Bis(μ-3-carb­oxy-2-oxidobenzoato)-κ3O1,O2:O3;κ3O3:O1,O2-bis­[aqua­(2,2′-bipyridine-κ2N,N′)copper(II)]

Gao, J.; Zhu, B.-Y.; Cui, D.-L.

doi:10.1107/S1600536808039913

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Pages m4-m5

doi:10.1107/S1600536808039913

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Bis(μ-3-carboxy-2-oxidobenzoato)-κ³O¹,O²:O³;κ³O³:O¹,O²-bis[aqua(2,2′-bipyridine-κ²N,N′)copper(II)]

Jing Gao,^a Bao-Yong Zhu ^b and De-Liang Cui ^c ^*

^aDepartment of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, People's Republic of China, ^bDepartment of Chemistry, Dezhou University, Dezhou 253023, People's Republic of China, and ^cInstitute of Crystalline Materials, Shandong University, Jinan 250100, People's Republic of China
^*Correspondence e-mail: cuidl@sdu.edu.cn

(Received 10 November 2008; accepted 27 November 2008; online 3 December 2008)

In the centrosymmetric dinuclear complex, [Cu₂(C₈H₄O₅)₂(C₁₀H₈N₂)₂(H₂O)₂], the Cu^II ion is coordinated by two N atoms from a bipyridine ligand, three O atoms from two 3-carboxy-2-oxidobenzoate dianions and the O atom of the water molecule in a distorted octahedral geometry. The Cu—-O(H) coordination [2.931 (3) Å] is very weak. In the crystal structure, the dinuclear units are linked into a two-dimensional network parallel to (010) by O—H⋯O hydrogen bonds.

Related literature

For related structures, see: Augustin et al. (2005 ); Tao et al. (2002 ); Zheng et al. (2004 ).

Experimental

Crystal data

[Cu₂(C₈H₄O₅)₂(C₁₀H₈N₂)₂(H₂O)₂]
M_r = 835.70
Triclinic, $[P \overline 1]$
a = 8.354 (5) Å
b = 10.635 (5) Å
c = 11.038 (5) Å
α = 66.812 (5)°
β = 68.070 (5)°
γ = 89.269 (5)°
V = 825.8 (7) Å³
Z = 1
Mo Kα radiation
μ = 1.36 mm⁻¹
T = 293 (2) K
0.20 × 0.20 × 0.17 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.772, T_max = 0.801
4985 measured reflections
3686 independent reflections
2989 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.084
S = 1.17
3686 reflections
247 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O3	1.8976 (18)
Cu1—O2	1.9325 (17)
Cu1—N2	2.004 (2)
Cu1—N1	2.007 (2)
Cu1—O1	2.301 (2)
Cu1—O5ⁱ	2.931 (2)
Symmetry code: (i) -x+2, -y+1, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O2	0.84	1.67	2.461 (2)	156
O1—H1B⋯O6ⁱⁱ	0.83	1.93	2.763 (3)	173
O1—H1A⋯O4ⁱⁱⁱ	0.83	1.89	2.706 (3)	167
Symmetry codes: (ii) -x+1, -y+1, -z+2; (iii) -x+2, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039913/ci2713sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808039913/ci2713Isup2.hkl

checkCIF report

Comment top

2,2-Bipyridine and benzenedicarboxylate (BDC) anion are good organic ligands for copper which can construct supramolecular structure via hydrogen bonds and π-π aromatic interactions. We present here the crystal structure of [Cu₂(bpy)₂(ipO)₂(H₂O)₂], where bpy is 2,2,-bipyridine and ipOH is 2-hydroxyisophthalate.

The title compound is a centrosymmetric dinuclear complex (Fig. 1). Each Cu^II ion is coordinated by two N atoms (N1 and N2) from a bipyridine ligand in a bidentate chelating fashion and three O atoms (O2, O3 and O5ⁱ) of two ipO dianions and the O atom (O1) of the solvent water molecule, in a distorted octahedral geometry. The Cu1—-O5ⁱ coordination [2.931 (3) Å] is very weak. The Cu^II atom is located 0.209 (1) Å above the basal plane formed by atoms N1, N2, O2 and O3. The mean Cu—N(bpy) distance of 2.006 (2) Å and the bite angle N1—Cu1—N2 of 80.43 (8)° are close to the corresponding values observed in related copper-bipyridine compounds (Augustin et al., 2005).

