Octa­aqua­bis(μ2-1H-pyrazole-3,5-di­carboxyl­ato)tricopper(II) tetra­hydrate

Li, Z.-G.; Li, S.-A.; Liu, D.-Q.; Huang, Y.-H.; Xu, J.-W.

doi:10.1107/S1600536810001595

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 2| February 2010| Page m216

https://doi.org/10.1107/S1600536810001595

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Octaaquabis(μ₂-1H-pyrazole-3,5-dicarboxylato)tricopper(II) tetrahydrate

Zhi-Gang Li,^a Shao-Ai Li,^a De-Quan Liu,^a Yi-Hua Huang ^b and Jing-Wei Xu ^c ^*

^aShenzhen Environmental Monitoring Center, Shenzhen 518008, People's Republic of China, ^bShenzhen Environmental Protecting Bureau, Shenzhen 518008, People's Republic of China, and ^cState Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, People's Republic of China
^*Correspondence e-mail: jwxu@ciac.jl.cn

(Received 22 November 2009; accepted 13 January 2010; online 30 January 2010)

In the trinucler Cu^II complex molecule of the title compound, [Cu₃(C₅HN₂O₄)₂(H₂O)₈]·4H₂O, the central Cu^II atom is located on an inversion centre and is coordinated in a distorted octahedral geometry. The equatorial sites are occupied by two N and two O atoms from two pyrazole-3,5-dicarboxylate ligands and the axial positions are occupied by two water molecules. The two other symmetry-related Cu^II atoms are pentacoordinated and assume a square-pyramidal geometry. In the crystal structure, coordinated and uncoordinated water molecules and carboxylate O atoms are linked by O—H⋯O hydrogen bonds.

Related literature

For general background to coordination polymers, see: Yaghi et al. (2003 ); Kitagawa et al. (2004 ). For related structures, see: King et al. (2003 ); Li (2005 ). For graph-set motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

[Cu₃(C₅HN₂O₄)₂(H₂O)₈]·4H₂O
M_r = 712.97
Triclinic, $[P \overline 1]$
a = 8.9455 (6) Å
b = 9.1018 (7) Å
c = 9.1125 (7) Å
α = 103.485 (1)°
β = 90.924 (1)°
γ = 117.505 (1)°
V = 633.31 (8) Å³
Z = 1
Mo Kα radiation
μ = 2.59 mm⁻¹
T = 293 K
0.17 × 0.13 × 0.05 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.666, T_max = 0.877
3535 measured reflections
2412 independent reflections
2198 reflections with I > 2σ(I)
R_int = 0.010

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.095
S = 1.08
2412 reflections
205 parameters
12 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.89 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5A⋯O1ⁱ	0.87 (3)	2.28 (4)	3.050 (4)	148 (4)
O5—H5B⋯O8ⁱⁱ	0.87 (4)	2.16 (4)	3.021 (5)	172 (4)
O6—H6A⋯O8ⁱⁱⁱ	0.87 (4)	2.38 (5)	3.078 (4)	137 (4)
O6—H6B⋯O2ⁱⁱⁱ	0.87 (6)	2.30 (6)	3.077 (4)	149 (4)
O7—H7A⋯O1ⁱⁱ	0.80 (4)	2.16 (4)	2.860 (4)	147 (4)
O7—H7B⋯O4^iv	0.81 (4)	1.91 (4)	2.715 (4)	171 (4)
O8—H8A⋯O7^v	0.81 (3)	2.06 (3)	2.854 (4)	169 (4)
O8—H8B⋯O1	0.81 (5)	2.03 (5)	2.836 (4)	175 (4)
O9—H9A⋯O4^vi	0.87 (4)	2.26 (4)	3.061 (4)	154 (4)
Symmetry codes: (i) x, y, z-1; (ii) -x+1, -y+2, -z+1; (iii) -x, -y+1, -z+1; (iv) x-1, y, z; (v) x, y, z+1; (vi) x-1, y-1, z.

