (5)

Geometric parameters (Å, º) top

Cu1—O2	1.9689 (16)	C7—C8	1.387 (4)
Cu1—O2ⁱ	2.5406 (17)	C7—H7	0.9300
Cu1—N1	1.971 (2)	C8—Cl1	1.733 (3)
Cu1—N2	2.000 (2)	C9—C10	1.366 (4)
Cu1—O1W	1.9700 (19)	C9—H9	0.9300
Cu1—O2W	2.753 (2)	C10—C12	1.397 (4)
O1—C1	1.224 (3)	C10—C11	1.506 (4)
O2—C1	1.284 (3)	C11—H11A	0.9600
O3—C2	1.230 (3)	C11—H11B	0.9600
O4—C2	1.256 (3)	C11—H11C	0.9600
O1W—H1WA	0.8500	C12—C13	1.363 (4)
O1W—H1WB	0.8500	C12—H12	0.9300
O2W—H2WA	0.8500	C13—C14	1.373 (4)
O2W—H2WB	0.8500	C13—H13	0.9300
N1—C9	1.341 (3)	C14—C15	1.474 (4)
N1—C14	1.352 (3)	C15—C16	1.382 (4)
N2—C20	1.334 (3)	C16—C17	1.370 (4)
N2—C15	1.350 (4)	C16—H16	0.9300
C1—C3	1.514 (4)	C17—C18	1.376 (4)
C2—C4	1.518 (4)	C17—H17	0.9300
C3—C8	1.387 (4)	C18—C20	1.389 (4)
C3—C4	1.400 (4)	C18—C19	1.498 (4)
C4—C5	1.390 (4)	C19—H19A	0.9600
C5—C6	1.373 (4)	C19—H19B	0.9600
C5—H5	0.9300	C19—H19C	0.9600
C6—C7	1.367 (5)	C20—H20	0.9300
C6—H6	0.9300

O2—Cu1—O1W	89.18 (7)	C6—C7—H7	120.6
O2—Cu1—N1	97.18 (8)	C8—C7—H7	120.6
O1W—Cu1—N1	170.06 (8)	C7—C8—C3	122.5 (3)
O2—Cu1—N2	177.20 (8)	C7—C8—Cl1	118.1 (2)
O1W—Cu1—N2	92.09 (9)	C3—C8—Cl1	119.4 (2)
N1—Cu1—N2	81.90 (9)	N1—C9—C10	123.9 (3)
O2—Cu1—O2W	101.68 (7)	N1—C9—H9	118.1
O1W—Cu1—O2W	85.94 (7)	C10—C9—H9	118.1
N1—Cu1—O2W	85.29 (8)	C9—C10—C12	116.7 (3)
N2—Cu1—O2W	80.91 (8)	C9—C10—C11	121.1 (3)
O1W—Cu1—O2ⁱ	101.31 (7)	C12—C10—C11	122.1 (3)
N1—Cu1—O2ⁱ	87.77 (8)	C10—C11—H11A	109.5
O2—Cu1—O2ⁱ	75.02 (7)	C10—C11—H11B	109.5
O2W—Cu1—O2ⁱ	171.88 (8)	H11A—C11—H11B	109.5
N2—Cu1—O2ⁱ	102.28 (7)	C10—C11—H11C	109.5
C1—O2—Cu1	119.12 (17)	H11A—C11—H11C	109.5
Cu1—O1W—H1WA	109.4	H11B—C11—H11C	109.5
Cu1—O1W—H1WB	109.5	C13—C12—C10	120.1 (3)
H1WA—O1W—H1WB	109.5	C13—C12—H12	120.0
Cu1—O2W—H2WA	109.5	C10—C12—H12	120.0
Cu1—O2W—H2WB	109.5	C12—C13—C14	120.0 (3)
H2WA—O2W—H2WB	109.5	C12—C13—H13	120.0
C9—N1—C14	118.6 (2)	C14—C13—H13	120.0
C9—N1—Cu1	126.69 (18)	N1—C14—C13	120.7 (3)
C14—N1—Cu1	114.75 (18)	N1—C14—C15	114.3 (2)
C20—N2—C15	119.2 (2)	C13—C14—C15	125.0 (3)
C20—N2—Cu1	127.0 (2)	N2—C15—C16	120.6 (3)
C15—N2—Cu1	113.24 (18)	N2—C15—C14	115.1 (2)
O1—C1—O2	125.7 (2)	C16—C15—C14	124.3 (3)
O1—C1—C3	117.9 (2)	C17—C16—C15	119.5 (3)
O2—C1—C3	116.3 (2)	C17—C16—H16	120.3
O3—C2—O4	124.6 (3)	C15—C16—H16	120.3
O3—C2—C4	118.4 (2)	C16—C17—C18	120.7 (3)
O4—C2—C4	117.0 (2)	C16—C17—H17	119.7
C8—C3—C4	118.0 (2)	C18—C17—H17	119.7
C8—C3—C1	118.4 (2)	C17—C18—C20	116.9 (3)
C4—C3—C1	123.6 (2)	C17—C18—C19	123.0 (3)
C5—C4—C3	119.0 (3)	C20—C18—C19	120.1 (3)
C5—C4—C2	119.3 (3)	C18—C19—H19A	109.5
C3—C4—C2	121.7 (2)	C18—C19—H19B	109.5
C6—C5—C4	121.7 (3)	H19A—C19—H19B	109.5
C6—C5—H5	119.2	C18—C19—H19C	109.5
C4—C5—H5	119.2	H19A—C19—H19C	109.5
C7—C6—C5	120.1 (3)	H19B—C19—H19C	109.5
C7—C6—H6	120.0	N2—C20—C18	123.1 (3)
C5—C6—H6	120.0	N2—C20—H20	118.4
C6—C7—C8	118.8 (3)	C18—C20—H20	118.4

