catena-Poly[[[aqua­bis­(1H-imidazole-κN3)copper(II)]-μ-furan-2,5-di­car­boxylato-κ2O2:O5] trihydrate]

Li, Y.-F.; Xu, Y.; Qin, X.-L.; Gao, W.-Y.; Gao, Y.

doi:10.1107/S1600536812016856

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m659

doi:10.1107/S1600536812016856

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catena-Poly[[[aquabis(1H-imidazole-κN³)copper(II)]-μ-furan-2,5-dicarboxylato-κ²O²:O⁵] trihydrate]

Ya-Feng Li,^a ^* Yue Xu,^a Xiao-Lin Qin,^a Wen-Yuan Gao ^a and Yue Gao ^a

^aSchool of Chemical Engineering, Changchun University of Technology, Changchun 130012, People's Republic of China
^*Correspondence e-mail: fly012345@sohu.com

(Received 2 April 2012; accepted 17 April 2012; online 21 April 2012)

In the title cooridnation polymer, {[Cu(C₆H₂O₅)(C₃H₄N₂)₂(H₂O)]·3H₂O}_n, an infinite chain is formed along [001] by linking of the Cu(C₃N₂H₄)₂(H₂O) entities with two bridging monodentate carboxylate groups of two different furan-2,5-dicarboxylate dianions. The geometry of the Cu²⁺ ion is a square-based pyramid with the water atom in the apical position and the ligand O and N atoms in a trans orientation. The dihedral angle between the imidazole planes is 83.96 (14)°. O_w–H⋯O and N_i–H⋯O (w = water and i = imidazole) hydrogen bonds help to establish the packing.

Related literature

For related structures and background to coordination polymers and their potential uses, see: Li et al. (2012a ,b ).

Experimental

Crystal data

[Cu(C₆H₂O₅)(C₃H₄N₂)₂(H₂O)]·3H₂O
M_r = 425.85
Monoclinic, P 2₁ /c
a = 7.5725 (15) Å
b = 13.339 (3) Å
c = 18.881 (5) Å
β = 113.42 (3)°
V = 1750.0 (7) Å³
Z = 4
Mo Kα radiation
μ = 1.30 mm⁻¹
T = 293 K
0.59 × 0.38 × 0.26 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.514, T_max = 0.728
16495 measured reflections
3977 independent reflections
3204 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.084
S = 1.03
3977 reflections
259 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N3	1.9638 (18)
Cu1—N1	1.9826 (17)
Cu1—O4ⁱ	1.9844 (14)
Cu1—O1	1.9858 (15)
Cu1—O1W	2.2797 (17)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2C⋯O4ⁱⁱ	0.86	2.10	2.953 (2)	169
N4—H4C⋯O3Wⁱⁱⁱ	0.86	1.95	2.756 (3)	156
O1W—H1A⋯O4W^iv	0.87 (2)	2.00 (2)	2.852 (3)	168 (2)
O1W—H1B⋯O2W^v	0.86 (2)	2.02 (2)	2.861 (3)	169 (3)
O2W—H2A⋯O5^vi	0.82 (2)	1.95 (2)	2.756 (2)	166 (3)
O2W—H2B⋯O2^vii	0.85 (2)	1.89 (2)	2.739 (2)	172 (2)
O3W—H3A⋯O1	0.84 (2)	2.22 (2)	3.013 (3)	157 (3)
O3W—H3B⋯O2W	0.81 (2)	1.93 (2)	2.705 (3)	161 (3)
O4W—H4A⋯O3W	0.88 (2)	2.23 (3)	2.878 (4)	130 (3)
O4W—H4B⋯O2^vii	0.90 (2)	2.16 (2)	3.052 (3)	171 (3)
Symmetry codes: (ii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x+1, -y+1, -z; (v) x+1, y, z; (vi) -x+1, -y+1, -z+1; (vii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812016856/hb6727sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016856/hb6727Isup2.hkl

checkCIF report

Comment top

Recently, we utilized furan-2,5-dicarboxyl acid as the ligand to construct coordination polymers (Li, et al., 2012a,b). As an extension of this work, a new chainlike compound, [Cu(C₃N₂H₄)₂(H₂O)(C₆H₂O₅)]^.3H₂O (I), is now described.