In the crystal structure, the centrosymmetric dinuclear units are linked into a two-dimensional network parallel to the (010) (Fig. 2) by O—H···O hydrogen bonds.

In [Cu₂(bpy)₂(ipO)₂(H₂O)₂], the isophthalic acid (ipa) was in situ oxidative hydroxylated before coordinating with Cu^II ion (Tao et al., 2002). Similar in situ oxidation has also been reported for 1,2,3-benzenetricarboxylic acid (Zheng et al., 2004).

Related literature top

For related structures, see: Augustin et al. (2005); Tao et al. (2002); Zheng et al. (2004).

Experimental top

Copper(II) chloride dihydrate (0.043 g, 0.251 mol), 2,2,-bipyridine (0.039 g, 0.249 mol), isophthalic acid (0.083 g, 0.500 mol), potassium hydroxide (0.055 g, 0.982 mol) and deionized water (18 ml) were mixed together. The mixture was sealed in a Teflon-lined stainless steel vessel (25 ml) and then heated at 453 K for 36 h under autogenous pressure and then cooled to room temperature. Light-green crystals were obtained by slow evaporation of the mother-liquor in the air for a few days.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The structure of the title complex, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry code: (i) -x + 2, -y + 1, -z + 2.
	Fig. 2. The crystal packing of the title compound. Hydrogen bonds are shown as dashed lines.

Bis(µ-3-carboxy-2-oxidobenzoato)- κ³O¹,O²:O³;κ³O³:O¹,O²- bis[aqua(2,2'-bipyridine-κ²N,N')copper(II)] top

Crystal data top

[Cu₂(C₈H₄O₅)₂(C₁₀H₈N₂)₂(H₂O)₂]	Z = 1
M_r = 835.70	F(000) = 426
Triclinic, P1	D_x = 1.680 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.354 (5) Å	Cell parameters from 3943 reflections
b = 10.635 (5) Å	θ = 2.1–28.2°
c = 11.038 (5) Å	µ = 1.36 mm⁻¹
α = 66.812 (5)°	T = 293 K
β = 68.070 (5)°	Block, green
γ = 89.269 (5)°	0.20 × 0.20 × 0.17 mm
V = 825.8 (7) Å³

Data collection top

Bruker APEXII area-detector diffractometer	3686 independent reflections
Radiation source: fine-focus sealed tube	2989 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 28.2°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −11→10
T_min = 0.772, T_max = 0.801	k = −11→14
4985 measured reflections	l = −14→14

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) = 0.084	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0284P)² + 0.2P] where P = (F_o² + 2F_c²)/3
3686 reflections	(Δ/σ)_max = 0.001
247 parameters	Δρ_max = 0.32 e Å⁻³
3 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Cu₂(C₈H₄O₅)₂(C₁₀H₈N₂)₂(H₂O)₂]	γ = 89.269 (5)°
M_r = 835.70	V = 825.8 (7) Å³
Triclinic, P1	Z = 1
a = 8.354 (5) Å	Mo Kα radiation
b = 10.635 (5) Å	µ = 1.36 mm⁻¹
c = 11.038 (5) Å	T = 293 K
α = 66.812 (5)°	0.20 × 0.20 × 0.17 mm
β = 68.070 (5)°