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810001595/is2499sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810001595/is2499Isup2.hkl

checkCIF report

Comment top

The design and synthesis of novel coordination architectures is a fertile field due to the intriguing network topologies and potential a pplications as new classes of materials (Yaghi et al., 2003; Kitagawa et al., 2004). The ligand of pyrazole-3,5-dicarboxylic acid has several potential coordination sites involving both two N atoms of the pyrazole ring and four carboxylate O atoms. These multifunctional coordination sites are highly accessible to metal ions, as such, the ligand can coordinate as a mono-, bi-, or tetradentate ligand and can act to link together metal centers through a number of bridging modes (Li, 2005). The divalent copper atoms are easily to precipitate with the OH^- when the pyrazole-3,5-dicarboxylic acids are deprotoned in base water solution, the mixed solution can obtain coordianted polymer single crystals in hydrothermal condition (King et al., 2003). Nevertheless, when the ammonia was added to the mixed solution, because of the complexing action between the copper atoms and NH₃, the turbid soltuion became clear. After the ammonia slowly evaporated, we obtained the blue crystals, compound (I), as shown in Fig.1, a copper(II) trimer.

The central copper atom, Cu1, lies on a crystallographic inversion center. The Cu1 atom has a six-coordinate octahedral geometry, in which two O atoms and two N atoms from two pyrazole-3,5-dicarboxylate ligands occupy the equatorial plane, and the axial coordination sites are occupied two water molecules; the Cu—N/O bond distances range from 2.003 (2) to 2.437 (3) Å. The other two symmetry-related copper atoms, Cu2, have a pentacoordinate square-pyramidal geometry, where a pyrazole nitrogen N2 and a carboxylate oxygen O3 from one pyrazole-3,5-dicarboxylate ligand occupy two coordination sites and the remaining three positions are occupied by water molecules; the Cu—N/O bond distances range from 1.984 (2) to 2.237 (2) Å. The pyrazole-3,5-dicarboxylate ligand is not strictly planar. Deviation from the mean plane defined by the pyrazole ring is seen for both carboxylate groups with values ranging from 0.034 (1) to 0.205 (1) Å. The dihedral angle between the two carboxylate mean planes is 11.3 (3)°. It can be seen that the ligand bite angle at the two different copper centers Cu1 and Cu2 is similar, 74.8 (4) and 80.6 (4)°, respectively. This implies that the pyrazole-3,5-dicarboxylate ligand is a fairly rigid ligand and retains its integrity on metal chelation.

In the asymmetric unit, there are two lattice water molecules, four coordinated water molecules and carboxylate O atoms, which form complexed hydrogen-bonding interactions. Two lattice water molecules and its symmetric equivalents together with two carboxylate O atoms from two trimers form a hydrogen-bonded chair conformation, generating an R₄⁶(6) motif (Bernstein et al., 1995). Meanwhile, the four lattice water molecules in each R₄⁶(6) motif also bind four another trimers by O7—H7B···O4 hydrogen bond interaction, and O5—H5B···O8 hydrogen bond interaction. Those strong hydrogen-bonding interactions as well as some weaker interactions, such as O5—H5A···O1, O6—H6A···O8, O6—H6B···O2 and O9—H9A···O4, extend the crystal structure into a three-dimensional supramolecular network (Fig. 2).

Related literature top

For general background to coordination polymers, see: Yaghi et al. (2003); Kitagawa et al. (2004). For related structures, see: King et al. (2003); Li (2005). For graph-set motifs, see: Bernstein et al. (1995).

Experimental top

The title complex was prepared by the addition of Cu(BF₄)₂ (20 mmol) and pyrazole-3,5-dicarboxylic acid (30 mmol) to 40 ml water. The mixture was stirred for 1 h, a blue precipitate was obtained. A minimum amount of ammonia (14 M) was added to give a blue solution. Suitable crystals were obtained after standing at room temperature for several days (yield 51% based on Cu).