O1W—Cu1—O2—C1	71.57 (19)	C4—C3—C8—C7	0.9 (4)
N1—Cu1—O2—C1	−100.76 (19)	C1—C3—C8—C7	−175.4 (3)
O2W—Cu1—O2—C1	−14.12 (19)	C4—C3—C8—Cl1	−177.8 (2)
O2—Cu1—N1—C9	−3.7 (2)	C1—C3—C8—Cl1	5.9 (3)
N2—Cu1—N1—C9	173.6 (2)	C14—N1—C9—C10	0.7 (4)
O2W—Cu1—N1—C9	−104.9 (2)	Cu1—N1—C9—C10	−178.8 (2)
O2—Cu1—N1—C14	176.77 (18)	N1—C9—C10—C12	−2.5 (4)
N2—Cu1—N1—C14	−5.90 (18)	N1—C9—C10—C11	175.7 (3)
O2W—Cu1—N1—C14	75.57 (18)	C9—C10—C12—C13	2.2 (5)
O1W—Cu1—N2—C20	7.1 (2)	C11—C10—C12—C13	−176.0 (3)
N1—Cu1—N2—C20	179.1 (2)	C10—C12—C13—C14	−0.2 (5)
O2W—Cu1—N2—C20	92.6 (2)	C9—N1—C14—C13	1.5 (4)
O1W—Cu1—N2—C15	−163.93 (18)	Cu1—N1—C14—C13	−178.9 (2)
N1—Cu1—N2—C15	8.11 (18)	C9—N1—C14—C15	−176.8 (2)
O2W—Cu1—N2—C15	−78.38 (18)	Cu1—N1—C14—C15	2.8 (3)
Cu1—O2—C1—O1	19.6 (4)	C12—C13—C14—N1	−1.7 (4)
Cu1—O2—C1—C3	−164.18 (17)	C12—C13—C14—C15	176.3 (3)
O1—C1—C3—C8	86.6 (3)	C20—N2—C15—C16	−0.2 (4)
O2—C1—C3—C8	−89.9 (3)	Cu1—N2—C15—C16	171.6 (2)
O1—C1—C3—C4	−89.5 (3)	C20—N2—C15—C14	179.4 (2)
O2—C1—C3—C4	94.0 (3)	Cu1—N2—C15—C14	−8.8 (3)
C8—C3—C4—C5	−0.7 (4)	N1—C14—C15—N2	4.1 (3)
C1—C3—C4—C5	175.4 (3)	C13—C14—C15—N2	−174.0 (3)
C8—C3—C4—C2	177.8 (2)	N1—C14—C15—C16	−176.3 (3)
C1—C3—C4—C2	−6.1 (4)	C13—C14—C15—C16	5.5 (4)
O3—C2—C4—C5	−177.1 (3)	N2—C15—C16—C17	−1.0 (4)
O4—C2—C4—C5	1.4 (4)	C14—C15—C16—C17	179.4 (3)
O3—C2—C4—C3	4.5 (4)	C15—C16—C17—C18	1.0 (4)
O4—C2—C4—C3	−177.1 (3)	C16—C17—C18—C20	0.2 (4)
C3—C4—C5—C6	−0.5 (5)	C16—C17—C18—C19	−179.7 (3)
C2—C4—C5—C6	−179.0 (3)	C15—N2—C20—C18	1.5 (4)
C4—C5—C6—C7	1.4 (5)	Cu1—N2—C20—C18	−169.0 (2)
C5—C6—C7—C8	−1.2 (5)	C17—C18—C20—N2	−1.5 (4)
C6—C7—C8—C3	0.0 (5)	C19—C18—C20—N2	178.3 (3)
C6—C7—C8—Cl1	178.7 (3)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3	0.85	1.79	2.622 (3)	164
O1W—H1WB···O4ⁱⁱ	0.85	1.82	2.655 (3)	167
O2W—H2WA···O1	0.85	2.17	2.731 (3)	124
O2W—H2WB···O4ⁱⁱ	0.85	2.06	2.786 (3)	143
C6—H6···Cl1ⁱⁱⁱ	0.93	2.82	3.609 (4)	144