Data collection top

Bruker APEXII area-detector diffractometer	3686 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2989 reflections with I > 2σ(I)
T_min = 0.772, T_max = 0.801	R_int = 0.016
4985 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	3 restraints
wR(F²) = 0.084	H-atom parameters constrained
S = 1.17	Δρ_max = 0.32 e Å⁻³
3686 reflections	Δρ_min = −0.25 e Å⁻³
247 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	1.02424 (4)	0.40419 (3)	0.79285 (3)	0.03492 (11)
O1	0.8041 (2)	0.2876 (2)	0.78123 (19)	0.0477 (5)
H1A	0.8460	0.2870	0.7003	0.050 (9)*
H1B	0.7220	0.3329	0.7808	0.073 (11)*
O2	0.8826 (2)	0.50132 (17)	0.89930 (16)	0.0386 (4)
O5	0.7156 (2)	0.47764 (18)	1.14597 (18)	0.0428 (4)
H5	0.7925	0.4761	1.0720	0.079 (11)*
O3	1.0772 (2)	0.56037 (18)	0.61539 (18)	0.0475 (5)
O6	0.4835 (2)	0.5775 (2)	1.19418 (19)	0.0472 (5)
O4	1.0474 (3)	0.7547 (2)	0.46051 (18)	0.0546 (5)
C1	0.8480 (3)	0.6833 (2)	0.6998 (2)	0.0328 (5)
C2	0.7521 (3)	0.7865 (3)	0.6566 (3)	0.0429 (6)
H2	0.7839	0.8396	0.5588	0.052*
N2	1.2225 (3)	0.3176 (2)	0.7039 (2)	0.0342 (5)
C5	0.6589 (3)	0.6344 (2)	0.9478 (2)	0.0319 (5)
C8	0.6095 (3)	0.5615 (3)	1.1045 (3)	0.0351 (5)
C6	0.8000 (3)	0.6034 (2)	0.8478 (2)	0.0297 (5)
C14	1.1417 (3)	0.1660 (2)	0.9492 (3)	0.0344 (5)
N1	1.0135 (3)	0.2428 (2)	0.9707 (2)	0.0343 (5)
C13	1.2642 (3)	0.2115 (2)	0.7976 (3)	0.0345 (5)
C9	1.3259 (3)	0.3668 (3)	0.5628 (3)	0.0420 (6)
H9	1.2961	0.4392	0.4976	0.050*
C10	1.4742 (4)	0.3132 (3)	0.5122 (3)	0.0507 (7)
H10	1.5434	0.3484	0.4142	0.061*
C4	0.5662 (3)	0.7384 (3)	0.8979 (3)	0.0416 (6)
H4	0.4723	0.7571	0.9635	0.050*
C7	0.9998 (3)	0.6649 (3)	0.5847 (3)	0.0371 (6)
C3	0.6113 (4)	0.8133 (3)	0.7535 (3)	0.0482 (7)
H3	0.5477	0.8815	0.7212	0.058*
C12	1.4127 (4)	0.1550 (3)	0.7521 (3)	0.0485 (7)
H12	1.4408	0.0823	0.8182	0.058*
C11	1.5186 (4)	0.2078 (3)	0.6077 (3)	0.0536 (8)
H11	1.6199	0.1717	0.5755	0.064*
C15	1.1534 (4)	0.0535 (3)	1.0627 (3)	0.0464 (7)
H15	1.2411	0.0001	1.0461	0.056*
C17	0.9043 (4)	0.1000 (3)	1.2207 (3)	0.0521 (7)
H17	0.8221	0.0799	1.3130	0.063*
C18	0.8958 (4)	0.2081 (3)	1.1050 (3)	0.0442 (6)
H18	0.8051	0.2593	1.1202	0.053*
C16	1.0337 (4)	0.0218 (3)	1.2004 (3)	0.0537 (8)
H16	1.0410	−0.0519	1.2783	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.04080 (18)	0.03336 (18)	0.02357 (16)	0.01615 (13)	−0.01105 (12)	−0.00717 (12)
O1	0.0447 (10)	0.0642 (13)	0.0384 (11)	0.0230 (10)	−0.0178 (9)	−0.0249 (10)
O2	0.0488 (10)	0.0383 (10)	0.0242 (8)	0.0205 (8)	−0.0135 (7)	−0.0103 (7)
O5	0.0467 (10)	0.0488 (11)	0.0264 (9)	0.0202 (9)	−0.0107 (8)	−0.0137 (8)
O3	0.0555 (11)	0.0443 (11)	0.0262 (9)	0.0261 (9)	−0.0092 (8)	−0.0059 (8)
O6	0.0440 (10)	0.0587 (12)	0.0378 (10)	0.0187 (9)	−0.0114 (8)	−0.0241 (9)
O4	0.0678 (13)	0.0475 (11)	0.0248 (9)	0.0273 (10)	−0.0096 (9)	−0.0011 (8)
C1	0.0371 (13)	0.0301 (13)	0.0296 (12)	0.0095 (10)	−0.0145 (10)	−0.0100 (10)
C2	0.0507 (16)	0.0395 (15)	0.0331 (14)	0.0143 (12)	−0.0185 (12)	−0.0085 (12)
N2	0.0383 (11)	0.0321 (11)	0.0316 (11)	0.0103 (9)	−0.0150 (9)	−0.0120 (9)
C5	0.0338 (12)	0.0318 (13)	0.0309 (12)	0.0079 (10)	−0.0134 (10)	−0.0136 (10)
C8	0.0346 (13)	0.0369 (14)	0.0344 (13)	0.0052 (11)	−0.0119 (11)	−0.0175 (11)
C6	0.0330 (12)	0.0277 (12)	0.0288 (12)	0.0082 (10)	−0.0136 (10)	−0.0110 (10)
C14	0.0427 (14)	0.0268 (12)	0.0368 (13)	0.0081 (10)	−0.0214 (11)	−0.0112 (11)
N1	0.0406 (11)	0.0293 (11)	0.0287 (10)	0.0083 (9)	−0.0135 (9)	−0.0083 (9)
C13	0.0378 (13)	0.0291 (13)	0.0386 (14)	0.0085 (10)	−0.0180 (11)	−0.0136 (11)
C9	0.0462 (15)	0.0398 (15)	0.0351 (14)	0.0097 (12)	−0.0124 (12)	−0.0148 (12)
C10	0.0457 (16)	0.0519 (18)	0.0434 (16)	0.0078 (13)	−0.0042 (13)	−0.0222 (14)
C4	0.0396 (14)	0.0444 (15)	0.0417 (15)	0.0171 (12)	−0.0144 (12)	−0.0210 (12)
C7	0.0430 (14)	0.0350 (14)	0.0262 (12)	0.0098 (11)	−0.0135 (11)	−0.0064 (11)
C3	0.0534 (16)	0.0428 (16)	0.0479 (16)	0.0251 (13)	−0.0246 (14)	−0.0149 (13)
C12	0.0488 (16)	0.0416 (16)	0.0586 (18)	0.0202 (13)	−0.0248 (14)	−0.0216 (14)
C11	0.0397 (15)	0.0534 (18)	0.062 (2)	0.0163 (13)	−0.0105 (14)	−0.0286 (16)
C15	0.0559 (17)	0.0329 (14)	0.0512 (17)	0.0139 (12)	−0.0295 (14)	−0.0108 (13)
C17	0.0705 (19)	0.0396 (16)	0.0288 (14)	0.0033 (14)	−0.0141 (13)	−0.0027 (12)
C18	0.0507 (16)	0.0360 (14)	0.0351 (14)	0.0103 (12)	−0.0132 (12)	−0.0082 (12)
C16	0.076 (2)	0.0358 (15)	0.0418 (16)	0.0098 (14)	−0.0311 (15)	−0.0020 (13)