The asymmetric unit of (I) is consisted of one Cu(II) cation, one furan-2,5-dicarboxylate anion, two imidazole molecules and four water molecules – one coordinated water molecule and three crystallizated water molecules (Fig.1). Cu cation is coordinated by two carboxylate O atoms (d_Cu1–O of 1.985 (8) Å and 1.986 (8) Å) from different furan-2,5-dicarboxylate, two trans-arranged imidazoles (d_Cu1–N of 1.964 (4) Å and 1.984 (4) Å) and one coordinated water molecule (d_Cu1–O1W = 2.280 (5) Å) which locates at the axial position, exhibiting distorted pyramid. Two monodentate coordinated carboxyls of furan-2,5-dicarboxylate involve in the formation of infinite chain. The furan-2,5-dicarboxylate shows bridging µ¹,µ¹ coordinated mode.

Cu cations are linked by two monodentate carboxylate of different furan-2,5-dicarboxylate to give rise to an infinite chain (Fig.2). O_water–H···O and N_imidazole–H···O H-bonding interactions together link the adjcent chains to supermolecular net. (Fig.3).

Related literature top

For related structures and background to coordination polymers and their potential uses, see: Li et al. (2012a,b).

Experimental top

In a typically synthesized route of (I), furan-2,5-dicarboxyl acid (0.0156 g, 0.10 mmol), Cu(NO₃)₂^.2.5H₂O (0.0233 g, 0.10 mmol), and C₃N₂H₄ (0.020, 0.30 mmol) and NaOH (0.004, 0.10 mmol) were dissolved in water (5 ml, 278 mmol) under stirring. The mixture with molar ratio of 1 (furan-2,5-dicarboxyl acid): 1 (Cu(NO₃)₂^.2.5H₂O): 3 (C₃N₂H₄): 1 NaOH: 2780 H₂O was layed under room temperature for 2 days. The blue block product was collected as a single phase.

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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The unit cell of (I), showing displacement ellipsoids at the 50% probability level. [Symmetry codes: (i) 1) x, 0.5 - y, -0.5 + z.]
	Fig. 2. The stick plot of (I), displaying the infinite chain along [001] direction formed by linking the Cu with two monodentate carboxyls of two different furan-2,5-dicarboxylate.
	Fig. 3. The ball-stick packing diagram of (I). O_water–H···O and N_imidazole–H···O H-bonding interactions together link the adjcent chains to supermolecular net.

catena-Poly[[[aquabis(1H-imidazole-κN³)copper(II)]- µ-furan-2,5-dicarboxylato-κ²O²:O⁵] trihydrate] top

Crystal data top

[Cu(C₆H₂O₅)(C₃H₄N₂)₂(H₂O)]·3H₂O	F(000) = 876
M_r = 425.85	D_x = 1.616 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2000 reflections
a = 7.5725 (15) Å	θ = 3.1–27.5°
b = 13.339 (3) Å	µ = 1.30 mm⁻¹
c = 18.881 (5) Å	T = 293 K
β = 113.42 (3)°	Block, blue
V = 1750.0 (7) Å³	0.59 × 0.38 × 0.26 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	3977 independent reflections
Radiation source: fine-focus sealed tube	3204 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.1°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −17→17
T_min = 0.514, T_max = 0.728	l = −24→24
16495 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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ²(F_o²) + (0.0436P)²] where P = (F_o² + 2F_c²)/3
3977 reflections	(Δ/σ)_max < 0.001
259 parameters	Δρ_max = 0.57 e Å⁻³
13 restraints	Δρ_min = −0.58 e Å⁻³

