Poly[[di­aqua­(μ4-benzene-1,2,4,5-tetra­carboxyl­ato)tetrakis­(1H-imidazole-κN3)dicopper(II)] N,N-di­methyl­formamide monosolvate]

Zhou, X.-F.; Xiao, H.-P.; Zhao, Y.-J.; Li, X.-H.

doi:10.1107/S1600536813010246

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 5| May 2013| Pages m273-m274

https://doi.org/10.1107/S1600536813010246

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Poly[[diaqua(μ₄-benzene-1,2,4,5-tetracarboxylato)tetrakis(1H-imidazole-κN³)dicopper(II)] N,N-dimethylformamide monosolvate]

Xiao-Fei Zhou,^a Hong-Ping Xiao,^a Ya-Juan Zhao ^a and Xin-Hua Li ^a ^*

^aCollege of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, People's Republic of China
^*Correspondence e-mail: lixinhua01@126.com

(Received 18 March 2013; accepted 14 April 2013; online 20 April 2013)

The asymmetric unit of the polymeric title compound, {[Cu₂(C₁₀H₂O₈)(C₃H₄N₂)₄(H₂O)₂]·C₃H₇NO}_n, contains two independent Cu^II ions, each coordinated by one water molecule, two imidazole N atoms and two carboxylate O atoms from benzene-1,2,4,5-tetracarboxylate anions in a distorted square-pyramidal geometry. The benzene-1,2,4,5-tetracarboxylate anion bridges four Cu^II ions, forming a polymeric sheet parallel to (010). In the crystal, extensive N—H⋯O and O—H⋯O hydrogen bonds link the polymeric sheets and dimethylformamide solvent molecules into a three-dimensional supramolecular structure.

Related literature

For background to the benzene-1,2,4,5-teracarboxylate ligand in coordination polymers, see: Andruh et al. (2011 ); Clarke et al. (2012 ); Jiang et al. (2008 ); Aghabozorg et al. (2007 ); Chu et al. (2001 ); Liu & Ding (2007 ); Wu et al. (2006 ). For related structures, see: Zhan & Li (2010 ); Luo et al. (2007 ); Yang et al. (2004 ). For the synthesis, see: Zhao et al. (2010 ).

Experimental

Crystal data

[Cu₂(C₁₀H₂O₈)(C₃H₄N₂)₄(H₂O)₂]·C₃H₇NO
M_r = 758.65
Monoclinic, P 2₁ /c
a = 8.999 (4) Å
b = 19.296 (8) Å
c = 18.926 (7) Å
β = 110.590 (18)°
V = 3076 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.46 mm⁻¹
T = 298 K
0.23 × 0.21 × 0.15 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.731, T_max = 0.811
17289 measured reflections
5445 independent reflections
4149 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.153
S = 1.11
5445 reflections
426 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N1	2.003 (4)
Cu1—N3	2.025 (4)
Cu1—O1	1.984 (3)
Cu1—O5ⁱ	1.985 (3)
Cu1—O9	2.344 (3)
Cu2—N5	1.985 (3)
Cu2—N7	1.980 (3)
Cu2—O3	2.243 (3)
Cu2—O7ⁱⁱ	2.003 (3)
Cu2—O10	2.043 (3)
Symmetry codes: (i) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O3ⁱⁱⁱ	0.86	2.01	2.807 (5)	153
N4—H4N⋯O7ⁱⁱ	0.86	2.35	3.099 (5)	146
N6—H6N⋯O6ⁱ	0.86	2.03	2.733 (5)	138
N8—H8N⋯O2^iv	0.86	2.35	2.952 (5)	127
N8—H8N⋯O4^iv	0.86	2.26	3.033 (6)	149
O9—H9B⋯O11^v	0.85	2.06	2.909 (5)	177
O9—H9C⋯O11^iv	0.85	2.02	2.805 (6)	153
O10—H10A⋯O8^vi	0.85	1.90	2.655 (4)	147
O10—H10B⋯O4	0.85	2.24	2.703 (5)	114
Symmetry codes: (i) $[x+1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x+1, y, z; (iv) x-1, y, z; (v) -x+2, -y+1, -z+1; (vi) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536813010246/xu5689sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536813010246/xu5689Isup2.hkl

