Poly[[(μ3-5,6-dicarboxy­bicyclo­[2.2.2]oct-7-ene-2,3-dicarboxyl­ato)(1,10-phenanthroline)copper(II)] monohydrate]

Liu, Y.-Y.; Zhuo, Y.-J.; Li, X.-Q.; Ma, J.-C.

doi:10.1107/S1600536808037999

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 12| December 2008| Page m1590

doi:10.1107/S1600536808037999

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Poly[[(μ₃-5,6-dicarboxybicyclo[2.2.2]oct-7-ene-2,3-dicarboxylato)(1,10-phenanthroline)copper(II)] monohydrate]

Yun-Yu Liu,^a ^* Yu-Jiang Zhuo,^a Xing-Qi Li ^a and Ji-Cheng Ma ^a

^aDepartment of Chemistry, Northeast Normal University, Changchun 130024, People's Republic of China
^*Correspondence e-mail: yunyuliu888@yahoo.com.cn

(Received 13 November 2008; accepted 15 November 2008; online 22 November 2008)

In the title compound, {[Cu(C₁₂H₁₀O₈)(C₁₂H₈N₂)]·H₂O}_n, the Cu^II ion is five-coordinated by two N atoms from one phenanthroline ligand and three O atoms from three different H₂L²⁻ anions (H₄L is bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid) in a distorted square-pyramidal geometry. Each H₂L²⁻ ion bridges three Cu^II atoms to form a zigzag sheet parallel to the ab plane. The crystal structure is consolidated by O—H⋯O hydrogen bonds.

Related literature

For general background, see: Yang et al. (2008 ).

Experimental

Crystal data

[Cu(C₁₂H₁₀O₈)(C₁₂H₈N₂)]·H₂O
M_r = 543.96
Monoclinic, P 2₁
a = 6.5900 (4) Å
b = 15.1650 (8) Å
c = 10.7490 (6) Å
β = 95.244 (9)°
V = 1069.73 (10) Å³
Z = 2
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 293 (2) K
0.33 × 0.21 × 0.20 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.696, T_max = 0.803
6580 measured reflections
4555 independent reflections
4343 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.065
S = 1.04
4555 reflections
333 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ), 1914 Friedel pairs
Flack parameter: 0.008 (8)

Table 1
Selected bond lengths (Å)

N1—Cu1	2.0072 (17)
N2—Cu1	2.0119 (19)
O2—Cu1	1.9640 (15)
Cu1—O3ⁱ	1.9355 (15)
Cu1—O7ⁱⁱ	2.3398 (18)
Symmetry codes: (i) x-1, y, z; (ii) $[-x+2, y-{\script{1\over 2}}, -z+2]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O1W	0.82	1.84	2.567 (2)	148
O8—H8⋯O2ⁱⁱⁱ	0.82	1.79	2.594 (2)	166
O1W—HW11⋯O4^iv	0.82 (3)	1.97 (3)	2.777 (3)	167 (3)
O1W—HW12⋯O1^v	0.82 (2)	2.05 (3)	2.763 (3)	145 (4)
Symmetry codes: (iii) $[-x+2, y+{\script{1\over 2}}, -z+2]$ ; (iv) x, y, z+1; (v) x+1, y, z+1.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808037999/ci2718sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808037999/ci2718Isup2.hkl

checkCIF report

Comment top

Coordination polymers based on poly(carboxylic acids) have been investigated in the area of solid state and material science (Yang et al., 2008). We selected bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid (H₄L) as a poly(carboxylic acid) ligand and phenanthroline (phen) as a secondary ligand, generating a new coordination polymer, [Cu(phen)(H₂L)]^.H₂O, which is reported here.

In the title compound, each Cu^II atom is five-coordinated by two N atoms from one phen ligand, and three O atoms from three different H₂L^2- anions in a distorted square-pyramidal geometry (Fig. 1 and Table 1). Each H₂L^2- bridges three Cu^II atoms to form a two-dimensional layer structure (Fig. 2). The O–H···O hydrogen bonds (Table 2) further consolidate the crystal structure.

