Bis[triaqua­(1H-1,2,4-triazole-3,5-dicarboxyl­ato-κ2O3,N4)copper(II)] di-μ-aqua-bis­[diaqua­(1H-1,2,4-triazole-3,5-dicarboxyl­ato-κ2O3,N4)copper(II)]

Xie, L.-X.; Li, X.; Xie, P.-H.; Jin, Q.

doi:10.1107/S1600536809026993

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m928-m929

doi:10.1107/S1600536809026993

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Bis[triaqua(1H-1,2,4-triazole-3,5-dicarboxylato-κ²O³,N⁴)copper(II)] di-μ-aqua-bis[diaqua(1H-1,2,4-triazole-3,5-dicarboxylato-κ²O³,N⁴)copper(II)]

Li-Xia Xie,^a ^* Xin Li,^a Pu-Hui Xie ^a and Qiu Jin ^a

^aCollege of Sciences, Henan Agricultural University, Zhengzhou, Henan 450002, People's Republic of China
^*Correspondence e-mail: toxielix@163.com

(Received 5 July 2009; accepted 9 July 2009; online 15 July 2009)

In the title compound, [Cu(C₄HN₃O₄)(H₂O)₃]₂[Cu₂(C₄HN₃O₄)₂(H₂O)₆], both monomeric and dimeric molecules are present in the solid state. In the monomeric compound, the Cu^II atom is five-coordinated in a square-pyramidal configuration by one O atom and one N atom from one 1H-1,2,4-triazole-3,5-dicarboxylate (TZDCA²⁻) ligand and three O atoms from water molecules. In the centrosymmetric binuclear complex, each Cu^II atom is six-coordinated in an octahedral geometry by one O atom and one N atom from one TZDCA²⁻ ligand and four O atoms from water molecules, two of which bridge the Cu^II atoms. In the structure, there are intramolecular O—H⋯O and N—H⋯O hydrogen bonds, and in the crystal, intermolecular O—H⋯O, O—H⋯N and N—H⋯O hydrogen bonds link symmetry-related molecules, forming a three-dimensional supramolecular structure.

Related literature

For related structures, see: Billing et al. (1970 ); Ouellette et al. (2006a ,b , 2007 ); Zhai et al. (2007 ). For the preparation of 1,2,4,-triazole-3,5-dicarboxylic acid, see: Baitalik et al. (2004 ).

Experimental

Crystal data

[Cu(C₄HN₃O₄)(H₂O)₃]₂[Cu₂(C₄HN₃O₄)₂(H₂O)₆]
M_r = 1090.70
Monoclinic, P 2₁ /c
a = 12.056 (2) Å
b = 11.432 (2) Å
c = 14.958 (3) Å
β = 123.65 (3)°
V = 1716.1 (5) Å³
Z = 2
Mo Kα radiation
μ = 2.57 mm⁻¹
T = 293 K
0.10 × 0.10 × 0.08 mm

Data collection

Mercury CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000 ) T_min = 0.783, T_max = 0.821
16043 measured reflections
3020 independent reflections
2866 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.115
S = 1.17
3020 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.64 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
N2—H2⋯O6ⁱ	0.85	1.87	2.709 (6)	169
N5—H5⋯O8	0.85	2.46	2.773 (5)	103
N5—H5⋯O2ⁱⁱ	0.85	1.89	2.655 (7)	148
O9—H9A⋯O1ⁱⁱⁱ	0.85	2.50	3.221 (5)	144
O9—H9A⋯O2ⁱⁱⁱ	0.85	2.49	3.256 (5)	150
O9—H9B⋯O7ⁱⁱ	0.85	1.85	2.596 (5)	145
O10—H10A⋯O2ⁱⁱ	0.85	2.02	2.798 (6)	151
O10—H10B⋯O5^iv	0.85	2.59	3.103 (6)	120
O10—H10B⋯N1ⁱⁱ	0.85	2.10	2.863 (5)	149
O11—H11A⋯O8ⁱⁱ	0.85	1.84	2.650 (5)	160
O11—H11B⋯O3	0.85	1.83	2.662 (6)	167
O12—H12A⋯O6ⁱ	0.83	2.15	2.811 (6)	137
O12—H12B⋯O1^v	0.83	2.49	3.111 (6)	132
O12—H12B⋯N4ⁱ	0.83	2.19	2.821 (5)	133
O13—H13A⋯O4ⁱ	0.85	1.89	2.714 (5)	164
O13—H13B⋯O7	0.85	1.81	2.654 (7)	172
O14—H14A⋯O10^v	0.85	1.86	2.686 (5)	163
O14—H14B⋯O3ⁱ	0.85	1.76	2.599 (5)	169
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y, -z; (iv) x+1, y, z; (v) x-1, y, z.