Crystal data top

[Cu(C₆H₂O₅)(C₃H₄N₂)₂(H₂O)]·3H₂O	V = 1750.0 (7) Å³
M_r = 425.85	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5725 (15) Å	µ = 1.30 mm⁻¹
b = 13.339 (3) Å	T = 293 K
c = 18.881 (5) Å	0.59 × 0.38 × 0.26 mm
β = 113.42 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3977 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	3204 reflections with I > 2σ(I)
T_min = 0.514, T_max = 0.728	R_int = 0.059
16495 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	13 restraints
wR(F²) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.57 e Å⁻³
3977 reflections	Δρ_min = −0.58 e Å⁻³
259 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	0.80735 (3)	0.279641 (17)	0.187220 (13)	0.02352 (9)
O1	0.7606 (2)	0.35512 (11)	0.26878 (8)	0.0341 (3)
O2	0.8142 (3)	0.22327 (10)	0.34881 (10)	0.0417 (4)
O3	0.81345 (18)	0.34055 (9)	0.46325 (7)	0.0244 (3)
O4	0.85663 (19)	0.29295 (10)	0.60515 (8)	0.0293 (3)
O5	0.7608 (3)	0.44502 (11)	0.62582 (9)	0.0440 (4)
N1	0.5261 (2)	0.27626 (12)	0.12482 (10)	0.0289 (4)
N2	0.2161 (3)	0.26486 (15)	0.08964 (13)	0.0416 (5)
H2C	0.1064	0.2561	0.0923	0.050*
N3	1.0749 (2)	0.25501 (13)	0.25855 (10)	0.0304 (4)
N4	1.3374 (3)	0.17360 (18)	0.32566 (13)	0.0510 (6)
H4C	1.4207	0.1260	0.3413	0.061*
C1	0.7868 (3)	0.31396 (15)	0.33307 (12)	0.0282 (4)
C2	0.7783 (3)	0.38283 (14)	0.39338 (11)	0.0246 (4)
C3	0.7261 (3)	0.47994 (15)	0.39320 (13)	0.0367 (5)
H3	0.6959	0.5251	0.3525	0.044*
C4	0.7265 (3)	0.49939 (15)	0.46681 (12)	0.0359 (5)
H4	0.6956	0.5597	0.4839	0.043*
C5	0.7806 (3)	0.41319 (14)	0.50774 (11)	0.0248 (4)
C6	0.8006 (3)	0.38347 (15)	0.58597 (11)	0.0259 (4)
C13	0.4381 (3)	0.29424 (18)	0.04730 (13)	0.0402 (5)
H13	0.5004	0.3088	0.0149	0.048*
C14	0.2447 (3)	0.28732 (19)	0.02537 (16)	0.0479 (6)
H14	0.1507	0.2963	−0.0241	0.058*
C15	0.3867 (3)	0.25861 (16)	0.14793 (14)	0.0352 (5)
H15	0.4053	0.2437	0.1985	0.042*
C16	1.1938 (3)	0.3177 (2)	0.31533 (13)	0.0415 (5)
H16	1.1667	0.3834	0.3240	0.050*
C17	1.3568 (3)	0.2670 (2)	0.35633 (16)	0.0556 (8)
H17	1.4627	0.2915	0.3979	0.067*
C18	1.1672 (3)	0.16913 (18)	0.26737 (14)	0.0396 (5)
H18	1.1190	0.1128	0.2367	0.048*
O1W	0.8545 (3)	0.42683 (13)	0.13588 (11)	0.0493 (4)
H1A	0.847 (4)	0.423 (2)	0.0890 (10)	0.059*
H1B	0.963 (3)	0.454 (2)	0.1640 (13)	0.059*
O2W	0.1888 (3)	0.54338 (12)	0.22157 (10)	0.0456 (4)