Related literature top

For general background, see: Yang et al. (2008).

Experimental top

A mixture of H₄L (0.5 mmol), phen (0.5 mmol), NaOH (1 mmol) and CuCl₂^.2H₂O (0.5 mmol) was suspended in deionized water (12 ml) and sealed in a 20-ml Teflon-lined autoclave. The mixture was heated at 373 K for 7 d and then the autoclave was slowly cooled to room temperature. The grown single crystals were collected, washed with deionized water and dried.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXTL-Plus (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the polymeric structure of the title compound, showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Symmetry codes: (i) x - 1, y, z; (ii) 2 - x, y - 1/2, 2 - z.
	Fig. 2. View of a zigzag sheet structure in the title compound.

Poly[[(µ₃-5,6-dicarboxybicyclo[2.2.2]oct-7-ene-2,3-dicarboxylato)(1,10- phenanthroline)copper(II)] monohydrate] top

Crystal data top

[Cu(C₁₂H₁₀O₈)(C₁₂H₈N₂)]·H₂O	F(000) = 558
M_r = 543.96	D_x = 1.689 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 4555 reflections
a = 6.5900 (4) Å	θ = 1.1–28.4°
b = 15.1650 (8) Å	µ = 1.08 mm⁻¹
c = 10.7490 (6) Å	T = 293 K
β = 95.244 (9)°	Block, blue
V = 1069.73 (10) Å³	0.33 × 0.21 × 0.20 mm
Z = 2

Data collection top

Bruker APEX CCD area-detector diffractometer	4555 independent reflections
Radiation source: fine-focus sealed tube	4343 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.696, T_max = 0.803	k = −19→17
6580 measured reflections	l = −6→14

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0256P)²] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
4555 reflections	Δρ_max = 0.31 e Å⁻³
333 parameters	Δρ_min = −0.37 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1914 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.008 (8)

Crystal data top

[Cu(C₁₂H₁₀O₈)(C₁₂H₈N₂)]·H₂O	V = 1069.73 (10) Å³
M_r = 543.96	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.5900 (4) Å	µ = 1.08 mm⁻¹
b = 15.1650 (8) Å	T = 293 K
c = 10.7490 (6) Å	0.33 × 0.21 × 0.20 mm
β = 95.244 (9)°

Data collection top

Bruker APEX CCD area-detector diffractometer	4555 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4343 reflections with I > 2σ(I)
T_min = 0.696, T_max = 0.803	R_int = 0.022
6580 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	Δρ_max = 0.31 e Å⁻³
S = 1.04	Δρ_min = −0.37 e Å⁻³
4555 reflections	Absolute structure: Flack (1983), 1914 Friedel pairs
333 parameters	Absolute structure parameter: 0.008 (8)
2 restraints