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalClear; 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: 10.1107/S1600536809026993/su2127sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809026993/su2127Isup2.hkl

checkCIF report

Comment top

As a ligand with multiple coordination sites, 1,2,4-triazole has been shown to be good organic linker in the generation of structurally versatile metal-organic frameworks. It can bridge different metal centers to afford coordination polymers that exhibit extraordinary structural diversity and facile accessibility of functionalized new magnetic materials (Ouellette et al., 2006a; Ouellette et al., 2006b; Ouellette et al., 2007; Zhai et al., 2007). Furthermore, functional groups such as carboxylate, amino and pyridyl, can be introduced in 1,2,4-triazole, which makes its chemistry more abundant and complex. Encouraged by this aspect we selected a simple bifunctional ligand containing both 1,2,4-triazole and carboxylate groups, 1,2,4,-triazole-3,5-dicarboxylic acid, to study its coordination chemistry. As a result, we report herein on the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) contains a monomeric complex (Scheme 1) and half of a centrosymmetric binuclear complex (Scheme 2). In the mononuclear complex atom Cu1 is five-coordinated, by one N atom and one O atom from one TZDCA^2- ligand and three water molecules, and has a slightly distorted square pyramidal geometry. In the binuclear dimeric complex the Cu2 ions adopt an octahedral coordination geometry, where one N-atom and one O-atom from one TZDCA^2- ligand and two water molecules are in the equatorial plane, while the apical positions are occupied by water molecules. Water O14 acts as a bridge to form a four-membered Cu2/O14/O14A/Cu2A ring (Symmetry code: (A)= -x, -y, -z+1). The bond length Cu2–O14A = 2.617 (3) Å, indicates a weak coordination interaction (Billing et al., 1970). Each TZDCA^2- is deprotonated and acts as a bidentate ligand.

In the crystal structure there intra- and inter-molecular hydrogen bonds (Table 1), which consolidate the structure (Fig. 2).

Related literature top

For related structures, see: Billing et al. (1970); Ouellette et al. (2006a,b, 2007); Zhai et al. (2007). For the preparation of 1,2,4,-triazole-3,5-dicarboxylic acid, see: Baitalik et al. (2004).

Experimental top

All solvents and chemicals were of analytical grade and were used without further purification. Ligand 1,2,4,-triazole-3,5-dicarboxylic acid was prepared by the literature method (Baitalik et al., 2004). The title compound was synthesized as follows: 1,2,4,-triazole-3,5-dicarboxylic acid (0.5 mmol) was added to 5 cm³ water and the resulting solution was adjusted to a pH of 7.0, using an aqueous solution of triethylamine. CuSO₄(0.5 mmol) was then added to the above solution, and the mixture was stirred for 30 min and then filtered. The filtrate was left to evaporate slowly in air. After six days, blue single crystals suitable for X-ray analysis were obtained. Anal. Calcd (%) for C₄H₇CuN₃O₇: C, 17.62; H, 2.59; N, 15.41. Found (%): C, 17.73; H, 2.45; N, 15.52.

Computing details top

Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear (Rigaku, 2000); data reduction: CrystalClear (Rigaku, 2000); 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 the molecular structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering (Symmetry code: (A) = -x, -y, -z+1).
	Fig. 2. A view along the b axis of the crystal packing of the title compound, showing the hydrogen bonds as pale-blue dashed lines (see Table 1 for details).