checkCIF report

Comment top

In recent years, many successful implementation of crystal engineering concepts has produced a great deal of coordination and supramolecular networks (Andruh et al., 2011), many of which exhibit unusual and fascinating architectures (Clarke et al., 2012). The benzene-1,2,4,5-teracarboxylate ligand as a multi-connecting ligand is also an excellent candidate for the structuring of coordination networks (Jiang et al., 2008), and comparatively few examples have been reported in relation to applying it to the building of coordination polymers (Aghabozorg et al., 2007; Chu et al., 2001; Liu & Ding, 2007; Wu et al., 2006). Here, the title complex, {[Cu₂(idz)₄(btc)(H₂O)₂]^.DMF}_n (idz=imidazole, DMF=N,N-dimethylformamide, btc=benzene-1,2,4,5-tetracarboxylato), (I), represents as a novel example.

As shown in Figure 1, the asymmetric unit of (I) consists of two crystallographically independent Cu^II atoms. Both are five-coordinate in a slight distorted tetragonal pyramid geometry, and chemical environment of them are similar. Each Cu^II cation is surrounded by two O atoms from two btc tetraanions, two N atoms from two monodentate idz ligands, and one water molecule (O9 or O10) which occupies the axial position. All the bond lengths fall within the typical range of Cu—N bond and Cu—O bond lengths (Luo et al., 2007; Yang et al., 2004).

Cu1 and Cu2 are bridged by a btc tetraanion, which acts as µ₄-bridge, forming a two-dimensional sheet along the a,c axis, as shown in Figure 2. The structure can be regarded as a grid sheets with (4,4) net topology which is constructed through Cu^II centers bridged by btc tetraanions. Adjacent two-dimensional sheets are parallel and are linked via hydrogen-bonding interactions (see Table 1) through uncoordinated DMF solvent molecules to form a sandwich structure(Zhan & Li, 2010).

Related literature top

For background to the benzene-1,2,4,5-teracarboxylate ligand in coordination polymers, see: Andruh et al. (2011); Clarke et al. (2012); Jiang et al. (2008); Aghabozorg et al. (2007); Chu et al. (2001); Liu & Ding (2007); Wu et al. (2006). For related structures, see: Zhan & Li (2010); Luo et al. (2007); Yang et al. (2004). For the synthesis, see: Zhao et al. (2010).

Experimental top

A dimethylformamide (DMF) solution (20 ml) of benzene-1,2,4,5-tetracarboxylic acid (0.1 mmol,0.0254 g) was added dropwise to an aqueous solution (10 ml) containing copper sulfate pentahydrate (0.2 mmol,0.0498 g), N,N-carbonyldiimidazole (0.3 mmol,0.0486 g) and NaOH (0.01 mmol, 0.0004 g) at room temperature (Zhao et al., 2010). The reaction mixture was filtered and the filtrate was left to stand for about three weeks until blue single crystals were obtained (yield 31%, based on Cu).

Structure description top

For background to the benzene-1,2,4,5-teracarboxylate ligand in coordination polymers, see: Andruh et al. (2011); Clarke et al. (2012); Jiang et al. (2008); Aghabozorg et al. (2007); Chu et al. (2001); Liu & Ding (2007); Wu et al. (2006). For related structures, see: Zhan & Li (2010); Luo et al. (2007); Yang et al. (2004). For the synthesis, see: Zhao et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Structure of the (I) with the atom numbering, showing displacement ellipsoids at the 30% probability level. H atoms and DMF molecule have been omitted for clarity.
	Fig. 2. Perspective view of the 2-D sheet of (I).