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
C1	0.8692 (4)	0.81993 (17)	0.5050 (2)	0.0327 (5)
H1	0.9536	0.8445	0.5700	0.039*
C2	0.9222 (4)	0.82867 (19)	0.3826 (2)	0.0382 (6)
H2	1.0408	0.8583	0.3669	0.046*
C3	0.7992 (4)	0.79351 (17)	0.2862 (2)	0.0362 (6)
H3	0.8341	0.7990	0.2047	0.043*
C4	0.6199 (3)	0.74901 (17)	0.31010 (18)	0.0285 (5)
C5	0.4749 (4)	0.71054 (18)	0.2161 (2)	0.0352 (6)
H5A	0.4972	0.7156	0.1322	0.042*
C6	0.3084 (4)	0.66765 (18)	0.2479 (2)	0.0361 (6)
H6	0.2186	0.6434	0.1853	0.043*
C7	0.2660 (4)	0.65841 (16)	0.3763 (2)	0.0291 (5)
C8	0.1009 (4)	0.61105 (18)	0.4178 (2)	0.0364 (6)
H8B	0.0083	0.5828	0.3606	0.044*
C9	0.0779 (4)	0.60707 (19)	0.5428 (2)	0.0377 (6)
H9	−0.0301	0.5758	0.5711	0.045*
C10	0.2174 (4)	0.65023 (17)	0.6279 (2)	0.0329 (5)
H10	0.1995	0.6473	0.7127	0.039*
C11	0.4003 (3)	0.69806 (15)	0.46831 (19)	0.0240 (4)
C12	0.5789 (3)	0.74318 (14)	0.43543 (18)	0.0237 (5)
C13	1.0048 (3)	0.90548 (13)	0.94151 (18)	0.0192 (4)
H13	0.9289	0.8814	1.0080	0.023*
C14	1.0387 (3)	1.00356 (15)	0.97408 (18)	0.0223 (4)
H14	0.9159	1.0382	0.9497	0.027*
C15	1.0971 (3)	1.00950 (14)	1.11723 (18)	0.0220 (4)
H15	0.9782	0.9919	1.1598	0.026*
C16	1.2682 (3)	0.94109 (14)	1.14952 (18)	0.0211 (4)
H16	1.1993	0.8873	1.1736	0.025*
C17	1.3679 (3)	0.91758 (15)	1.02845 (19)	0.0229 (4)
H17	1.4990	0.8879	1.0479	0.027*
C18	1.2122 (3)	0.85576 (14)	0.95247 (18)	0.0203 (4)
H18	1.1978	0.8014	1.0002	0.024*
C19	1.3913 (3)	0.99816 (16)	0.94838 (19)	0.0288 (5)
H19	1.5166	1.0168	0.9246	0.035*
C20	1.2195 (4)	1.03987 (15)	0.91496 (19)	0.0268 (5)
H20	1.2108	1.0873	0.8600	0.032*
C21	0.8703 (3)	0.88961 (15)	0.82048 (19)	0.0208 (4)
C22	1.2984 (3)	0.83259 (15)	0.82983 (19)	0.0237 (4)
C23	1.4200 (4)	0.96369 (15)	1.2593 (2)	0.0265 (5)
C24	1.1515 (3)	1.10347 (15)	1.1550 (2)	0.0240 (5)
N1	0.7020 (3)	0.77771 (12)	0.53121 (15)	0.0253 (4)
N2	0.3738 (3)	0.69509 (13)	0.59172 (16)	0.0251 (4)
O1	0.7941 (3)	0.95074 (11)	0.75885 (15)	0.0331 (4)
O2	0.8349 (2)	0.80701 (10)	0.79532 (13)	0.0256 (3)
O1W	1.4570 (4)	0.98510 (18)	1.59374 (17)	0.0537 (6)
O3	1.4401 (2)	0.77476 (12)	0.84210 (14)	0.0323 (4)
O4	1.2381 (2)	0.86940 (12)	0.73066 (14)	0.0323 (4)
O5	1.3290 (3)	0.95633 (14)	1.36461 (15)	0.0406 (4)
H5	1.4105	0.9685	1.4244	0.061*
O6	1.5975 (3)	0.97879 (13)	1.25429 (17)	0.0402 (4)
O7	1.2819 (3)	1.12253 (12)	1.23587 (16)	0.0358 (4)
O8	1.0345 (3)	1.16299 (13)	1.09436 (17)	0.0443 (5)
H8	1.0703	1.2125	1.1181	0.066*
Cu1	0.59195 (3)	0.760541 (17)	0.697564 (19)	0.02264 (7)
HW11	1.378 (5)	0.952 (2)	1.625 (3)	0.050 (10)*
HW12	1.575 (4)	0.969 (3)	1.613 (4)	0.078 (14)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0300 (12)	0.0339 (14)	0.0336 (12)	−0.0050 (11)	0.0001 (10)	0.0004 (10)