Bis[triaqua(1H-1,2,4-triazole-3,5-dicarboxylato- κ²O³,N⁴)copper(II)] di-µ-aqua-bis[diaqua(1H-1,2,4-triazole-3,5-dicarboxylato- κ²O³,N⁴)copper(II)] top

Crystal data top

[Cu(C₄HN₃O₄)(H₂O)₃]₂[Cu₂(C₄HN₃O₄)₂(H₂O)₆]	F(000) = 1096
M_r = 1090.70	D_x = 2.111 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3290 reflections
a = 12.056 (2) Å	θ = 2.0–31.0°
b = 11.432 (2) Å	µ = 2.57 mm⁻¹
c = 14.958 (3) Å	T = 293 K
β = 123.65 (3)°	Prism, blue
V = 1716.1 (5) Å³	0.10 × 0.10 × 0.08 mm
Z = 2

Data collection top

Mercury CCD diffractometer	3020 independent reflections
Radiation source: fine-focus sealed tube	2866 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	h = −14→14
T_min = 0.783, T_max = 0.821	k = −13→13
16043 measured reflections	l = −17→17

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.17	w = 1/[σ²(F_o²) + (0.0397P)² + 6.4925P] where P = (F_o² + 2F_c²)/3
3020 reflections	(Δ/σ)_max < 0.001
272 parameters	Δρ_max = 0.64 e Å⁻³
0 restraints	Δρ_min = −0.54 e Å⁻³

Crystal data top

[Cu(C₄HN₃O₄)(H₂O)₃]₂[Cu₂(C₄HN₃O₄)₂(H₂O)₆]	V = 1716.1 (5) Å³
M_r = 1090.70	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.056 (2) Å	µ = 2.57 mm⁻¹
b = 11.432 (2) Å	T = 293 K
c = 14.958 (3) Å	0.10 × 0.10 × 0.08 mm
β = 123.65 (3)°