Geometric parameters (Å, º) top

Cu1—O3	1.8976 (18)	C5—C8	1.477 (3)
Cu1—O2	1.9325 (17)	C14—N1	1.346 (3)
Cu1—N2	2.004 (2)	C14—C15	1.385 (3)
Cu1—N1	2.007 (2)	C14—C13	1.475 (3)
Cu1—O1	2.301 (2)	N1—C18	1.338 (3)
Cu1—O5ⁱ	2.931 (2)	C13—C12	1.380 (3)
O1—H1A	0.83	C9—C10	1.374 (4)
O1—H1B	0.83	C9—H9	0.93
O2—C6	1.328 (3)	C10—C11	1.362 (4)
O5—C8	1.324 (3)	C10—H10	0.93
O5—H5	0.84	C4—C3	1.369 (4)
O3—C7	1.272 (3)	C4—H4	0.93
O6—C8	1.211 (3)	C3—H3	0.93
O4—C7	1.233 (3)	C12—C11	1.376 (4)
C1—C2	1.387 (3)	C12—H12	0.93
C1—C6	1.407 (3)	C11—H11	0.93
C1—C7	1.499 (3)	C15—C16	1.376 (4)
C2—C3	1.378 (4)	C15—H15	0.93
C2—H2	0.93	C17—C16	1.361 (4)
N2—C13	1.344 (3)	C17—C18	1.367 (4)
N2—C9	1.346 (3)	C17—H17	0.93
C5—C4	1.394 (3)	C18—H18	0.93
C5—C6	1.422 (3)	C16—H16	0.93