C2	0.0364 (14)	0.0379 (15)	0.0413 (13)	−0.0056 (12)	0.0101 (11)	0.0070 (11)
C3	0.0433 (15)	0.0387 (14)	0.0276 (11)	0.0050 (11)	0.0095 (10)	0.0068 (9)
C4	0.0351 (11)	0.0263 (13)	0.0238 (9)	0.0057 (11)	0.0014 (8)	0.0009 (9)
C5	0.0486 (16)	0.0344 (15)	0.0218 (10)	0.0106 (11)	−0.0018 (10)	−0.0044 (9)
C6	0.0425 (15)	0.0343 (14)	0.0292 (11)	0.0029 (12)	−0.0098 (10)	−0.0086 (10)
C7	0.0311 (12)	0.0253 (12)	0.0300 (11)	0.0023 (10)	−0.0023 (9)	−0.0075 (9)
C8	0.0286 (12)	0.0344 (14)	0.0446 (14)	−0.0020 (11)	−0.0059 (10)	−0.0113 (10)
C9	0.0314 (13)	0.0350 (15)	0.0465 (14)	−0.0084 (11)	0.0030 (11)	−0.0058 (11)
C10	0.0318 (13)	0.0335 (14)	0.0339 (12)	−0.0055 (11)	0.0066 (10)	−0.0044 (10)
C11	0.0260 (11)	0.0210 (11)	0.0244 (10)	0.0044 (9)	−0.0014 (8)	−0.0037 (8)
C12	0.0270 (10)	0.0196 (13)	0.0240 (9)	0.0042 (8)	−0.0003 (8)	−0.0017 (7)
C13	0.0199 (10)	0.0184 (11)	0.0194 (9)	−0.0018 (8)	0.0014 (8)	−0.0009 (7)
C14	0.0236 (11)	0.0192 (10)	0.0229 (10)	0.0006 (9)	−0.0049 (8)	−0.0024 (8)
C15	0.0198 (10)	0.0224 (11)	0.0236 (10)	−0.0003 (8)	−0.0002 (8)	−0.0015 (8)
C16	0.0233 (10)	0.0187 (10)	0.0208 (9)	−0.0020 (8)	−0.0007 (8)	−0.0015 (7)
C17	0.0175 (10)	0.0259 (12)	0.0247 (10)	0.0002 (9)	−0.0007 (8)	−0.0037 (8)
C18	0.0199 (10)	0.0215 (11)	0.0190 (9)	0.0006 (8)	−0.0004 (7)	−0.0012 (7)
C19	0.0284 (12)	0.0312 (13)	0.0276 (11)	−0.0119 (10)	0.0062 (9)	−0.0042 (9)
C20	0.0357 (12)	0.0215 (11)	0.0223 (10)	−0.0076 (10)	−0.0026 (9)	0.0017 (8)
C21	0.0182 (10)	0.0220 (12)	0.0216 (10)	−0.0008 (9)	−0.0006 (8)	−0.0013 (8)
C22	0.0212 (10)	0.0254 (12)	0.0248 (10)	−0.0034 (8)	0.0036 (8)	−0.0029 (8)
C23	0.0330 (13)	0.0197 (11)	0.0256 (10)	0.0030 (9)	−0.0043 (9)	0.0010 (8)
C24	0.0238 (11)	0.0221 (12)	0.0262 (11)	0.0028 (9)	0.0031 (9)	−0.0032 (8)
N1	0.0252 (9)	0.0254 (12)	0.0251 (8)	−0.0010 (8)	0.0008 (7)	−0.0022 (7)
N2	0.0242 (9)	0.0245 (10)	0.0264 (9)	0.0010 (8)	0.0006 (7)	−0.0030 (7)
O1	0.0381 (10)	0.0263 (9)	0.0323 (9)	0.0023 (8)	−0.0117 (7)	0.0020 (7)
O2	0.0265 (8)	0.0205 (8)	0.0283 (7)	−0.0040 (7)	−0.0051 (6)	−0.0019 (6)
O1W	0.0514 (14)	0.0778 (17)	0.0291 (9)	−0.0253 (13)	−0.0121 (9)	0.0156 (10)
O3	0.0290 (8)	0.0397 (12)	0.0282 (7)	0.0106 (8)	0.0033 (6)	−0.0084 (7)
O4	0.0349 (9)	0.0392 (10)	0.0225 (7)	0.0009 (8)	0.0016 (6)	0.0024 (7)
O5	0.0447 (10)	0.0543 (13)	0.0211 (7)	−0.0153 (9)	−0.0054 (7)	−0.0004 (7)
O6	0.0254 (9)	0.0509 (13)	0.0424 (10)	0.0001 (8)	−0.0069 (7)	−0.0105 (8)
O7	0.0387 (10)	0.0224 (9)	0.0427 (10)	0.0004 (7)	−0.0164 (8)	−0.0049 (7)
O8	0.0502 (11)	0.0249 (10)	0.0528 (11)	0.0103 (9)	−0.0222 (9)	−0.0094 (8)
Cu1	0.02218 (12)	0.02490 (13)	0.02043 (10)	−0.00053 (12)	−0.00032 (8)	−0.00387 (11)