Data collection top

Mercury CCD diffractometer	3020 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2000)	2866 reflections with I > 2σ(I)
T_min = 0.783, T_max = 0.821	R_int = 0.051
16043 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.17	Δρ_max = 0.64 e Å⁻³
3020 reflections	Δρ_min = −0.54 e Å⁻³
272 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
Cu2	−0.00361 (5)	0.00777 (4)	0.38176 (4)	0.0204 (2)
O5	−0.0608 (3)	0.1733 (3)	0.3706 (3)	0.0251 (10)
O6	0.0026 (3)	0.3562 (3)	0.3659 (3)	0.0273 (10)
O7	0.2747 (4)	−0.1431 (3)	0.3948 (3)	0.0386 (13)
O8	0.4173 (3)	−0.0451 (3)	0.3711 (3)	0.0322 (11)
O12	−0.1496 (3)	−0.0099 (3)	0.1914 (3)	0.0299 (10)
O13	0.0607 (3)	−0.1507 (3)	0.4033 (3)	0.0401 (13)
O14	−0.1385 (3)	−0.0368 (3)	0.4098 (2)	0.0229 (9)
N4	0.2191 (4)	0.2525 (3)	0.3602 (3)	0.0239 (11)
N5	0.2979 (4)	0.1643 (3)	0.3662 (3)	0.0224 (11)
N6	0.1440 (3)	0.0784 (3)	0.3743 (3)	0.0179 (10)
C5	0.1271 (4)	0.1964 (4)	0.3656 (3)	0.0194 (12)
C6	0.0143 (4)	0.2496 (4)	0.3669 (3)	0.0195 (12)
C7	0.2535 (4)	0.0614 (4)	0.3741 (3)	0.0190 (12)
C8	0.3216 (4)	−0.0531 (4)	0.3805 (4)	0.0234 (12)
Cu1	0.51531 (5)	0.10043 (5)	0.13087 (5)	0.0233 (2)
O1	0.5666 (3)	−0.0657 (3)	0.1367 (3)	0.0280 (10)
O2	0.4995 (3)	−0.2483 (3)	0.1359 (3)	0.0271 (10)
O3	0.2329 (3)	0.2532 (3)	0.1120 (3)	0.0302 (10)
O4	0.0728 (3)	0.1515 (3)	0.1110 (3)	0.0310 (10)
O9	0.6516 (3)	0.1440 (3)	0.1069 (3)	0.0302 (10)
O10	0.6585 (3)	0.1163 (3)	0.3205 (3)	0.0316 (10)
O11	0.4531 (3)	0.2599 (3)	0.1113 (3)	0.0351 (10)
N1	0.2712 (4)	−0.1437 (3)	0.1204 (3)	0.0253 (11)
N2	0.1924 (3)	−0.0561 (3)	0.1154 (3)	0.0229 (11)
N3	0.3567 (3)	0.0310 (3)	0.1222 (3)	0.0210 (11)
C1	0.3685 (4)	−0.0882 (4)	0.1249 (4)	0.0217 (12)
C2	0.4882 (4)	−0.1371 (4)	0.1318 (3)	0.0215 (11)
C3	0.2427 (4)	0.0478 (4)	0.1159 (3)	0.0199 (12)
C4	0.1757 (4)	0.1610 (4)	0.1129 (4)	0.0212 (12)
H5	0.36710	0.16420	0.36410	0.0270*
H12A	−0.09350	−0.01230	0.17580	0.0450*
H12B	−0.19850	−0.06340	0.18780	0.0450*
H13A	0.01660	−0.21390	0.38700	0.0600*
H13B	0.12470	−0.14650	0.39470	0.0600*
H14A	−0.21270	−0.00110	0.37720	0.0340*
H14B	−0.16800	−0.10650	0.39590	0.0340*
H2	0.12460	−0.08260	0.11240	0.0280*
H9A	0.61880	0.14370	0.03990	0.0460*
H9B	0.68010	0.21210	0.13200	0.0460*
H10A	0.60750	0.13340	0.34120	0.0480*
H10B	0.70320	0.17910	0.33550	0.0480*
H11A	0.50060	0.32140	0.13270	0.0530*
H11B	0.38230	0.26930	0.11000	0.0530*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu2	0.0215 (3)	0.0096 (3)	0.0376 (3)	0.0003 (2)	0.0211 (3)	0.0019 (2)
O5	0.0252 (16)	0.0143 (15)	0.047 (2)	−0.0007 (12)	0.0270 (15)	0.0022 (13)
O6	0.0313 (17)	0.0137 (16)	0.049 (2)	0.0024 (13)	0.0298 (17)	0.0010 (14)
O7	0.040 (2)	0.0133 (16)	0.082 (3)	0.0048 (15)	0.046 (2)	0.0052 (17)
O8	0.0322 (18)	0.0224 (17)	0.059 (2)	0.0065 (14)	0.0359 (18)	0.0019 (16)
O12	0.0283 (17)	0.0197 (16)	0.046 (2)	−0.0011 (13)	0.0232 (16)	−0.0058 (14)
O13	0.038 (2)	0.0178 (17)	0.084 (3)	0.0009 (15)	0.046 (2)	0.0049 (17)
O14	0.0207 (15)	0.0112 (14)	0.0397 (18)	−0.0004 (12)	0.0185 (14)	0.0021 (13)
N4	0.0247 (19)	0.0134 (18)	0.042 (2)	0.0041 (15)	0.0237 (18)	0.0021 (16)
N5	0.0193 (17)	0.0155 (18)	0.041 (2)	0.0007 (14)	0.0221 (17)	−0.0007 (16)
N6	0.0217 (18)	0.0070 (16)	0.0291 (19)	0.0020 (13)	0.0166 (16)	0.0015 (14)
C5	0.021 (2)	0.013 (2)	0.030 (2)	−0.0005 (16)	0.0177 (19)	−0.0002 (17)
C6	0.022 (2)	0.012 (2)	0.028 (2)	−0.0005 (17)	0.0161 (19)	−0.0009 (17)
C7	0.021 (2)	0.013 (2)	0.025 (2)	0.0027 (17)	0.0140 (18)	0.0022 (16)
C8	0.026 (2)	0.015 (2)	0.031 (2)	0.0035 (18)	0.017 (2)	−0.0009 (18)
Cu1	0.0210 (3)	0.0137 (3)	0.0399 (4)	−0.0015 (2)	0.0198 (3)	0.0011 (2)
O1	0.0277 (17)	0.0152 (16)	0.052 (2)	0.0029 (13)	0.0290 (16)	−0.0010 (14)
O2	0.0264 (16)	0.0140 (16)	0.052 (2)	0.0028 (13)	0.0287 (16)	0.0021 (14)
O3	0.0283 (17)	0.0115 (15)	0.056 (2)	0.0022 (13)	0.0267 (17)	0.0002 (14)
O4	0.0278 (17)	0.0203 (17)	0.052 (2)	0.0039 (13)	0.0266 (17)	0.0024 (15)
O9	0.0302 (17)	0.0166 (16)	0.053 (2)	−0.0025 (13)	0.0289 (17)	0.0021 (15)
O10	0.0275 (17)	0.0252 (17)	0.045 (2)	0.0013 (14)	0.0219 (16)	−0.0071 (15)
O11	0.0296 (17)	0.0144 (16)	0.069 (2)	−0.0006 (13)	0.0321 (18)	0.0027 (16)
N1	0.0240 (19)	0.0114 (18)	0.047 (2)	−0.0011 (14)	0.0237 (19)	−0.0015 (16)
N2	0.0178 (18)	0.0157 (19)	0.039 (2)	0.0003 (14)	0.0182 (17)	0.0012 (16)
N3	0.0189 (17)	0.0170 (18)	0.032 (2)	0.0016 (14)	0.0172 (16)	0.0017 (15)
C1	0.023 (2)	0.013 (2)	0.032 (2)	0.0018 (17)	0.017 (2)	0.0003 (17)
C2	0.0107 (19)	0.026 (2)	0.024 (2)	0.0070 (17)	0.0072 (18)	−0.0032 (18)
C3	0.022 (2)	0.013 (2)	0.026 (2)	−0.0004 (17)	0.0142 (19)	0.0021 (17)
C4	0.017 (2)	0.018 (2)	0.030 (2)	0.0040 (17)	0.0139 (19)	0.0020 (18)