Structure description top

For general background to coordination polymers, see: Yaghi et al. (2003); Kitagawa et al. (2004). For related structures, see: King et al. (2003); Li (2005). For graph-set motifs, see: Bernstein et al. (1995).

Computing details top

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

Figures top

	Fig. 1. A view of (I), with the atom-labeling scheme and 30% probability displacement ellipsoids. [Symmetry code: (A) 1 - x, 1 - y, -z.]
	Fig. 2. Perspective view of packing structure of (I) along the c axis. For the sake of clarity, H atoms not involved in hydrogen bonds have been omitted.

Octaaquabis(µ₂-1H-pyrazole-3,5-dicarboxylato)tricopper(II) tetrahydrate top

Crystal data top

[Cu₃(C₅HN₂O₄)₂(H₂O)₈]·4H₂O	Z = 1
M_r = 712.97	F(000) = 361
Triclinic, P1	D_x = 1.869 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.9455 (6) Å	Cell parameters from 2128 reflections
b = 9.1018 (7) Å	θ = 2.3–26.0°
c = 9.1125 (7) Å	µ = 2.59 mm⁻¹
α = 103.485 (1)°	T = 293 K
β = 90.924 (1)°	Tabular, blue
γ = 117.505 (1)°	0.17 × 0.13 × 0.05 mm
V = 633.31 (8) Å³

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	2198 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.010
φ and ω scans	θ_max = 26.0°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
T_min = 0.666, T_max = 0.877	k = −11→9
3535 measured reflections	l = −11→9