Geometric parameters (Å, º) top

C1—N1	1.326 (3)	C15—C16	1.548 (3)
C1—C2	1.398 (3)	C15—H15	0.98
C1—H1	0.93	C16—C23	1.515 (3)
C2—C3	1.364 (4)	C16—C17	1.552 (3)
C2—H2	0.93	C16—H16	0.98
C3—C4	1.405 (4)	C17—C19	1.511 (3)
C3—H3	0.93	C17—C18	1.564 (3)
C4—C12	1.401 (3)	C17—H17	0.98
C4—C5	1.448 (3)	C18—C22	1.523 (3)
C5—C6	1.346 (4)	C18—H18	0.98
C5—H5A	0.93	C19—C20	1.318 (3)
C6—C7	1.440 (3)	C19—H19	0.93
C6—H6	0.93	C20—H20	0.93
C7—C11	1.401 (3)	C21—O1	1.220 (3)
C7—C8	1.410 (3)	C21—O2	1.298 (3)
C8—C9	1.367 (3)	C22—O4	1.236 (3)
C8—H8B	0.93	C22—O3	1.279 (3)
C9—C10	1.399 (3)	C23—O6	1.198 (3)
C9—H9	0.93	C23—O5	1.334 (3)
C10—N2	1.323 (3)	C24—O7	1.200 (3)
C10—H10	0.93	C24—O8	1.320 (3)
C11—N2	1.354 (3)	N1—Cu1	2.0072 (17)
C11—C12	1.434 (3)	N2—Cu1	2.0119 (19)
C12—N1	1.356 (3)	O2—Cu1	1.9640 (15)
C13—C21	1.525 (3)	O1W—HW11	0.82 (3)
C13—C14	1.540 (3)	O1W—HW12	0.822 (19)
C13—C18	1.556 (3)	O3—Cu1ⁱ	1.9355 (15)
C13—H13	0.98	O5—H5	0.82
C14—C20	1.505 (3)	O7—Cu1ⁱⁱ	2.3398 (18)
C14—C15	1.554 (3)	O8—H8	0.82
C14—H14	0.98	Cu1—O3ⁱⁱⁱ	1.9355 (15)
C15—C24	1.516 (3)	Cu1—O7^iv	2.3398 (18)