Geometric parameters (Å, º) top

Cu2—O5	1.989 (4)	O4—C4	1.230 (7)
Cu2—O12	2.386 (4)	O9—H9A	0.8500
Cu2—O13	1.926 (4)	O9—H9B	0.8500
Cu2—O14	1.959 (4)	O10—H10B	0.8500
Cu2—N6	2.013 (4)	O10—H10A	0.8500
Cu2—O14ⁱ	2.617 (3)	O11—H11A	0.8500
Cu1—N3	2.007 (4)	O11—H11B	0.8500
Cu1—O9	1.931 (4)	N4—N5	1.354 (6)
Cu1—O10	2.373 (4)	N4—C5	1.322 (7)
Cu1—O1	1.984 (4)	N5—C7	1.325 (6)
Cu1—O11	1.931 (4)	N6—C7	1.336 (7)
O5—C6	1.280 (6)	N6—C5	1.360 (6)
O6—C6	1.226 (6)	N5—H5	0.8500
O7—C8	1.248 (6)	N1—N2	1.354 (6)
O8—C8	1.241 (7)	N1—C1	1.302 (8)
O12—H12B	0.8300	N2—C3	1.332 (6)
O12—H12A	0.8300	N3—C1	1.368 (6)
O13—H13A	0.8500	N3—C3	1.338 (7)
O13—H13B	0.8500	N2—H2	0.8500
O14—H14A	0.8500	C5—C6	1.500 (7)
O14—H14B	0.8500	C7—C8	1.520 (7)
O1—C2	1.220 (6)	C1—C2	1.497 (8)
O2—C2	1.276 (6)	C3—C4	1.513 (7)
O3—C4	1.264 (6)