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) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0495P)² + 1.615P] where P = (F_o² + 2F_c²)/3
2412 reflections	(Δ/σ)_max = 0.042
205 parameters	Δρ_max = 0.89 e Å⁻³
12 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Cu₃(C₅HN₂O₄)₂(H₂O)₈]·4H₂O	γ = 117.505 (1)°
M_r = 712.97	V = 633.31 (8) Å³
Triclinic, P1	Z = 1
a = 8.9455 (6) Å	Mo Kα radiation
b = 9.1018 (7) Å	µ = 2.59 mm⁻¹
c = 9.1125 (7) Å	T = 293 K
α = 103.485 (1)°	0.17 × 0.13 × 0.05 mm
β = 90.924 (1)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	2412 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2198 reflections with I > 2σ(I)
T_min = 0.666, T_max = 0.877	R_int = 0.010
3535 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	12 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.89 e Å⁻³
2412 reflections	Δρ_min = −0.54 e Å⁻³
205 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	0.5000	0.5000	0.0000	0.01250 (16)
Cu2	0.18693 (5)	0.39943 (5)	0.35269 (4)	0.01365 (14)
O1	0.4661 (3)	0.8149 (3)	0.7106 (3)	0.0205 (5)
O2	0.2463 (3)	0.5801 (3)	0.5590 (3)	0.0180 (5)
O3	0.8061 (3)	0.6833 (3)	0.0762 (3)	0.0187 (5)
O4	0.9786 (3)	0.8716 (3)	0.2903 (3)	0.0198 (5)
O5	0.4555 (4)	0.6959 (4)	−0.0015 (3)	0.0319 (7)
H5A	0.420 (6)	0.690 (7)	−0.093 (3)	0.038*
H5B	0.541 (5)	0.797 (4)	0.040 (5)	0.038*
O6	−0.0225 (4)	0.2439 (4)	0.4269 (4)	0.0318 (7)
H6A	−0.091 (5)	0.148 (4)	0.360 (5)	0.038*
H6B	−0.083 (6)	0.291 (6)	0.468 (5)	0.038*
O7	0.2443 (4)	0.8545 (4)	0.1630 (3)	0.0268 (6)
H7A	0.330 (4)	0.923 (5)	0.219 (5)	0.032*
H7B	0.159 (4)	0.848 (6)	0.198 (5)	0.032*
O8	0.2631 (4)	0.9378 (4)	0.8781 (3)	0.0280 (6)
H8A	0.245 (6)	0.913 (6)	0.958 (3)	0.034*
H8B	0.316 (5)	0.899 (6)	0.826 (5)	0.034*
O9	0.1851 (4)	0.2020 (4)	0.1939 (4)	0.0335 (7)
H9A	0.104 (5)	0.102 (4)	0.195 (6)	0.040*
H9B	0.282 (4)	0.202 (7)	0.197 (6)	0.040*
O10	0.0459 (4)	0.4770 (5)	0.2092 (4)	0.0415 (8)
H10A	0.102 (6)	0.580 (4)	0.202 (6)	0.050*
H10B	−0.052 (4)	0.452 (7)	0.238 (6)	0.050*
N1	0.5326 (3)	0.5804 (4)	0.2330 (3)	0.0135 (6)
N2	0.4214 (3)	0.5670 (4)	0.3334 (3)	0.0136 (6)
C1	0.5045 (4)	0.6944 (4)	0.4637 (4)	0.0136 (6)
C2	0.6742 (4)	0.7934 (4)	0.4484 (4)	0.0151 (7)
H2	0.7597	0.8884	0.5196	0.015*
C3	0.6852 (4)	0.7162 (4)	0.3012 (4)	0.0125 (6)
C4	0.4011 (4)	0.6993 (4)	0.5882 (4)	0.0153 (7)
C5	0.8344 (4)	0.7607 (4)	0.2152 (4)	0.0136 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0145 (3)	0.0118 (3)	0.0090 (3)	0.0055 (2)	0.0011 (2)	0.0007 (2)
Cu2	0.0111 (2)	0.0123 (2)	0.0137 (2)	0.00298 (17)	0.00279 (15)	0.00235 (16)
O1	0.0194 (12)	0.0210 (13)	0.0134 (12)	0.0060 (11)	0.0028 (10)	−0.0012 (10)
O2	0.0141 (12)	0.0167 (12)	0.0181 (12)	0.0045 (10)	0.0046 (9)	0.0018 (10)
O3	0.0171 (12)	0.0216 (13)	0.0122 (12)	0.0056 (10)	0.0040 (9)	0.0030 (10)
O4	0.0116 (11)	0.0210 (13)	0.0172 (12)	0.0012 (10)	0.0018 (9)	0.0026 (10)
O5	0.0366 (17)	0.0299 (16)	0.0294 (16)	0.0160 (14)	0.0037 (13)	0.0082 (13)
O6	0.0251 (15)	0.0303 (16)	0.0354 (17)	0.0099 (13)	0.0063 (12)	0.0076 (13)
O7	0.0209 (14)	0.0209 (14)	0.0335 (16)	0.0080 (12)	0.0098 (12)	0.0025 (12)
O8	0.0286 (15)	0.0294 (16)	0.0257 (15)	0.0154 (13)	0.0053 (12)	0.0033 (12)
O9	0.0323 (16)	0.0270 (16)	0.0358 (17)	0.0100 (13)	0.0082 (13)	0.0076 (13)
O10	0.0351 (18)	0.0381 (19)	0.054 (2)	0.0156 (16)	0.0024 (16)	0.0220 (16)
N1	0.0125 (13)	0.0140 (14)	0.0123 (13)	0.0050 (11)	0.0035 (10)	0.0035 (11)
N2	0.0119 (13)	0.0146 (14)	0.0112 (13)	0.0044 (11)	0.0020 (10)	0.0018 (11)
C1	0.0136 (15)	0.0139 (16)	0.0119 (15)	0.0057 (13)	0.0014 (12)	0.0032 (12)
C2	0.0125 (15)	0.0157 (17)	0.0132 (16)	0.0039 (13)	0.0005 (12)	0.0031 (13)
C3	0.0127 (15)	0.0126 (16)	0.0103 (15)	0.0047 (13)	−0.0010 (12)	0.0027 (12)
C4	0.0149 (16)	0.0166 (17)	0.0152 (16)	0.0081 (14)	0.0031 (13)	0.0047 (13)
C5	0.0150 (16)	0.0130 (17)	0.0133 (16)	0.0064 (14)	0.0037 (13)	0.0048 (13)