N1—C1—C2	122.0 (2)	C15—C16—C17	108.75 (16)
N1—C1—H1	119.0	C23—C16—H16	105.8
C2—C1—H1	119.0	C15—C16—H16	105.8
C3—C2—C1	119.7 (2)	C17—C16—H16	105.8
C3—C2—H2	120.2	C19—C17—C16	111.41 (18)
C1—C2—H2	120.2	C19—C17—C18	106.48 (17)
C2—C3—C4	120.0 (2)	C16—C17—C18	105.53 (16)
C2—C3—H3	120.0	C19—C17—H17	111.1
C4—C3—H3	120.0	C16—C17—H17	111.1
C12—C4—C3	116.4 (2)	C18—C17—H17	111.1
C12—C4—C5	118.2 (2)	C22—C18—C13	116.14 (16)
C3—C4—C5	125.3 (2)	C22—C18—C17	108.15 (17)
C6—C5—C4	121.3 (2)	C13—C18—C17	106.20 (16)
C6—C5—H5A	119.4	C22—C18—H18	108.7
C4—C5—H5A	119.4	C13—C18—H18	108.7
C5—C6—C7	121.6 (2)	C17—C18—H18	108.7
C5—C6—H6	119.2	C20—C19—C17	114.4 (2)
C7—C6—H6	119.2	C20—C19—H19	122.8
C11—C7—C8	116.8 (2)	C17—C19—H19	122.8
C11—C7—C6	118.0 (2)	C19—C20—C14	113.8 (2)
C8—C7—C6	125.2 (2)	C19—C20—H20	123.1
C9—C8—C7	119.4 (2)	C14—C20—H20	123.1
C9—C8—H8B	120.3	O1—C21—O2	124.26 (19)
C7—C8—H8B	120.3	O1—C21—C13	121.4 (2)
C8—C9—C10	119.8 (2)	O2—C21—C13	114.15 (18)
C8—C9—H9	120.1	O4—C22—O3	124.92 (19)
C10—C9—H9	120.1	O4—C22—C18	121.8 (2)
N2—C10—C9	122.1 (2)	O3—C22—C18	113.28 (18)
N2—C10—H10	119.0	O6—C23—O5	124.8 (2)
C9—C10—H10	119.0	O6—C23—C16	125.9 (2)
N2—C11—C7	123.2 (2)	O5—C23—C16	109.01 (19)
N2—C11—C12	116.08 (19)	O7—C24—O8	122.7 (2)
C7—C11—C12	120.70 (19)	O7—C24—C15	123.8 (2)
N1—C12—C4	123.4 (2)	O8—C24—C15	113.40 (19)
N1—C12—C11	116.42 (17)	C1—N1—C12	118.41 (18)
C4—C12—C11	120.14 (19)	C1—N1—Cu1	128.81 (15)
C21—C13—C14	114.04 (17)	C12—N1—Cu1	112.72 (14)
C21—C13—C18	115.24 (16)	C10—N2—C11	118.6 (2)
C14—C13—C18	110.05 (17)	C10—N2—Cu1	128.54 (16)
C21—C13—H13	105.5	C11—N2—Cu1	112.83 (15)
C14—C13—H13	105.5	C21—O2—Cu1	125.43 (14)
C18—C13—H13	105.5	HW11—O1W—HW12	109 (4)
C20—C14—C13	111.19 (17)	C22—O3—Cu1ⁱ	114.82 (14)
C20—C14—C15	105.24 (17)	C23—O5—H5	109.5
C13—C14—C15	107.38 (17)	C24—O7—Cu1ⁱⁱ	130.37 (16)
C20—C14—H14	110.9	C24—O8—H8	109.5
C13—C14—H14	110.9	O3ⁱⁱⁱ—Cu1—O2	89.24 (7)
C15—C14—H14	110.9	O3ⁱⁱⁱ—Cu1—N1	162.98 (7)
C24—C15—C16	114.85 (17)	O2—Cu1—N1	94.97 (7)
C24—C15—C14	110.54 (18)	O3ⁱⁱⁱ—Cu1—N2	96.53 (7)
C16—C15—C14	107.01 (16)	O2—Cu1—N2	170.11 (7)
C24—C15—H15	108.1	N1—Cu1—N2	81.84 (7)
C16—C15—H15	108.1	O3ⁱⁱⁱ—Cu1—O7^iv	92.84 (7)
C14—C15—H15	108.1	O2—Cu1—O7^iv	84.71 (6)
C23—C16—C15	116.02 (18)	N1—Cu1—O7^iv	103.96 (7)
C23—C16—C17	113.89 (18)	N2—Cu1—O7^iv	86.97 (7)