O5—Cu2—O12	89.33 (14)	Cu1—O10—H10B	108.00
O5—Cu2—O13	175.94 (16)	Cu1—O10—H10A	105.00
O5—Cu2—O14	88.58 (17)	Cu1—O11—H11B	115.00
O5—Cu2—N6	83.67 (16)	H11A—O11—H11B	111.00
O5—Cu2—O14ⁱ	86.96 (14)	Cu1—O11—H11A	127.00
O12—Cu2—O13	94.73 (14)	N5—N4—C5	102.5 (4)
O12—Cu2—O14	94.74 (13)	N4—N5—C7	111.3 (5)
O12—Cu2—N6	93.33 (15)	Cu2—N6—C7	147.9 (3)
O12—Cu2—O14ⁱ	174.72 (14)	Cu2—N6—C5	108.3 (3)
O13—Cu2—O14	91.41 (17)	C5—N6—C7	103.9 (4)
O13—Cu2—N6	95.76 (17)	N4—N5—H5	132.00
O13—Cu2—O14ⁱ	89.02 (14)	C7—N5—H5	117.00
O14—Cu2—N6	168.74 (14)	N2—N1—C1	103.1 (4)
O14—Cu2—O14ⁱ	81.43 (12)	N1—N2—C3	110.9 (4)
O14ⁱ—Cu2—N6	90.00 (14)	Cu1—N3—C1	108.2 (3)
O9—Cu1—N3	165.50 (16)	Cu1—N3—C3	148.5 (3)
O1—Cu1—O9	88.77 (17)	C1—N3—C3	103.4 (4)
O1—Cu1—O10	91.04 (14)	C3—N2—H2	138.00
O1—Cu1—O11	174.72 (16)	N1—N2—H2	111.00
O1—Cu1—N3	83.50 (17)	N4—C5—N6	113.6 (5)
O9—Cu1—O10	94.13 (16)	N6—C5—C6	119.3 (4)
O9—Cu1—O11	91.57 (17)	N4—C5—C6	127.0 (4)
O11—Cu1—N3	95.02 (17)	O5—C6—O6	126.8 (5)
O10—Cu1—O11	94.20 (14)	O5—C6—C5	113.1 (4)
O10—Cu1—N3	98.25 (15)	O6—C6—C5	120.1 (5)
Cu2—O5—C6	115.6 (4)	N5—C7—N6	108.6 (4)
Cu2—O14—Cu2ⁱ	98.57 (13)	N6—C7—C8	128.7 (4)
Cu2—O12—H12A	99.00	N5—C7—C8	122.7 (5)
Cu2—O12—H12B	100.00	O8—C8—C7	115.7 (4)
H12A—O12—H12B	128.00	O7—C8—O8	128.2 (5)
Cu2—O13—H13A	129.00	O7—C8—C7	116.1 (5)
Cu2—O13—H13B	104.00	N1—C1—N3	114.1 (5)
H13A—O13—H13B	119.00	N1—C1—C2	128.9 (4)
Cu2—O14—H14B	118.00	N3—C1—C2	117.0 (5)
H14A—O14—H14B	98.00	O1—C2—O2	127.2 (5)
Cu2ⁱ—O14—H14A	114.00	O1—C2—C1	116.1 (4)
Cu2—O14—H14A	119.00	O2—C2—C1	116.6 (5)
Cu2ⁱ—O14—H14B	109.00	N3—C3—C4	129.5 (4)
Cu1—O1—C2	115.2 (4)	N2—C3—N3	108.6 (4)
Cu1—O9—H9B	109.00	N2—C3—C4	121.9 (5)
H9A—O9—H9B	110.00	O3—C4—C3	115.4 (5)
Cu1—O9—H9A	109.00	O4—C4—C3	116.1 (4)
H10A—O10—H10B	101.00	O3—C4—O4	128.5 (5)