H2A	0.224 (4)	0.5465 (18)	0.2687 (9)	0.055*
H2B	0.182 (3)	0.6015 (13)	0.2018 (13)	0.055*
O3W	0.4606 (3)	0.49932 (15)	0.16719 (15)	0.0676 (6)
H3A	0.552 (3)	0.458 (2)	0.1840 (19)	0.081*
H3B	0.387 (4)	0.500 (2)	0.1888 (18)	0.081*
O4W	0.2270 (4)	0.5961 (2)	0.02425 (14)	0.0892 (8)
H4A	0.264 (5)	0.5371 (16)	0.046 (2)	0.107*
H4B	0.202 (5)	0.636 (2)	0.0576 (18)	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.02336 (13)	0.03122 (14)	0.01630 (13)	0.00077 (9)	0.00822 (9)	−0.00176 (9)
O1	0.0403 (8)	0.0447 (8)	0.0176 (7)	0.0118 (7)	0.0117 (6)	0.0003 (6)
O2	0.0651 (11)	0.0320 (8)	0.0369 (10)	−0.0002 (8)	0.0297 (9)	−0.0051 (6)
O3	0.0307 (7)	0.0262 (6)	0.0169 (7)	0.0018 (6)	0.0101 (6)	−0.0004 (5)
O4	0.0310 (7)	0.0353 (7)	0.0256 (8)	0.0065 (6)	0.0156 (6)	0.0080 (6)
O5	0.0704 (11)	0.0414 (8)	0.0265 (9)	0.0090 (8)	0.0258 (8)	−0.0022 (6)
N1	0.0247 (8)	0.0383 (9)	0.0245 (9)	−0.0025 (7)	0.0107 (7)	−0.0036 (7)
N2	0.0247 (9)	0.0530 (11)	0.0484 (13)	−0.0066 (8)	0.0159 (8)	−0.0058 (9)
N3	0.0260 (8)	0.0385 (9)	0.0251 (9)	−0.0011 (7)	0.0084 (7)	0.0004 (7)
N4	0.0297 (10)	0.0728 (15)	0.0469 (14)	0.0107 (10)	0.0115 (9)	0.0212 (12)
C1	0.0269 (10)	0.0379 (10)	0.0208 (10)	−0.0006 (8)	0.0103 (8)	−0.0050 (8)
C2	0.0269 (9)	0.0307 (9)	0.0162 (9)	−0.0005 (8)	0.0085 (8)	0.0018 (7)
C3	0.0564 (14)	0.0320 (10)	0.0247 (11)	0.0066 (10)	0.0193 (10)	0.0067 (8)
C4	0.0568 (13)	0.0278 (10)	0.0265 (11)	0.0063 (10)	0.0201 (10)	0.0009 (8)
C5	0.0267 (9)	0.0292 (9)	0.0192 (10)	0.0013 (8)	0.0100 (8)	−0.0020 (7)
C6	0.0245 (9)	0.0337 (10)	0.0194 (10)	−0.0016 (8)	0.0087 (8)	−0.0007 (8)
C13	0.0312 (11)	0.0641 (15)	0.0247 (12)	−0.0038 (10)	0.0104 (9)	0.0001 (10)
C14	0.0299 (11)	0.0687 (17)	0.0375 (15)	−0.0005 (11)	0.0051 (10)	−0.0023 (12)
C15	0.0337 (11)	0.0407 (11)	0.0338 (12)	−0.0052 (9)	0.0161 (10)	0.0003 (9)
C16	0.0406 (12)	0.0503 (13)	0.0297 (12)	−0.0143 (10)	0.0100 (10)	−0.0041 (10)
C17	0.0308 (12)	0.097 (2)	0.0308 (14)	−0.0189 (13)	0.0033 (10)	0.0092 (14)
C18	0.0300 (11)	0.0509 (13)	0.0406 (14)	0.0020 (10)	0.0168 (10)	0.0045 (11)
O1W	0.0618 (11)	0.0474 (9)	0.0358 (10)	−0.0173 (9)	0.0164 (9)	0.0027 (8)
O2W	0.0711 (12)	0.0367 (8)	0.0329 (10)	−0.0039 (8)	0.0247 (9)	0.0019 (7)
O3W	0.0549 (12)	0.0521 (11)	0.0975 (19)	0.0156 (10)	0.0322 (12)	−0.0010 (11)
O4W	0.126 (2)	0.0902 (17)	0.0541 (16)	0.0284 (17)	0.0381 (15)	0.0092 (13)

