catena-Poly[[[aqua­bis(1H-imidazole-κN3)copper(II)]-μ-naphthalene-1,4-dicarboxyl­ato-κ2O1:O4] dihydrate]

Li, J.-H.; Nie, J.-J.; Xu, D.-J.

doi:10.1107/S1600536808018515

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Pages m948-m949

doi:10.1107/S1600536808018515

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catena-Poly[[[aquabis(1H-imidazole-κN³)copper(II)]-μ-naphthalene-1,4-dicarboxylato-κ²O¹:O⁴] dihydrate]

Jun-Hua Li,^a Jing-Jing Nie ^a and Duan-Jun Xu ^a ^*

^aDepartment of Chemistry, Zhejiang University, People's Republic of China
^*Correspondence e-mail: xudj@mail.hz.zj.cn

(Received 17 June 2008; accepted 18 June 2008; online 21 June 2008)

In the title compound, {[Cu(C₁₂H₆O₄)(C₃H₄N₂)₂(H₂O)]·2H₂O}_n, the Cu^II cation is coordinated by two naphthalene-1,4-dicarboxylate (naph) dianions, two imidazole molecules and one water molecule in a distorted square-pyramidal geometry. The Cu—O bond distance in the apical direction is 0.509 (3) Å longer than the mean Cu—O bond distance in the basal plane. The naph dianion bridges two Cu^II cations, forming a one-dimensional polymeric chain. The coordinated water molecule is hydrogen-bonded to the carboxylate groups and imidazole ligands of adjacent polymeric chains, forming a three-dimensional supramolecular structure. No π–π stacking is observed in the crystal structure. One solvent water molecule is disordered equally over two positions.

Related literature

For general background, see: Su & Xu (2004 ); Li et al. (2005 ). For related structures, see: Derissen et al. (1979 ); Li et al. (2008 ).

Experimental

Crystal data

[Cu(C₁₂H₆O₄)(C₃H₄N₂)₂(H₂O)]·2H₂O
M_r = 467.92
Monoclinic, P 2₁ /n
a = 12.571 (2) Å
b = 14.698 (3) Å
c = 12.636 (2) Å
β = 119.011 (6)°
V = 2041.8 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.12 mm⁻¹
T = 295 (2) K
0.33 × 0.30 × 0.24 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.660, T_max = 0.765
23205 measured reflections
3989 independent reflections
3251 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.097
S = 1.06
3989 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu—N1	1.992 (2)
Cu—N3	1.990 (2)
Cu—O1	1.9819 (17)
Cu—O3ⁱ	2.0116 (17)
Cu—O5	2.506 (2)
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O3	0.87	1.99	2.846 (3)	170
O1W—H1B⋯O4ⁱⁱ	0.89	1.93	2.789 (3)	162
O2WA—H2A⋯O1W	0.91	1.97	2.828 (13)	155
O2WB—H2C⋯O2WA	0.85	1.55	2.156 (16)	126
N2—H2N⋯O1Wⁱⁱⁱ	0.86	1.96	2.798 (4)	165
N4—H4N⋯O5^iv	0.86	2.02	2.866 (3)	166
O5—H5A⋯O2ⁱⁱ	0.85	1.90	2.716 (3)	162
O5—H5B⋯O4^v	0.85	1.95	2.791 (3)	172
C17—H17⋯O2^vi	0.93	2.50	3.389 (4)	160
Symmetry codes: (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1; (v) x, y, z-1; (vi) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018515/sg2252sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808018515/sg2252Isup2.hkl

checkCIF report

Comment top

As part of our investigation on the nature of π-π stacking between aromatic rings (Li et al., 2005), the title polymeric complex of Cu^II incorporating imidazole and naphthalenedicarboxylate (naph) ligands has been prepared and its crystal structure is reported here.

The Cu^II cation is coordinated by two naph dianions, two imidazole molecules and one water molecule in a distorted square pyramidal geometry. The Cu—O(water) bond distance in the apical direction is longer than mean Cu—O(carboxyl) bond distance in the basal plane by 0.509 (3) Å. The naph dianion bridges two Cu^II cations by two carboxyl groups to form the one dimensional polymeric chain (Fig. 1). Two carboxyl groups of the naph dianion are twisted with respect to the C1-benzene ring with the dihedral angles of 32.0 (2)° and 38.2 (2)°, which are close to that found in the free naphthalenedicarboxylic acid (ca 40°; Derissen et al., 1979) but are much smaller than those [52.5 (3)° and 48.7 (3)°] found in a Mn^II complex with the uncoordinated naph dianion (Li et al., 2008). The coordinated water molecule (O5) is hydrogen bonded to carboxyl groups and imidazole ligand of adjacent polymeric chains (Table 2) to form the three dimensional supra-molecular structure.