Geometric parameters (Å, º) top

Cu1—O5	2.001 (3)	O6—H6B	0.87 (6)
Cu1—O5ⁱ	2.001 (3)	O7—H7A	0.80 (2)
Cu1—N1	2.047 (3)	O7—H7B	0.81 (2)
Cu1—N1ⁱ	2.047 (3)	O8—H8A	0.81 (2)
Cu1—O3ⁱ	2.437 (2)	O8—H8B	0.81 (5)
Cu1—O3	2.437 (2)	O9—H9A	0.87 (2)
Cu2—N2	1.985 (3)	O9—H9B	0.87 (5)
Cu2—O6	2.002 (3)	O10—H10A	0.85 (2)
Cu2—O9	2.021 (3)	O10—H10B	0.86 (5)
Cu2—O2	2.059 (2)	N1—N2	1.345 (4)
Cu2—O10	2.236 (3)	N1—C3	1.354 (4)
O1—C4	1.247 (4)	N2—C1	1.357 (4)
O2—C4	1.277 (4)	C1—C2	1.392 (5)
O3—C5	1.255 (4)	C1—C4	1.481 (5)
O4—C5	1.264 (4)	C2—C3	1.390 (5)
O5—H5A	0.87 (2)	C2—H2	0.9300
O5—H5B	0.87 (2)	C3—C5	1.497 (4)
O6—H6A	0.87 (2)