Poly[[diaqua(µ₄-benzene-1,2,4,5-tetracarboxylato)tetrakis(1H-imidazole-κN³)dicopper(II)] N,N-dimethylformamide monosolvate] top

Crystal data top

[Cu₂(C₁₀H₂O₈)(C₃H₄N₂)₄(H₂O)₂]·C₃H₇NO	F(000) = 1552
M_r = 758.65	D_x = 1.638 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4538 reflections
a = 8.999 (4) Å	θ = 2.3–25.1°
b = 19.296 (8) Å	µ = 1.46 mm⁻¹
c = 18.926 (7) Å	T = 298 K
β = 110.590 (18)°	Block, blue
V = 3076 (2) Å³	0.23 × 0.21 × 0.15 mm
Z = 4

Data collection top

Bruker APEXII area-detector diffractometer	5445 independent reflections
Radiation source: fine-focus sealed tube	4149 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
φ and ω scans	θ_max = 25.1°, θ_min = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −10→7
T_min = 0.731, T_max = 0.811	k = −11→23
17289 measured reflections	l = −22→22

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.094P)² + 0.3347P] where P = (F_o² + 2F_c²)/3
5445 reflections	(Δ/σ)_max = 0.001
426 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[Cu₂(C₁₀H₂O₈)(C₃H₄N₂)₄(H₂O)₂]·C₃H₇NO	V = 3076 (2) Å³
M_r = 758.65	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.999 (4) Å	µ = 1.46 mm⁻¹
b = 19.296 (8) Å	T = 298 K
c = 18.926 (7) Å	0.23 × 0.21 × 0.15 mm
β = 110.590 (18)°