Geometric parameters (Å, º) top

Cu1—N3	1.9638 (18)	C2—C3	1.354 (3)
Cu1—N1	1.9826 (17)	C3—C4	1.413 (3)
Cu1—O4ⁱ	1.9844 (14)	C3—H3	0.9300
Cu1—O1	1.9858 (15)	C4—C5	1.355 (3)
Cu1—O1W	2.2797 (17)	C4—H4	0.9300
O1—C1	1.274 (2)	C5—C6	1.478 (3)
O2—C1	1.243 (2)	C13—C14	1.357 (3)
O3—C2	1.360 (2)	C13—H13	0.9300
O3—C5	1.368 (2)	C14—H14	0.9300
O4—C6	1.283 (2)	C15—H15	0.9300
O5—C6	1.229 (2)	C16—C17	1.349 (3)
N1—C15	1.314 (3)	C16—H16	0.9300
N1—C13	1.367 (3)	C17—H17	0.9300
N2—C15	1.326 (3)	C18—H18	0.9300
N2—C14	1.349 (3)	O1W—H1A	0.866 (16)
N2—H2C	0.8600	O1W—H1B	0.858 (16)
N3—C18	1.318 (3)	O2W—H2A	0.822 (16)
N3—C16	1.375 (3)	O2W—H2B	0.853 (15)
N4—C18	1.322 (3)	O3W—H3A	0.843 (17)
N4—C17	1.357 (4)	O3W—H3B	0.808 (17)
N4—H4C	0.8600	O4W—H4A	0.884 (18)
C1—C2	1.484 (3)	O4W—H4B	0.900 (18)

N3—Cu1—N1	167.24 (7)	C2—C3—C4	106.66 (18)
N3—Cu1—O4ⁱ	89.48 (7)	C2—C3—H3	126.7
N1—Cu1—O4ⁱ	90.91 (7)	C4—C3—H3	126.7
N3—Cu1—O1	90.35 (7)	C5—C4—C3	106.69 (18)
N1—Cu1—O1	89.54 (7)	C5—C4—H4	126.7
O4ⁱ—Cu1—O1	178.68 (6)	C3—C4—H4	126.7
N3—Cu1—O1	90.35 (7)	C4—C5—O3	109.77 (17)
N1—Cu1—O1	89.54 (7)	C4—C5—C6	133.28 (18)
O4ⁱ—Cu1—O1	178.68 (6)	O3—C5—C6	116.88 (16)
N3—Cu1—O1W	98.18 (7)	O5—C6—O4	126.13 (19)
N1—Cu1—O1W	94.58 (7)	O5—C6—C5	118.68 (18)
O4ⁱ—Cu1—O1W	88.76 (6)	O4—C6—C5	115.19 (17)
O1—Cu1—O1W	89.96 (7)	C14—C13—N1	108.8 (2)
O1—Cu1—O1W	89.96 (7)	C14—C13—H13	125.6
C1—O1—Cu1	120.82 (13)	N1—C13—H13	125.6
C2—O3—C5	106.77 (14)	N2—C14—C13	106.3 (2)
C6—O4—Cu1ⁱⁱ	122.40 (13)	N2—C14—H14	126.9
C15—N1—C13	105.82 (18)	C13—C14—H14	126.9
C15—N1—Cu1	128.44 (16)	N1—C15—N2	111.1 (2)
C13—N1—Cu1	125.73 (15)	N1—C15—H15	124.5
C15—N2—C14	107.98 (19)	N2—C15—H15	124.5
C15—N2—H2C	126.0	C17—C16—N3	108.0 (2)
C14—N2—H2C	126.0	C17—C16—H16	126.0
C18—N3—C16	106.23 (19)	N3—C16—H16	126.0
C18—N3—Cu1	125.66 (15)	C16—C17—N4	107.2 (2)
C16—N3—Cu1	127.62 (16)	C16—C17—H17	126.4
C18—N4—C17	107.5 (2)	N4—C17—H17	126.4
C18—N4—H4C	126.2	N3—C18—N4	111.0 (2)
C17—N4—H4C	126.2	N3—C18—H18	124.5
O2—C1—O1	126.51 (19)	N4—C18—H18	124.5
O2—C1—O1	126.51 (19)	Cu1—O1W—H1A	115.2 (18)
O2—C1—C2	118.23 (18)	Cu1—O1W—H1B	111.8 (19)
O1—C1—C2	115.25 (18)	H1A—O1W—H1B	109 (2)
O1—C1—C2	115.25 (18)	H2A—O2W—H2B	111 (2)
C3—C2—O3	110.09 (17)	H3A—O3W—H3B	117 (3)
C3—C2—C1	133.77 (19)	H4A—O4W—H4B	108 (2)
O3—C2—C1	115.85 (16)