The parallel C8-benzene and C8ⁱⁱⁱ-benzene rings from the adjacent polymeric chains overlap as shown in Fig. 2 [symmetry code: (iii) 1 - x, 1 - y, 2 - z] with a face-to-face separation of 3.67 (2) Å indicating no π-π stacking existing between benzene rings, a similar situation to that found in the Mn^II complex with uncoordinated naph dianion (Li et al., 2008). The face-to-face distances between parallel N1-imidazole and N1^iv-imidazole rings and between parallel N3-imidazole and N3^v-imidazole rings are 3.310 (4) and 3.050 (17) Å, respectively [symmetry codes: (iv) 1 - x, -y, 1 - z; (v) 1 - x, 1 - y, 1 - z]. However the imidazole rings are not overlapping each other in the crystal structure (Fig. 3), therefore no π-p\ stacking exists between parallel imidazole rings too.

Related literature top

For general background, see: Su & Xu (2004); Li et al. (2005). For related structures, see: Derissen et al. (1979); Li et al. (2008).

Experimental top

A water-ethanol solution (12 ml, 1:1) containing naphthalene-1,4-dicarboxyllic acid (0.162 g, 0.75 mmol), sodium hydroxide (0.053 g, 1.3 mmol), sodium acetate trihydrate (0.204 g, 1.5 mmol), cupric chloride dihydrate (0.085 g, 0.5 mmol) and imidazole (0.034 g, 0.5 mmol) was refluxed for 3 h. After cooling to room temperature the solution was filtered. The single crystals of the title compound were obtained from the filtrate after 8 d.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. A segment of the polymeric chain of the title compound with 30% probability displacement ellipsoids (arbitrary spheres for H atoms); dashed lines indicate hydrogen bonding [symmetry codes: (i) x + 1/2, -y + 1/2, z - 1/2; (ii) x - 1/2, -y + 1/2, z + 1/2].
	Fig. 2. A digram showing the ovelapped arrangement of adjacent naphthaline ligands [symmetry code: (iii) 1 - x, 1 - y, 2 - z].
	Fig. 3. A diagram showing the contacts between imidazole rings [symmetry codes: (iv) 1 - x, -y, 1 - z; (v) 1 - x, 1 - y, 1 - z].

catena-Poly[[[aquabis(1H-imidazole-κN³)copper(II)]- µ-naphthalene-1,4-dicarboxylato-κ²O¹:O⁴] dihydrate] top

Crystal data top

[Cu(C₁₂H₆O₄)(C₃H₄N₂)₂(H₂O)]·2H₂O	F(000) = 964
M_r = 467.92	D_x = 1.522 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5466 reflections
a = 12.571 (2) Å	θ = 2.0–24.5°
b = 14.698 (3) Å	µ = 1.12 mm⁻¹
c = 12.636 (2) Å	T = 295 K
β = 119.011 (6)°	Prism, blue
V = 2041.8 (6) Å³	0.33 × 0.30 × 0.24 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	3989 independent reflections
Radiation source: fine-focus sealed tube	3251 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 10.0 pixels mm^-1	θ_max = 26.0°, θ_min = 1.9°
ω scans	h = −15→15
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −18→17
T_min = 0.660, T_max = 0.765	l = −15→15
23205 measured reflections