N1—C1—C2—C3	0.4 (4)	C15—C14—C20—C19	57.3 (2)
C1—C2—C3—C4	0.2 (4)	C14—C13—C21—O1	−1.8 (3)
C2—C3—C4—C12	−0.3 (4)	C18—C13—C21—O1	−130.5 (2)
C2—C3—C4—C5	178.6 (2)	C14—C13—C21—O2	−177.45 (17)
C12—C4—C5—C6	−2.2 (4)	C18—C13—C21—O2	53.9 (2)
C3—C4—C5—C6	178.8 (3)	C13—C18—C22—O4	17.8 (3)
C4—C5—C6—C7	0.4 (4)	C17—C18—C22—O4	−101.4 (2)
C5—C6—C7—C11	2.0 (4)	C13—C18—C22—O3	−164.32 (18)
C5—C6—C7—C8	−176.8 (3)	C17—C18—C22—O3	76.5 (2)
C11—C7—C8—C9	0.9 (4)	C15—C16—C23—O6	−114.2 (3)
C6—C7—C8—C9	179.8 (2)	C17—C16—C23—O6	13.2 (3)
C7—C8—C9—C10	0.3 (4)	C15—C16—C23—O5	71.4 (2)
C8—C9—C10—N2	−0.4 (4)	C17—C16—C23—O5	−161.24 (19)
C8—C7—C11—N2	−2.3 (3)	C16—C15—C24—O7	−23.1 (3)
C6—C7—C11—N2	178.8 (2)	C14—C15—C24—O7	−144.3 (2)
C8—C7—C11—C12	176.3 (2)	C16—C15—C24—O8	160.03 (19)
C6—C7—C11—C12	−2.6 (3)	C14—C15—C24—O8	38.8 (2)
C3—C4—C12—N1	−0.1 (3)	C2—C1—N1—C12	−0.8 (4)
C5—C4—C12—N1	−179.1 (2)	C2—C1—N1—Cu1	−177.84 (18)
C3—C4—C12—C11	−179.3 (2)	C4—C12—N1—C1	0.6 (3)
C5—C4—C12—C11	1.6 (3)	C11—C12—N1—C1	179.9 (2)
N2—C11—C12—N1	0.2 (3)	C4—C12—N1—Cu1	178.13 (18)
C7—C11—C12—N1	−178.5 (2)	C11—C12—N1—Cu1	−2.6 (2)
N2—C11—C12—C4	179.5 (2)	C9—C10—N2—C11	−0.9 (4)
C7—C11—C12—C4	0.8 (3)	C9—C10—N2—Cu1	−179.39 (19)
C21—C13—C14—C20	−88.1 (2)	C7—C11—N2—C10	2.3 (3)
C18—C13—C14—C20	43.2 (2)	C12—C11—N2—C10	−176.4 (2)
C21—C13—C14—C15	157.29 (17)	C7—C11—N2—Cu1	−179.00 (18)
C18—C13—C14—C15	−71.42 (19)	C12—C11—N2—Cu1	2.3 (2)
C20—C14—C15—C24	56.4 (2)	O1—C21—O2—Cu1	−23.2 (3)
C13—C14—C15—C24	174.93 (17)	C13—C21—O2—Cu1	152.23 (14)
C20—C14—C15—C16	−69.3 (2)	O4—C22—O3—Cu1ⁱ	9.8 (3)
C13—C14—C15—C16	49.2 (2)	C18—C22—O3—Cu1ⁱ	−167.97 (14)
C24—C15—C16—C23	26.6 (3)	O8—C24—O7—Cu1ⁱⁱ	−7.8 (4)
C14—C15—C16—C23	149.70 (18)	C15—C24—O7—Cu1ⁱⁱ	175.59 (14)
C24—C15—C16—C17	−103.3 (2)	C21—O2—Cu1—O3ⁱⁱⁱ	−77.88 (17)
C14—C15—C16—C17	19.8 (2)	C21—O2—Cu1—N1	85.60 (17)
C23—C16—C17—C19	−91.2 (2)	C21—O2—Cu1—O7^iv	−170.81 (17)
C15—C16—C17—C19	39.8 (2)	C1—N1—Cu1—O3ⁱⁱⁱ	94.5 (3)
C23—C16—C17—C18	153.60 (18)	C12—N1—Cu1—O3ⁱⁱⁱ	−82.7 (3)
C15—C16—C17—C18	−75.3 (2)	C1—N1—Cu1—O2	−9.3 (2)
C21—C13—C18—C22	26.2 (3)	C12—N1—Cu1—O2	173.52 (15)
C14—C13—C18—C22	−104.5 (2)	C1—N1—Cu1—N2	−179.9 (2)
C21—C13—C18—C17	146.43 (17)	C12—N1—Cu1—N2	2.94 (15)
C14—C13—C18—C17	15.8 (2)	C1—N1—Cu1—O7^iv	−95.1 (2)
C19—C17—C18—C22	59.7 (2)	C12—N1—Cu1—O7^iv	87.74 (15)
C16—C17—C18—C22	178.16 (17)	C10—N2—Cu1—O3ⁱⁱⁱ	−21.4 (2)
C19—C17—C18—C13	−65.7 (2)	C11—N2—Cu1—O3ⁱⁱⁱ	160.06 (15)
C16—C17—C18—C13	52.9 (2)	C10—N2—Cu1—N1	175.7 (2)
C16—C17—C19—C20	−57.8 (2)	C11—N2—Cu1—N1	−2.86 (15)
C18—C17—C19—C20	56.8 (2)	C10—N2—Cu1—O7^iv	71.1 (2)
C17—C19—C20—C14	5.7 (3)	C11—N2—Cu1—O7^iv	−107.43 (15)
C13—C14—C20—C19	−58.6 (2)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1W	0.82	1.84	2.567 (2)	148
O8—H8···O2ⁱⁱ	0.82	1.79	2.594 (2)	166
O1W—HW11···O4^v	0.82 (3)	1.97 (3)	2.777 (3)	167 (3)
O1W—HW12···O1^vi	0.82 (2)	2.05 (3)	2.763 (3)	145 (4)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₀O₈)(C₁₂H₈N₂)]·H₂O
M_r	543.96
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	293
a, b, c (Å)	6.5900 (4), 15.1650 (8), 10.7490 (6)
β (°)	95.244 (9)
V (Å³)	1069.73 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.33 × 0.21 × 0.20