O12—Cu2—O5—C6	−95.3 (3)	C5—N6—C7—C8	−179.2 (4)
O14—Cu2—O5—C6	170.0 (3)	Cu2—N6—C5—N4	179.9 (3)
N6—Cu2—O5—C6	−1.9 (3)	C7—N6—C5—N4	−0.1 (5)
O14ⁱ—Cu2—O5—C6	88.5 (3)	C5—N6—C7—N5	0.3 (4)
O5—Cu2—O14—Cu2ⁱ	−87.14 (15)	Cu2—N6—C5—C6	2.0 (4)
O12—Cu2—O14—Cu2ⁱ	−176.35 (12)	Cu2—N6—C7—C8	0.9 (8)
O13—Cu2—O14—Cu2ⁱ	88.80 (15)	Cu2—N6—C7—N5	−179.7 (4)
O14ⁱ—Cu2—O14—Cu2ⁱ	−0.02 (13)	C7—N6—C5—C6	−178.0 (3)
O5—Cu2—N6—C5	−0.2 (3)	C1—N1—N2—C3	0.6 (5)
O5—Cu2—N6—C7	179.7 (6)	N2—N1—C1—N3	−0.5 (5)
O12—Cu2—N6—C5	88.8 (3)	N2—N1—C1—C2	179.9 (5)
O12—Cu2—N6—C7	−91.3 (6)	N1—N2—C3—N3	−0.5 (5)
O13—Cu2—N6—C5	−176.2 (3)	N1—N2—C3—C4	−178.9 (4)
O13—Cu2—N6—C7	3.8 (6)	C3—N3—C1—C2	179.9 (4)
O14ⁱ—Cu2—N6—C5	−87.1 (3)	C3—N3—C1—N1	0.2 (5)
O14ⁱ—Cu2—N6—C7	92.8 (6)	Cu1—N3—C1—N1	179.6 (3)
O5—Cu2—O14ⁱ—Cu2ⁱ	89.02 (17)	C1—N3—C3—C4	178.4 (4)
O13—Cu2—O14ⁱ—Cu2ⁱ	−91.57 (18)	Cu1—N3—C3—C4	−0.5 (9)
O14—Cu2—O14ⁱ—Cu2ⁱ	0.02 (16)	Cu1—N3—C1—C2	−0.7 (5)
N6—Cu2—O14ⁱ—Cu2ⁱ	172.68 (16)	Cu1—N3—C3—N2	−178.7 (4)
O11—Cu1—N3—C3	−6.2 (6)	C1—N3—C3—N2	0.2 (4)
O9—Cu1—O1—C2	−166.9 (3)	N6—C5—C6—O6	175.4 (4)
O10—Cu1—O1—C2	99.0 (3)	N4—C5—C6—O6	−2.2 (6)
N3—Cu1—O1—C2	0.8 (3)	N6—C5—C6—O5	−3.6 (5)
O1—Cu1—N3—C1	0.0 (3)	N4—C5—C6—O5	178.8 (4)
O1—Cu1—N3—C3	178.9 (6)	N6—C7—C8—O7	−5.1 (7)
O10—Cu1—N3—C1	−90.1 (3)	N6—C7—C8—O8	175.1 (4)
O10—Cu1—N3—C3	88.8 (6)	N5—C7—C8—O8	−4.3 (6)
O11—Cu1—N3—C1	174.9 (3)	N5—C7—C8—O7	175.5 (4)
Cu2—O5—C6—O6	−175.7 (4)	N1—C1—C2—O1	−178.9 (5)
Cu2—O5—C6—C5	3.3 (4)	N3—C1—C2—O1	1.5 (6)
Cu1—O1—C2—C1	−1.4 (5)	N3—C1—C2—O2	179.0 (4)
Cu1—O1—C2—O2	−178.6 (3)	N1—C1—C2—O2	−1.4 (7)
C5—N4—N5—C7	0.4 (4)	N2—C3—C4—O3	−178.9 (4)
N5—N4—C5—C6	177.5 (4)	N2—C3—C4—O4	0.7 (6)
N5—N4—C5—N6	−0.2 (5)	N3—C3—C4—O3	3.1 (7)
N4—N5—C7—N6	−0.4 (5)	N3—C3—C4—O4	−177.4 (4)
N4—N5—C7—C8	179.1 (4)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O6ⁱⁱ	0.85	1.87	2.709 (6)	169
N5—H5···O8	0.85	2.46	2.773 (5)	103
N5—H5···O2ⁱⁱⁱ	0.85	1.89	2.655 (7)	148
O9—H9A···O1^iv	0.85	2.50	3.221 (5)	144
O9—H9A···O2^iv	0.85	2.49	3.256 (5)	150
O9—H9B···O7ⁱⁱⁱ	0.85	1.85	2.596 (5)	145
O10—H10A···O2ⁱⁱⁱ	0.85	2.02	2.798 (6)	151
O10—H10B···O5^v	0.85	2.59	3.103 (6)	120
O10—H10B···N1ⁱⁱⁱ	0.85	2.10	2.863 (5)	149
O11—H11A···O8ⁱⁱⁱ	0.85	1.84	2.650 (5)	160
O11—H11B···O3	0.85	1.83	2.662 (6)	167
O12—H12A···O6ⁱⁱ	0.83	2.15	2.811 (6)	137
O12—H12B···O1^vi	0.83	2.49	3.111 (6)	132
O12—H12B···N4ⁱⁱ	0.83	2.19	2.821 (5)	133
O13—H13A···O4ⁱⁱ	0.85	1.89	2.714 (5)	164
O13—H13B···O7	0.85	1.81	2.654 (7)	172
O14—H14A···O10^vi	0.85	1.86	2.686 (5)	163
O14—H14B···O3ⁱⁱ	0.85	1.76	2.599 (5)	169