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) = 0.097	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0469P)² + 1.2324P] where P = (F_o² + 2F_c²)/3
3989 reflections	(Δ/σ)_max = 0.001
280 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Cu(C₁₂H₆O₄)(C₃H₄N₂)₂(H₂O)]·2H₂O	V = 2041.8 (6) Å³
M_r = 467.92	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.571 (2) Å	µ = 1.12 mm⁻¹
b = 14.698 (3) Å	T = 295 K
c = 12.636 (2) Å	0.33 × 0.30 × 0.24 mm
β = 119.011 (6)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	3989 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3251 reflections with I > 2σ(I)
T_min = 0.660, T_max = 0.765	R_int = 0.043
23205 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.06	Δρ_max = 0.50 e Å⁻³
3989 reflections	Δρ_min = −0.39 e Å⁻³
280 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)
Cu	0.61473 (3)	0.26395 (2)	0.57692 (3)	0.02692 (12)
N1	0.60619 (19)	0.13328 (15)	0.6141 (2)	0.0324 (5)
N2	0.5581 (2)	0.00805 (16)	0.6757 (2)	0.0408 (6)
H2N	0.5252	−0.0276	0.7056	0.049*
N3	0.64575 (19)	0.39456 (14)	0.56052 (19)	0.0310 (5)
N4	0.6481 (2)	0.54324 (16)	0.5765 (2)	0.0423 (6)
H4N	0.6401	0.5966	0.5997	0.051*
O1	0.52250 (17)	0.29662 (13)	0.66172 (17)	0.0356 (4)
O2	0.69612 (18)	0.29561 (17)	0.8353 (2)	0.0515 (6)
O3	0.19639 (16)	0.27227 (12)	0.98022 (16)	0.0311 (4)
O4	0.37130 (19)	0.25600 (14)	1.14909 (18)	0.0436 (5)
O5	0.41477 (17)	0.27662 (13)	0.38636 (17)	0.0387 (5)
H5A	0.3510	0.2580	0.3861	0.058*
H5B	0.4082	0.2721	0.3166	0.058*
O1W	0.0571 (2)	0.37164 (15)	0.7624 (2)	0.0548 (6)
H1A	0.1072	0.3426	0.8274	0.082*
H1B	0.0011	0.3328	0.7129	0.082*
O2WA	0.1105 (11)	0.4187 (8)	0.5762 (10)	0.181 (5)	0.50
H2A	0.0710	0.4002	0.6169	0.271*	0.50
H2B	0.1794	0.3868	0.6144	0.271*	0.50
O2WB	−0.0010 (9)	0.5394 (6)	0.5243 (9)	0.127 (3)	0.50
H2C	0.0693	0.5188	0.5711	0.190*	0.50
H2D	−0.0381	0.5579	0.5650	0.190*	0.50
C1	0.5111 (2)	0.30793 (18)	0.8430 (2)	0.0294 (6)
C2	0.3978 (2)	0.26894 (18)	0.7913 (2)	0.0325 (6)
H2	0.3638	0.2466	0.7127	0.039*
C3	0.3324 (2)	0.26212 (18)	0.8547 (2)	0.0327 (6)
H3	0.2564	0.2343	0.8181	0.039*
C4	0.3787 (2)	0.29591 (18)	0.9699 (2)	0.0283 (5)
C5	0.5331 (3)	0.3954 (2)	1.1323 (2)	0.0376 (6)
H5	0.4903	0.3923	1.1750	0.045*
C6	0.6357 (3)	0.4476 (2)	1.1762 (3)	0.0441 (7)
H6	0.6605	0.4810	1.2468	0.053*
C7	0.7035 (3)	0.4508 (2)	1.1152 (3)	0.0452 (7)
H7	0.7740	0.4856	1.1463	0.054*
C8	0.6671 (3)	0.4035 (2)	1.0115 (3)	0.0399 (7)
H8	0.7144	0.4053	0.9733	0.048*
C9	0.5581 (2)	0.35118 (17)	0.9593 (2)	0.0287 (5)
C10	0.4903 (2)	0.34582 (17)	1.0226 (2)	0.0284 (5)
C11	0.5842 (3)	0.30043 (18)	0.7771 (3)	0.0329 (6)
C12	0.3125 (2)	0.27394 (17)	1.0399 (2)	0.0289 (6)
C13	0.6235 (2)	0.46473 (19)	0.6125 (2)	0.0352 (6)
H13	0.5945	0.4598	0.6674	0.042*
C14	0.6877 (3)	0.5244 (2)	0.4974 (3)	0.0585 (9)