N3—Cu1—O1—O1	0.00 (17)	O2—C1—C2—C3	−169.3 (2)
N1—Cu1—O1—O1	0.00 (17)	O1—C1—C2—C3	9.3 (3)
N3—Cu1—O1—C1	−57.95 (16)	O1—C1—C2—C3	9.3 (3)
N1—Cu1—O1—C1	109.29 (16)	O2—C1—C2—O3	3.8 (3)
O1—Cu1—O1—C1	0 (100)	O1—C1—C2—O3	−177.51 (16)
O1W—Cu1—O1—C1	−156.13 (16)	O1—C1—C2—O3	−177.51 (16)
N3—Cu1—N1—C15	46.9 (4)	O3—C2—C3—C4	−0.7 (3)
O4ⁱ—Cu1—N1—C15	138.59 (19)	C1—C2—C3—C4	172.8 (2)
O1—Cu1—N1—C15	−42.66 (19)	C2—C3—C4—C5	0.5 (3)
O1—Cu1—N1—C15	−42.66 (19)	C3—C4—C5—O3	−0.2 (2)
O1W—Cu1—N1—C15	−132.59 (19)	C3—C4—C5—C6	−177.0 (2)
N3—Cu1—N1—C13	−134.4 (3)	C2—O3—C5—C4	−0.2 (2)
O4ⁱ—Cu1—N1—C13	−42.69 (18)	C2—O3—C5—C6	177.16 (16)
O1—Cu1—N1—C13	136.07 (18)	Cu1ⁱⁱ—O4—C6—O5	21.2 (3)
O1—Cu1—N1—C13	136.07 (18)	Cu1ⁱⁱ—O4—C6—C5	−157.71 (13)
O1W—Cu1—N1—C13	46.14 (19)	C4—C5—C6—O5	0.9 (4)
N1—Cu1—N3—C18	46.9 (4)	O3—C5—C6—O5	−175.63 (17)
O4ⁱ—Cu1—N3—C18	−44.92 (18)	C4—C5—C6—O4	179.9 (2)
O1—Cu1—N3—C18	136.40 (19)	O3—C5—C6—O4	3.4 (3)
O1—Cu1—N3—C18	136.40 (19)	C15—N1—C13—C14	0.3 (3)
O1W—Cu1—N3—C18	−133.59 (18)	Cu1—N1—C13—C14	−178.68 (16)
N1—Cu1—N3—C16	−124.0 (3)	C15—N2—C14—C13	0.0 (3)
O4ⁱ—Cu1—N3—C16	144.21 (19)	N1—C13—C14—N2	−0.2 (3)
O1—Cu1—N3—C16	−34.47 (19)	C13—N1—C15—N2	−0.3 (3)
O1—Cu1—N3—C16	−34.47 (19)	Cu1—N1—C15—N2	178.64 (14)
O1W—Cu1—N3—C16	55.5 (2)	C14—N2—C15—N1	0.2 (3)
O1—O1—C1—O2	0.00 (14)	C18—N3—C16—C17	0.7 (3)
Cu1—O1—C1—O2	−11.2 (3)	Cu1—N3—C16—C17	173.02 (16)
Cu1—O1—C1—O1	0 (100)	N3—C16—C17—N4	−0.7 (3)
O1—O1—C1—C2	0.0 (2)	C18—N4—C17—C16	0.4 (3)
Cu1—O1—C1—C2	170.28 (12)	C16—N3—C18—N4	−0.5 (3)
C5—O3—C2—C3	0.5 (2)	Cu1—N3—C18—N4	−172.96 (15)
C5—O3—C2—C1	−174.22 (16)	C17—N4—C18—N3	0.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O4ⁱⁱⁱ	0.86	2.10	2.953 (2)	169
N4—H4C···O3W^iv	0.86	1.95	2.756 (3)	156
O1W—H1A···O4W^v	0.87 (2)	2.00 (2)	2.852 (3)	168 (2)
O1W—H1B···O2W^vi	0.86 (2)	2.02 (2)	2.861 (3)	169 (3)
O2W—H2A···O5^vii	0.82 (2)	1.95 (2)	2.756 (2)	166 (3)
O2W—H2B···O2^viii	0.85 (2)	1.89 (2)	2.739 (2)	172 (2)
O3W—H3A···O1	0.84 (2)	2.22 (2)	3.013 (3)	157 (3)
O3W—H3B···O2W	0.81 (2)	1.93 (2)	2.705 (3)	161 (3)
O4W—H4A···O3W	0.88 (2)	2.23 (3)	2.878 (4)	130 (3)
O4W—H4B···O2^viii	0.90 (2)	2.16 (2)	3.052 (3)	171 (3)