O3—Cu1—O2	91.52 (8)	C15—C14—C13	124.1 (2)
O3—Cu1—N2	92.25 (8)	C18—N1—C14	118.6 (2)
O2—Cu1—N2	162.60 (8)	C18—N1—Cu1	126.46 (17)
O3—Cu1—N1	169.99 (8)	C14—N1—Cu1	114.96 (15)
O2—Cu1—N1	93.53 (8)	N2—C13—C12	121.3 (2)
N2—Cu1—N1	80.43 (8)	N2—C13—C14	114.3 (2)
O3—Cu1—O1	96.20 (8)	C12—C13—C14	124.5 (2)
O2—Cu1—O1	98.23 (8)	N2—C9—C10	121.9 (3)
N2—Cu1—O1	98.25 (8)	N2—C9—H9	119.0
N1—Cu1—O1	91.63 (8)	C10—C9—H9	119.0
O3—Cu1—O5ⁱ	92.34 (8)	C11—C10—C9	119.1 (3)
O2—Cu1—O5ⁱ	79.41 (8)	C11—C10—H10	120.5
N2—Cu1—O5ⁱ	83.47 (8)	C9—C10—H10	120.5
N1—Cu1—O5ⁱ	80.11 (8)	C3—C4—C5	120.9 (2)
O1—Cu1—O5ⁱ	171.22 (6)	C3—C4—H4	119.5
Cu1—O1—H1A	105.3	C5—C4—H4	119.5
Cu1—O1—H1B	110.7	O4—C7—O3	121.6 (2)
H1A—O1—H1B	104.9	O4—C7—C1	117.8 (2)
C6—O2—Cu1	124.77 (15)	O3—C7—C1	120.6 (2)
C8—O5—H5	107.2	C4—C3—C2	119.3 (2)
C7—O3—Cu1	130.12 (16)	C4—C3—H3	120.3
C2—C1—C6	118.8 (2)	C2—C3—H3	120.3
C2—C1—C7	117.6 (2)	C11—C12—C13	119.1 (3)
C6—C1—C7	123.6 (2)	C11—C12—H12	120.4
C3—C2—C1	122.4 (2)	C13—C12—H12	120.4
C3—C2—H2	118.8	C10—C11—C12	119.7 (3)
C1—C2—H2	118.8	C10—C11—H11	120.2
C13—N2—C9	118.9 (2)	C12—C11—H11	120.2
C13—N2—Cu1	115.19 (16)	C16—C15—C14	119.2 (3)
C9—N2—Cu1	125.39 (17)	C16—C15—H15	120.4
C4—C5—C6	119.7 (2)	C14—C15—H15	120.4
C4—C5—C8	118.5 (2)	C16—C17—C18	119.8 (3)
C6—C5—C8	121.8 (2)	C16—C17—H17	120.1
O6—C8—O5	119.4 (2)	C18—C17—H17	120.1
O6—C8—C5	124.2 (2)	N1—C18—C17	122.2 (3)
O5—C8—C5	116.3 (2)	N1—C18—H18	118.9
O2—C6—C1	123.1 (2)	C17—C18—H18	118.9
O2—C6—C5	118.1 (2)	C17—C16—C15	118.9 (3)
C1—C6—C5	118.8 (2)	C17—C16—H16	120.5
N1—C14—C15	121.3 (2)	C15—C16—H16	120.5
N1—C14—C13	114.6 (2)