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

Experimental details

Crystal data
Chemical formula	[Cu(C₄HN₃O₄)(H₂O)₃]₂[Cu₂(C₄HN₃O₄)₂(H₂O)₆]
M_r	1090.70
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	12.056 (2), 11.432 (2), 14.958 (3)
β (°)	123.65 (3)
V (Å³)	1716.1 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.57
Crystal size (mm)	0.10 × 0.10 × 0.08

Data collection
Diffractometer	Mercury CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2000)
T_min, T_max	0.783, 0.821
No. of measured, independent and observed [I > 2σ(I)] reflections	16043, 3020, 2866
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.115, 1.17
No. of reflections	3020
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.54

Computer programs: CrystalClear (Rigaku, 2000), 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
N2—H2···O6ⁱ	0.85	1.87	2.709 (6)	169
N5—H5···O8	0.85	2.46	2.773 (5)	103
N5—H5···O2ⁱⁱ	0.85	1.89	2.655 (7)	148
O9—H9A···O1ⁱⁱⁱ	0.85	2.50	3.221 (5)	144
O9—H9A···O2ⁱⁱⁱ	0.85	2.49	3.256 (5)	150
O9—H9B···O7ⁱⁱ	0.85	1.85	2.596 (5)	145
O10—H10A···O2ⁱⁱ	0.85	2.02	2.798 (6)	151
O10—H10B···O5^iv	0.85	2.59	3.103 (6)	120
O10—H10B···N1ⁱⁱ	0.85	2.10	2.863 (5)	149
O11—H11A···O8ⁱⁱ	0.85	1.84	2.650 (5)	160
O11—H11B···O3	0.85	1.83	2.662 (6)	167
O12—H12A···O6ⁱ	0.83	2.15	2.811 (6)	137
O12—H12B···O1^v	0.83	2.49	3.111 (6)	132
O12—H12B···N4ⁱ	0.83	2.19	2.821 (5)	133
O13—H13A···O4ⁱ	0.85	1.89	2.714 (5)	164
O13—H13B···O7	0.85	1.81	2.654 (7)	172
O14—H14A···O10^v	0.85	1.86	2.686 (5)	163
O14—H14B···O3ⁱ	0.85	1.76	2.599 (5)	169

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

Acknowledgements

This work was sponsored by the start-up fund of Henan Agricultural University (grant No. 30700061).

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