H14	0.7112	0.5661	0.4572	0.070*
C15	0.6865 (3)	0.4329 (2)	0.4878 (3)	0.0561 (9)
H15	0.7099	0.4006	0.4391	0.067*
C16	0.5431 (3)	0.0979 (2)	0.6621 (3)	0.0418 (7)
H16	0.4940	0.1315	0.6838	0.050*
C17	0.6345 (3)	−0.0168 (2)	0.6339 (3)	0.0405 (7)
H17	0.6612	−0.0754	0.6316	0.049*
C18	0.6642 (3)	0.05965 (19)	0.5964 (3)	0.0389 (6)
H18	0.7161	0.0627	0.5635	0.047*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu	0.03055 (19)	0.02963 (19)	0.03180 (19)	0.00027 (12)	0.02397 (15)	−0.00133 (13)
N1	0.0350 (12)	0.0336 (13)	0.0378 (12)	0.0004 (10)	0.0250 (10)	−0.0019 (10)
N2	0.0484 (14)	0.0342 (14)	0.0467 (14)	−0.0069 (11)	0.0287 (12)	0.0010 (11)
N3	0.0341 (12)	0.0315 (12)	0.0365 (12)	0.0011 (9)	0.0241 (10)	0.0009 (9)
N4	0.0448 (14)	0.0314 (13)	0.0511 (15)	−0.0005 (10)	0.0234 (12)	−0.0021 (11)
O1	0.0446 (11)	0.0381 (11)	0.0412 (11)	0.0005 (8)	0.0344 (10)	−0.0015 (8)
O2	0.0333 (12)	0.0736 (15)	0.0599 (14)	0.0010 (10)	0.0323 (11)	−0.0102 (11)
O3	0.0295 (10)	0.0387 (10)	0.0359 (10)	−0.0006 (8)	0.0243 (9)	0.0022 (8)
O4	0.0398 (11)	0.0662 (14)	0.0322 (11)	0.0016 (10)	0.0233 (9)	0.0083 (9)
O5	0.0379 (11)	0.0476 (12)	0.0360 (10)	−0.0086 (9)	0.0222 (9)	−0.0074 (9)
O1W	0.0509 (13)	0.0544 (14)	0.0585 (14)	0.0047 (11)	0.0261 (11)	−0.0028 (11)
O2WA	0.216 (12)	0.203 (12)	0.214 (12)	−0.016 (9)	0.175 (11)	0.029 (9)
O2WB	0.117 (6)	0.131 (8)	0.126 (7)	−0.021 (6)	0.054 (6)	−0.012 (6)
C1	0.0315 (14)	0.0311 (14)	0.0351 (14)	0.0024 (11)	0.0236 (12)	0.0008 (11)
C2	0.0341 (15)	0.0403 (16)	0.0315 (14)	−0.0037 (11)	0.0225 (12)	−0.0070 (11)
C3	0.0287 (14)	0.0423 (16)	0.0350 (14)	−0.0053 (11)	0.0218 (12)	−0.0046 (12)
C4	0.0290 (13)	0.0336 (14)	0.0311 (13)	0.0035 (10)	0.0215 (11)	0.0028 (11)
C5	0.0421 (16)	0.0464 (17)	0.0325 (14)	−0.0013 (13)	0.0245 (13)	−0.0036 (12)
C6	0.0501 (18)	0.0453 (18)	0.0374 (16)	−0.0077 (14)	0.0217 (14)	−0.0098 (13)
C7	0.0369 (16)	0.0500 (19)	0.0490 (18)	−0.0146 (13)	0.0211 (14)	−0.0088 (14)
C8	0.0360 (15)	0.0437 (17)	0.0478 (17)	−0.0077 (13)	0.0265 (14)	−0.0009 (13)
C9	0.0290 (13)	0.0304 (14)	0.0329 (13)	0.0021 (10)	0.0200 (11)	0.0016 (10)
C10	0.0309 (13)	0.0295 (14)	0.0304 (13)	0.0027 (10)	0.0192 (11)	0.0016 (10)
C11	0.0417 (17)	0.0273 (14)	0.0469 (17)	−0.0020 (11)	0.0351 (14)	−0.0013 (11)
C12	0.0332 (14)	0.0292 (14)	0.0345 (14)	0.0018 (11)	0.0245 (12)	−0.0001 (11)
C13	0.0354 (15)	0.0381 (16)	0.0348 (14)	−0.0012 (12)	0.0192 (12)	−0.0017 (12)
C14	0.080 (2)	0.0393 (19)	0.087 (3)	0.0010 (16)	0.065 (2)	0.0105 (17)
C15	0.087 (3)	0.0380 (18)	0.081 (2)	0.0069 (16)	0.070 (2)	0.0094 (16)
C16	0.0528 (18)	0.0339 (16)	0.0551 (18)	−0.0020 (13)	0.0390 (16)	−0.0023 (13)
C17	0.0414 (16)	0.0339 (16)	0.0454 (16)	0.0028 (12)	0.0206 (14)	0.0011 (13)
C18	0.0403 (16)	0.0370 (16)	0.0467 (17)	0.0057 (12)	0.0268 (14)	0.0023 (13)