O3—Cu1—O2—C6	27.15 (19)	O2—Cu1—N1—C14	−158.90 (17)
N2—Cu1—O2—C6	129.6 (3)	N2—Cu1—N1—C14	4.66 (17)
N1—Cu1—O2—C6	−161.50 (19)	O1—Cu1—N1—C14	102.75 (18)
O1—Cu1—O2—C6	−69.34 (19)	C9—N2—C13—C12	1.7 (4)
O2—Cu1—O3—C7	−19.2 (2)	Cu1—N2—C13—C12	−170.8 (2)
N2—Cu1—O3—C7	177.8 (2)	C9—N2—C13—C14	−179.9 (2)
N1—Cu1—O3—C7	−139.5 (4)	Cu1—N2—C13—C14	7.6 (3)
O1—Cu1—O3—C7	79.3 (2)	N1—C14—C13—N2	−3.7 (3)
C6—C1—C2—C3	−0.2 (4)	C15—C14—C13—N2	176.0 (2)
C7—C1—C2—C3	−179.3 (2)	N1—C14—C13—C12	174.7 (2)
O3—Cu1—N2—C13	166.35 (18)	C15—C14—C13—C12	−5.6 (4)
O2—Cu1—N2—C13	64.0 (3)	C13—N2—C9—C10	−1.1 (4)
N1—Cu1—N2—C13	−6.78 (17)	Cu1—N2—C9—C10	170.6 (2)
O1—Cu1—N2—C13	−97.06 (18)	N2—C9—C10—C11	−0.5 (4)
O3—Cu1—N2—C9	−5.6 (2)	C6—C5—C4—C3	−1.4 (4)
O2—Cu1—N2—C9	−107.9 (3)	C8—C5—C4—C3	177.2 (2)
N1—Cu1—N2—C9	−178.7 (2)	Cu1—O3—C7—O4	−176.2 (2)
O1—Cu1—N2—C9	91.0 (2)	Cu1—O3—C7—C1	4.4 (4)
C4—C5—C8—O6	6.7 (4)	C2—C1—C7—O4	10.8 (4)
C6—C5—C8—O6	−174.7 (2)	C6—C1—C7—O4	−168.3 (2)
C4—C5—C8—O5	−170.9 (2)	C2—C1—C7—O3	−169.8 (3)
C6—C5—C8—O5	7.6 (3)	C6—C1—C7—O3	11.1 (4)
Cu1—O2—C6—C1	−21.3 (3)	C5—C4—C3—C2	−0.9 (4)
Cu1—O2—C6—C5	160.03 (16)	C1—C2—C3—C4	1.8 (4)
C2—C1—C6—O2	179.2 (2)	N2—C13—C12—C11	−0.7 (4)
C7—C1—C6—O2	−1.8 (4)	C14—C13—C12—C11	−178.9 (3)
C2—C1—C6—C5	−2.2 (4)	C9—C10—C11—C12	1.4 (5)
C7—C1—C6—C5	176.8 (2)	C13—C12—C11—C10	−0.8 (4)
C4—C5—C6—O2	−178.3 (2)	N1—C14—C15—C16	−1.5 (4)
C8—C5—C6—O2	3.1 (3)	C13—C14—C15—C16	178.8 (2)
C4—C5—C6—C1	3.0 (4)	C14—N1—C18—C17	1.7 (4)
C8—C5—C6—C1	−175.6 (2)	Cu1—N1—C18—C17	−176.6 (2)
C15—C14—N1—C18	−0.2 (4)	C16—C17—C18—N1	−1.5 (5)
C13—C14—N1—C18	179.5 (2)	C18—C17—C16—C15	−0.2 (5)
C15—C14—N1—Cu1	178.29 (19)	C14—C15—C16—C17	1.6 (4)
C13—C14—N1—Cu1	−2.0 (3)	O5ⁱ—Cu1—O2—C6	119.26 (19)
O3—Cu1—N1—C18	139.6 (4)	O5ⁱ—Cu1—O3—C7	−98.6 (3)
O2—Cu1—N1—C18	19.4 (2)	O5ⁱ—Cu1—N2—C13	74.20 (18)
N2—Cu1—N1—C18	−177.0 (2)	O5ⁱ—Cu1—N2—C9	−97.7 (2)
O1—Cu1—N1—C18	−78.9 (2)	O5ⁱ—Cu1—N1—C18	98.1 (2)
O3—Cu1—N1—C14	−38.7 (5)	O5ⁱ—Cu1—N1—C14	−80.29 (18)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2	0.84	1.67	2.461 (2)	156
O1—H1B···O6ⁱⁱ	0.83	1.93	2.763 (3)	173
O1—H1A···O4ⁱⁱⁱ	0.83	1.89	2.706 (3)	167

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₄O₅)₂(C₁₀H₈N₂)₂(H₂O)₂]
M_r	835.70
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.354 (5), 10.635 (5), 11.038 (5)
α, β, γ (°)	66.812 (5), 68.070 (5), 89.269 (5)
V (Å³)	825.8 (7)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.36
Crystal size (mm)	0.20 × 0.20 × 0.17

Data collection
Diffractometer	Bruker APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.772, 0.801
No. of measured, independent and observed [I > 2σ(I)] reflections	4985, 3686, 2989
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.664

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.084, 1.17
No. of reflections	3686
No. of parameters	247
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.25

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu1—O3	1.8976 (18)	Cu1—N1	2.007 (2)
Cu1—O2	1.9325 (17)	Cu1—O1	2.301 (2)
Cu1—N2	2.004 (2)	Cu1—O5ⁱ	2.931 (2)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O2	0.84	1.67	2.461 (2)	156
O1—H1B···O6ⁱⁱ	0.83	1.93	2.763 (3)	173
O1—H1A···O4ⁱⁱⁱ	0.83	1.89	2.706 (3)	167

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

Acknowledgements

We thank Professor Dao-Feng Sun and Dr Xi-Feng Lu for the data collection and helpful discussions. This work was supported by the National Natural Science Foundation of China (grant Nos. 50672048 and 50721002).

References

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