O5—Cu1—O5ⁱ	180.0	Cu2—O6—H6B	116 (3)
O5—Cu1—N1	87.36 (12)	H6A—O6—H6B	108 (5)
O5ⁱ—Cu1—N1	92.64 (12)	H7A—O7—H7B	113 (5)
O5—Cu1—N1ⁱ	92.64 (12)	H8A—O8—H8B	117 (5)
O5ⁱ—Cu1—N1ⁱ	87.36 (12)	Cu2—O9—H9A	114 (3)
N1—Cu1—N1ⁱ	180.00 (18)	Cu2—O9—H9B	114 (3)
O5—Cu1—O3ⁱ	85.89 (11)	H9A—O9—H9B	110 (5)
O5ⁱ—Cu1—O3ⁱ	94.11 (11)	Cu2—O10—H10A	115 (4)
N1—Cu1—O3ⁱ	105.11 (9)	Cu2—O10—H10B	109 (4)
N1ⁱ—Cu1—O3ⁱ	74.89 (9)	H10A—O10—H10B	114 (6)
O5—Cu1—O3	94.11 (11)	N2—N1—C3	107.6 (3)
O5ⁱ—Cu1—O3	85.89 (11)	N2—N1—Cu1	132.2 (2)
N1—Cu1—O3	74.89 (9)	C3—N1—Cu1	116.3 (2)
N1ⁱ—Cu1—O3	105.11 (9)	N1—N2—C1	108.4 (3)
O3ⁱ—Cu1—O3	180.0	N1—N2—Cu2	137.8 (2)
N2—Cu2—O6	165.29 (12)	C1—N2—Cu2	113.2 (2)
N2—Cu2—O9	93.98 (12)	N2—C1—C2	110.0 (3)
O6—Cu2—O9	92.94 (13)	N2—C1—C4	115.9 (3)
N2—Cu2—O2	80.69 (10)	C2—C1—C4	134.1 (3)
O6—Cu2—O2	88.18 (11)	C3—C2—C1	103.4 (3)
O9—Cu2—O2	158.66 (12)	C3—C2—H2	128.3
N2—Cu2—O10	97.78 (12)	C1—C2—H2	128.3
O6—Cu2—O10	93.87 (13)	N1—C3—C2	110.6 (3)
O9—Cu2—O10	99.41 (14)	N1—C3—C5	119.3 (3)
O2—Cu2—O10	101.78 (12)	C2—C3—C5	130.1 (3)
C4—O2—Cu2	114.3 (2)	O1—C4—O2	124.6 (3)
C5—O3—Cu1	109.0 (2)	O1—C4—C1	120.1 (3)
Cu1—O5—H5A	111 (3)	O2—C4—C1	115.2 (3)
Cu1—O5—H5B	115 (3)	O3—C5—O4	125.8 (3)
H5A—O5—H5B	110 (5)	O3—C5—C3	117.4 (3)
Cu2—O6—H6A	115 (3)	O4—C5—C3	116.8 (3)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1ⁱⁱ	0.87 (3)	2.28 (4)	3.050 (4)	148 (4)
O5—H5B···O8ⁱⁱⁱ	0.87 (4)	2.16 (4)	3.021 (5)	172 (4)
O6—H6A···O8^iv	0.87 (4)	2.38 (5)	3.078 (4)	137 (4)
O6—H6B···O2^iv	0.87 (6)	2.30 (6)	3.077 (4)	149 (4)
O7—H7A···O1ⁱⁱⁱ	0.80 (4)	2.16 (4)	2.860 (4)	147 (4)
O7—H7B···O4^v	0.81 (4)	1.91 (4)	2.715 (4)	171 (4)
O8—H8A···O7^vi	0.81 (3)	2.06 (3)	2.854 (4)	169 (4)
O8—H8B···O1	0.81 (5)	2.03 (5)	2.836 (4)	175 (4)
O9—H9A···O4^vii	0.87 (4)	2.26 (4)	3.061 (4)	154 (4)

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

Experimental details

Crystal data
Chemical formula	[Cu₃(C₅HN₂O₄)₂(H₂O)₈]·4H₂O
M_r	712.97
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.9455 (6), 9.1018 (7), 9.1125 (7)
α, β, γ (°)	103.485 (1), 90.924 (1), 117.505 (1)
V (Å³)	633.31 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.59
Crystal size (mm)	0.17 × 0.13 × 0.05

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.666, 0.877
No. of measured, independent and observed [I > 2σ(I)] reflections	3535, 2412, 2198
R_int	0.010
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.095, 1.08
No. of reflections	2412
No. of parameters	205
No. of restraints	12
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.89, −0.54

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O5—H5A···O1ⁱ	0.87 (3)	2.28 (4)	3.050 (4)	148 (4)
O5—H5B···O8ⁱⁱ	0.87 (4)	2.16 (4)	3.021 (5)	172 (4)
O6—H6A···O8ⁱⁱⁱ	0.87 (4)	2.38 (5)	3.078 (4)	137 (4)
O6—H6B···O2ⁱⁱⁱ	0.87 (6)	2.30 (6)	3.077 (4)	149 (4)
O7—H7A···O1ⁱⁱ	0.80 (4)	2.16 (4)	2.860 (4)	147 (4)
O7—H7B···O4^iv	0.81 (4)	1.91 (4)	2.715 (4)	171 (4)
O8—H8A···O7^v	0.81 (3)	2.06 (3)	2.854 (4)	169 (4)
O8—H8B···O1	0.81 (5)	2.03 (5)	2.836 (4)	175 (4)
O9—H9A···O4^vi	0.87 (4)	2.26 (4)	3.061 (4)	154 (4)

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

Acknowledgements

This work was supported by the National Analytical Research Center of Electrochemistry and Spectroscopy, Changchun Institute of Applied Chemistry.

References

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