Geometric parameters (Å, º) top

Cu—N1	1.992 (2)	C1—C2	1.371 (4)
Cu—N3	1.990 (2)	C1—C9	1.439 (4)
Cu—O1	1.9819 (17)	C1—C11	1.515 (3)
Cu—O3ⁱ	2.0116 (17)	C2—C3	1.404 (4)
Cu—O5	2.506 (2)	C2—H2	0.9300
N1—C16	1.317 (3)	C3—C4	1.372 (4)
N1—C18	1.382 (3)	C3—H3	0.9300
N2—C16	1.333 (4)	C4—C10	1.430 (4)
N2—C17	1.351 (4)	C4—C12	1.514 (3)
N2—H2N	0.8600	C5—C6	1.365 (4)
N3—C13	1.323 (3)	C5—C10	1.421 (4)
N3—C15	1.372 (4)	C5—H5	0.9300
N4—C13	1.331 (4)	C6—C7	1.400 (4)
N4—C14	1.344 (4)	C6—H6	0.9300
N4—H4N	0.8600	C7—C8	1.352 (4)
O1—C11	1.278 (3)	C7—H7	0.9300
O2—C11	1.234 (3)	C8—C9	1.424 (4)
O3—C12	1.277 (3)	C8—H8	0.9300
O3—Cuⁱⁱ	2.0116 (17)	C9—C10	1.426 (3)
O4—C12	1.237 (3)	C13—H13	0.9300
O5—H5A	0.8450	C14—C15	1.351 (5)
O5—H5B	0.8478	C14—H14	0.9300
O1W—H1A	0.8670	C15—H15	0.9300
O1W—H1B	0.8864	C16—H16	0.9300
O2WA—H2A	0.9128	C17—C18	1.340 (4)
O2WA—H2B	0.8933	C17—H17	0.9300
O2WB—H2C	0.8461	C18—H18	0.9300
O2WB—H2D	0.8876

O1—Cu—N3	91.04 (8)	C6—C5—H5	119.3
O1—Cu—N1	89.64 (8)	C10—C5—H5	119.3
N3—Cu—N1	172.02 (9)	C5—C6—C7	120.2 (3)
O1—Cu—O3ⁱ	175.67 (8)	C5—C6—H6	119.9
N3—Cu—O3ⁱ	90.49 (8)	C7—C6—H6	119.9
N1—Cu—O3ⁱ	89.41 (8)	C8—C7—C6	120.4 (3)
O5—Cu—N1	98.89 (8)	C8—C7—H7	119.8
O5—Cu—N3	89.09 (8)	C6—C7—H7	119.8
O5—Cu—O1	85.66 (7)	C7—C8—C9	121.6 (3)
O5—Cu—O3ⁱ	90.32 (7)	C7—C8—H8	119.2
C16—N1—C18	104.3 (2)	C9—C8—H8	119.2
C16—N1—Cu	127.07 (19)	C8—C9—C10	118.2 (2)
C18—N1—Cu	128.61 (18)	C8—C9—C1	122.6 (2)
C16—N2—C17	107.4 (2)	C10—C9—C1	119.1 (2)
C16—N2—H2N	126.3	C5—C10—C9	118.2 (2)
C17—N2—H2N	126.3	C5—C10—C4	122.6 (2)
C13—N3—C15	104.5 (2)	C9—C10—C4	119.1 (2)
C13—N3—Cu	126.94 (18)	O2—C11—O1	124.2 (2)
C15—N3—Cu	128.44 (19)	O2—C11—C1	119.8 (2)
C13—N4—C14	107.9 (3)	O1—C11—C1	115.9 (2)
C13—N4—H4N	126.0	O4—C12—O3	123.3 (2)
C14—N4—H4N	126.0	O4—C12—C4	119.7 (2)
C11—O1—Cu	115.93 (16)	O3—C12—C4	117.0 (2)
C12—O3—Cuⁱⁱ	114.83 (16)	N3—C13—N4	111.5 (2)
H5A—O5—H5B	110.9	N3—C13—H13	124.3
H1A—O1W—H1B	108.4	N4—C13—H13	124.3
H2A—O2WA—H2B	100.9	N4—C14—C15	106.2 (3)
H2C—O2WB—H2D	111.6	N4—C14—H14	126.9
C2—C1—C9	119.3 (2)	C15—C14—H14	126.9
C2—C1—C11	118.3 (2)	C14—C15—N3	109.9 (3)
C9—C1—C11	122.4 (2)	C14—C15—H15	125.0
C1—C2—C3	121.2 (2)	N3—C15—H15	125.0
C1—C2—H2	119.4	N1—C16—N2	111.8 (3)
C3—C2—H2	119.4	N1—C16—H16	124.1
C4—C3—C2	121.0 (2)	N2—C16—H16	124.1
C4—C3—H3	119.5	C18—C17—N2	106.5 (3)
C2—C3—H3	119.5	C18—C17—H17	126.7
C3—C4—C10	119.7 (2)	N2—C17—H17	126.7
C3—C4—C12	118.1 (2)	C17—C18—N1	109.9 (2)
C10—C4—C12	122.1 (2)	C17—C18—H18	125.1
C6—C5—C10	121.4 (2)	N1—C18—H18	125.1