Data collection top

Bruker APEXII area-detector diffractometer	5445 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	4149 reflections with I > 2σ(I)
T_min = 0.731, T_max = 0.811	R_int = 0.038
17289 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.11	Δρ_max = 0.51 e Å⁻³
5445 reflections	Δρ_min = −0.60 e Å⁻³
426 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	0.49949 (5)	0.66350 (3)	0.40320 (2)	0.02190 (17)
Cu2	−0.01800 (5)	0.90670 (3)	0.40567 (2)	0.02186 (17)
O3	0.0200 (3)	0.83286 (14)	0.32205 (15)	0.0254 (6)
O4	0.1425 (4)	0.90382 (15)	0.26628 (17)	0.0308 (7)
O2	0.3393 (3)	0.77371 (15)	0.32593 (16)	0.0302 (7)
O1	0.3008 (3)	0.65963 (14)	0.31383 (15)	0.0265 (7)
O5	−0.3003 (3)	0.82712 (14)	−0.00888 (15)	0.0259 (7)
O6	−0.3577 (3)	0.71481 (15)	−0.01062 (16)	0.0289 (7)
O8	−0.0973 (4)	0.58140 (16)	0.04247 (18)	0.0432 (9)
O7	−0.0517 (3)	0.66614 (14)	−0.02611 (14)	0.0245 (6)
O10	0.0235 (3)	0.98875 (15)	0.34694 (16)	0.0313 (7)
H10A	0.0156	1.0262	0.3690	0.047*
H10B	0.1166	0.9855	0.3454	0.047*
O9	0.5490 (4)	0.54417 (17)	0.41879 (19)	0.0445 (8)
H9B	0.5993	0.5356	0.4651	0.067*
H9C	0.4612	0.5225	0.4044	0.067*
N1	0.6196 (4)	0.67888 (18)	0.33332 (19)	0.0276 (8)
N7	−0.2465 (4)	0.91606 (18)	0.34494 (19)	0.0273 (8)
N3	0.3720 (4)	0.67091 (19)	0.4723 (2)	0.0316 (9)
N5	0.2083 (4)	0.91014 (18)	0.47251 (19)	0.0265 (8)
C7	−0.2741 (4)	0.7665 (2)	0.0167 (2)	0.0227 (9)
C2	0.1268 (4)	0.7328 (2)	0.2199 (2)	0.0193 (8)
C4	0.0744 (4)	0.8489 (2)	0.2715 (2)	0.0224 (9)
C1	0.2665 (4)	0.7223 (2)	0.2915 (2)	0.0247 (9)
C10	0.0832 (4)	0.6832 (2)	0.1639 (2)	0.0220 (9)
H10	0.1380	0.6414	0.1718	0.026*
N8	−0.5031 (4)	0.8996 (2)	0.2980 (2)	0.0443 (11)
H8N	−0.5959	0.8840	0.2928	0.053*
C3	0.0416 (4)	0.7953 (2)	0.20941 (19)	0.0173 (8)
C6	−0.1278 (4)	0.7559 (2)	0.0861 (2)	0.0191 (8)
C8	−0.0412 (4)	0.6942 (2)	0.09592 (19)	0.0176 (8)
C5	−0.0858 (4)	0.8058 (2)	0.1428 (2)	0.0220 (9)
H5	−0.1438	0.8467	0.1360	0.026*
C13	0.5758 (6)	0.6644 (3)	0.2580 (3)	0.0410 (12)
H13	0.4916	0.6360	0.2308	0.049*
C17	0.3268 (5)	0.8762 (2)	0.4620 (3)	0.0358 (11)
H17	0.3161	0.8477	0.4209	0.043*
C11	0.7426 (5)	0.7202 (2)	0.3478 (3)	0.0310 (10)
H11	0.7981	0.7385	0.3953	0.037*
N6	0.4627 (4)	0.8883 (2)	0.5180 (2)	0.0450 (11)
H6N	0.5540	0.8715	0.5222	0.054*
C20	−0.3691 (5)	0.8842 (2)	0.3536 (2)	0.0336 (11)
H20	−0.3622	0.8547	0.3935	0.040*
C9	−0.0702 (4)	0.6424 (2)	0.0330 (2)	0.0239 (9)
N2	0.7785 (5)	0.7327 (2)	0.2862 (2)	0.0396 (10)
H2N	0.8543	0.7584	0.2834	0.047*
C14	0.4166 (6)	0.6577 (3)	0.5468 (3)	0.0455 (13)
H14	0.5065	0.6326	0.5745	0.055*
C19	0.2747 (5)	0.9448 (3)	0.5398 (3)	0.0404 (12)
H19	0.2200	0.9727	0.5626	0.048*
C22	−0.3115 (6)	0.9542 (3)	0.2796 (3)	0.0466 (14)
H22	−0.2548	0.9828	0.2586	0.056*
C21	−0.4691 (6)	0.9439 (3)	0.2511 (3)	0.0531 (15)
H21	−0.5405	0.9635	0.2074	0.064*
C18	0.4314 (6)	0.9319 (3)	0.5673 (3)	0.0496 (14)
H18	0.5046	0.9495	0.6116	0.060*