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

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₂O₅)(C₃H₄N₂)₂(H₂O)]·3H₂O
M_r	425.85
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.5725 (15), 13.339 (3), 18.881 (5)
β (°)	113.42 (3)
V (Å³)	1750.0 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.30
Crystal size (mm)	0.59 × 0.38 × 0.26

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.514, 0.728
No. of measured, independent and observed [I > 2σ(I)] reflections	16495, 3977, 3204
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.084, 1.03
No. of reflections	3977
No. of parameters	259
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.58

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2000).

Selected bond lengths (Å) top

Cu1—N3	1.9638 (18)	Cu1—O1	1.9858 (15)
Cu1—N1	1.9826 (17)	Cu1—O1W	2.2797 (17)
Cu1—O4ⁱ	1.9844 (14)

Symmetry code: (i) x, −y+1/2, z−1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2C···O4ⁱⁱ	0.86	2.10	2.953 (2)	169
N4—H4C···O3Wⁱⁱⁱ	0.86	1.95	2.756 (3)	156
O1W—H1A···O4W^iv	0.866 (16)	1.999 (16)	2.852 (3)	168 (2)
O1W—H1B···O2W^v	0.858 (16)	2.015 (17)	2.861 (3)	169 (3)
O2W—H2A···O5^vi	0.822 (16)	1.953 (17)	2.756 (2)	166 (3)
O2W—H2B···O2^vii	0.853 (15)	1.891 (16)	2.739 (2)	172 (2)
O3W—H3A···O1	0.843 (17)	2.22 (2)	3.013 (3)	157 (3)
O3W—H3B···O2W	0.808 (17)	1.928 (16)	2.705 (3)	161 (3)
O4W—H4A···O3W	0.884 (18)	2.23 (3)	2.878 (4)	130 (3)
O4W—H4B···O2^vii	0.900 (18)	2.16 (2)	3.052 (3)	171 (3)

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

Acknowledgements

This project was sponsored by the Scientific Research Foundation for the Returned Overseas Team, Chinese Education Ministry.

References

Brandenburg, K. (2000). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
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Rigaku (1998). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
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