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O3	0.87	1.99	2.846 (3)	170
O1W—H1B···O4ⁱⁱⁱ	0.89	1.93	2.789 (3)	162
O2WA—H2A···O1W	0.91	1.97	2.828 (13)	155
O2WB—H2C···O2WA	0.85	1.55	2.156 (16)	126
N2—H2N···O1W^iv	0.86	1.96	2.798 (4)	165
N4—H4N···O5^v	0.86	2.02	2.866 (3)	166
O5—H5A···O2ⁱⁱⁱ	0.85	1.90	2.716 (3)	162
O5—H5B···O4^vi	0.85	1.95	2.791 (3)	172
C17—H17···O2^vii	0.93	2.50	3.389 (4)	160

Symmetry codes: (iii) x−1/2, −y+1/2, z−1/2; (iv) −x+1/2, y−1/2, −z+3/2; (v) −x+1, −y+1, −z+1; (vi) x, y, z−1; (vii) −x+3/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₆O₄)(C₃H₄N₂)₂(H₂O)]·2H₂O
M_r	467.92
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	12.571 (2), 14.698 (3), 12.636 (2)
β (°)	119.011 (6)
V (Å³)	2041.8 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.12
Crystal size (mm)	0.33 × 0.30 × 0.24

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.660, 0.765
No. of measured, independent and observed [I > 2σ(I)] reflections	23205, 3989, 3251
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.097, 1.06
No. of reflections	3989
No. of parameters	280
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.39

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Cu—N1	1.992 (2)	Cu—O3ⁱ	2.0116 (17)
Cu—N3	1.990 (2)	Cu—O5	2.506 (2)
Cu—O1	1.9819 (17)

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O3	0.87	1.99	2.846 (3)	170
O1W—H1B···O4ⁱⁱ	0.89	1.93	2.789 (3)	162
O2WA—H2A···O1W	0.91	1.97	2.828 (13)	155
O2WB—H2C···O2WA	0.85	1.55	2.156 (16)	126
N2—H2N···O1Wⁱⁱⁱ	0.86	1.96	2.798 (4)	165
N4—H4N···O5^iv	0.86	2.02	2.866 (3)	166
O5—H5A···O2ⁱⁱ	0.85	1.90	2.716 (3)	162
O5—H5B···O4^v	0.85	1.95	2.791 (3)	172
C17—H17···O2^vi	0.93	2.50	3.389 (4)	160

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

Acknowledgements

The work was supported by the ZIJIN project of Zhejiang University, China.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Derissen, J. L., Timmermans, C. & Schoone, J. C. (1979). Cryst. Struct. Commun. 8, 533–536. CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Li, J.-H., Nie, J.-J. & Xu, D.-J. (2008). Acta Cryst. E64, m729. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, H., Yin, K.-L. & Xu, D.-J. (2005). Acta Cryst. C61, m19–m21. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Su, J.-R. & Xu, D.-J. (2004). J. Coord. Chem. 57, 223–229. Web of Science CSD CrossRef CAS Google Scholar

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