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₃ClO₄)₂(C₁₂H₁₂N₂)₂(H₂O)₄]
M_r	964.72
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	11.6908 (7), 11.8643 (6), 17.2869 (13)
β (°)	124.806 (5)
V (Å³)	1968.8 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.21 × 0.20 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.774, 0.792
No. of measured, independent and observed [I > 2σ(I)] reflections	7602, 3450, 2845
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.07
No. of reflections	3450
No. of parameters	273
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.29

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O3	0.85	1.79	2.622 (3)	164
O1W—H1WB···O4ⁱ	0.85	1.82	2.655 (3)	167
O2W—H2WA···O1	0.85	2.17	2.731 (3)	124
O2W—H2WB···O4ⁱ	0.85	2.06	2.786 (3)	143
C6—H6···Cl1ⁱⁱ	0.93	2.82	3.609 (4)	144

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

Acknowledgements

We thank the Science Research Foundation for High-level Talents of Pingdingshan University (No. 2006046) for support.

References

Baca, S. G., Filippova, I. G., Ambrus, C., Gdaniec, M., Simonov, Y. A., Gerbeleu, N., Gherco, O. A. & Decurtins, S. (2005). Eur. J. Inorg. Chem. pp. 3118–3130. Web of Science CSD CrossRef Google Scholar
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. (2004). Hydrogen Bonding. Encyclopedia of Supramolecular Chemistry, edited by J. L. Atwood & J. W. Steed, pp. 658–665. New York: Marcel Dekker Inc. Google Scholar
Ma, C.-B., Wang, W.-G., Zhang, X.-F., Chen, C.-N., Liu, Q.-T., Zhu, H.-P., Liao, D.-Z. & Li, L.-C. (2004). Eur. J. Inorg. Chem. pp. 3522–3532. Web of Science CSD CrossRef Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Song, L. J. & Iyoda, T. (2009). J. Inorg. Organomet. Polym. 19, 124–132. Web of Science CSD CrossRef CAS Google Scholar
Thirumurugan, A. & Rao, C. N. R. (2005). J. Mater. Chem. 15, 3852–3858. Web of Science CSD CrossRef CAS Google Scholar
Wang, X.-S., Li, Q., Wu, J.-R. & Zhang, M.-M. (2011). J. Chem. Crystallogr. 41, 59–63. Web of Science CSD CrossRef CAS Google Scholar
Zang, S.-Q., Li, J.-B., Li, Q.-Y., Hou, H.-W. & Mak, T. C. W. (2010). Polyhedron, 29, 2907–2915. Web of Science CSD CrossRef CAS Google Scholar

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