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.696, 0.803
No. of measured, independent and observed [I > 2σ(I)] reflections	6580, 4555, 4343
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.065, 1.04
No. of reflections	4555
No. of parameters	333
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.37
Absolute structure	Flack (1983), 1914 Friedel pairs
Absolute structure parameter	0.008 (8)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Selected bond lengths (Å) top

N1—Cu1	2.0072 (17)	Cu1—O3ⁱ	1.9355 (15)
N2—Cu1	2.0119 (19)	Cu1—O7ⁱⁱ	2.3398 (18)
O2—Cu1	1.9640 (15)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5···O1W	0.82	1.84	2.567 (2)	148
O8—H8···O2ⁱⁱⁱ	0.82	1.79	2.594 (2)	166
O1W—HW11···O4^iv	0.82 (3)	1.97 (3)	2.777 (3)	167 (3)
O1W—HW12···O1^v	0.82 (2)	2.05 (3)	2.763 (3)	145 (4)

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

Acknowledgements

The authors thank the Science Foundation for Young Teachers of Northeast Normal University (grant Nos. 20080305 and 20080304) for financial support.

References

Bruker (1998). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, J., Ma, J.-F., Batten, S. R. & Su, Z.-M. (2008). Chem. Commun. pp. 2233–2235. Web of Science CSD CrossRef Google Scholar

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