N4	0.2023 (5)	0.7178 (3)	0.5191 (3)	0.0549 (12)
H4N	0.1222	0.7405	0.5218	0.066*
C16	0.2400 (5)	0.7077 (3)	0.4577 (3)	0.0441 (12)
H16	0.1806	0.7246	0.4101	0.053*
C15	0.3138 (7)	0.6855 (4)	0.5755 (4)	0.0633 (17)
H15	0.3192	0.6828	0.6254	0.076*
C12	0.6730 (6)	0.6973 (3)	0.2298 (3)	0.0525 (14)
H12	0.6683	0.6960	0.1799	0.063*
O11	1.2716 (4)	0.4804 (2)	0.4224 (2)	0.0636 (12)
N9	1.0139 (5)	0.5105 (2)	0.3827 (3)	0.0555 (12)
C24	0.9597 (8)	0.4537 (4)	0.4157 (4)	0.073 (2)
H24A	0.9436	0.4139	0.3834	0.110*
H24B	0.8614	0.4660	0.4217	0.110*
H24C	1.0376	0.4431	0.4641	0.110*
C23	1.1617 (7)	0.5176 (3)	0.3867 (3)	0.0634 (17)
H23	1.1843	0.5542	0.3600	0.076*
C25	0.8863 (10)	0.5547 (4)	0.3310 (6)	0.132 (4)
H25A	0.9320	0.5877	0.3066	0.198*
H25B	0.8327	0.5788	0.3595	0.198*
H25C	0.8117	0.5261	0.2936	0.198*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0181 (3)	0.0249 (3)	0.0169 (3)	−0.00076 (19)	−0.00107 (19)	0.0007 (2)
Cu2	0.0243 (3)	0.0221 (3)	0.0170 (3)	0.00021 (19)	0.0045 (2)	0.00088 (19)
O3	0.0329 (15)	0.0251 (17)	0.0207 (14)	−0.0055 (12)	0.0123 (12)	−0.0071 (12)
O4	0.0410 (17)	0.0231 (18)	0.0303 (16)	−0.0099 (13)	0.0149 (13)	−0.0024 (13)
O2	0.0269 (15)	0.0292 (18)	0.0246 (15)	−0.0017 (13)	−0.0034 (12)	−0.0083 (13)
O1	0.0223 (13)	0.0270 (18)	0.0223 (15)	0.0006 (12)	−0.0017 (11)	0.0024 (13)
O5	0.0264 (14)	0.0209 (17)	0.0222 (15)	0.0019 (12)	−0.0017 (11)	0.0024 (12)
O6	0.0229 (14)	0.0276 (18)	0.0291 (16)	−0.0052 (12)	0.0003 (12)	−0.0042 (13)
O8	0.074 (2)	0.0191 (19)	0.0305 (18)	−0.0097 (16)	0.0105 (16)	−0.0003 (14)
O7	0.0304 (14)	0.0242 (17)	0.0184 (14)	−0.0015 (12)	0.0081 (11)	−0.0029 (12)
O10	0.0335 (15)	0.0196 (17)	0.0401 (17)	0.0000 (13)	0.0120 (13)	−0.0002 (13)
O9	0.0472 (19)	0.030 (2)	0.053 (2)	−0.0015 (15)	0.0126 (16)	0.0056 (16)
N1	0.0276 (18)	0.026 (2)	0.0263 (19)	−0.0016 (15)	0.0055 (14)	−0.0036 (15)
N7	0.0266 (18)	0.029 (2)	0.0240 (18)	−0.0003 (15)	0.0060 (14)	0.0036 (15)
N3	0.0258 (18)	0.035 (2)	0.032 (2)	−0.0033 (15)	0.0071 (15)	0.0034 (17)
N5	0.0288 (18)	0.023 (2)	0.0249 (18)	0.0021 (15)	0.0064 (14)	0.0010 (15)
C7	0.0177 (18)	0.029 (3)	0.020 (2)	0.0013 (17)	0.0060 (15)	−0.0044 (18)
C2	0.0225 (18)	0.022 (2)	0.0096 (17)	−0.0001 (16)	0.0008 (14)	0.0012 (15)
C4	0.0200 (18)	0.020 (2)	0.022 (2)	0.0035 (16)	0.0009 (15)	−0.0021 (17)
C1	0.0188 (18)	0.029 (3)	0.024 (2)	0.0015 (17)	0.0045 (16)	−0.0004 (19)
C10	0.0226 (19)	0.019 (2)	0.023 (2)	0.0034 (16)	0.0061 (15)	−0.0001 (17)
N8	0.0246 (19)	0.055 (3)	0.046 (2)	−0.0078 (18)	0.0035 (17)	0.006 (2)
C3	0.0184 (17)	0.019 (2)	0.0125 (18)	−0.0038 (15)	0.0034 (14)	−0.0031 (15)
C6	0.0233 (18)	0.020 (2)	0.0109 (17)	−0.0009 (16)	0.0029 (14)	−0.0005 (15)
C8	0.0197 (17)	0.021 (2)	0.0102 (17)	−0.0042 (16)	0.0028 (13)	−0.0008 (15)
C5	0.0210 (18)	0.021 (2)	0.022 (2)	0.0009 (16)	0.0042 (15)	0.0005 (17)
C13	0.041 (3)	0.057 (4)	0.023 (2)	−0.012 (2)	0.0088 (19)	−0.012 (2)
C17	0.038 (2)	0.036 (3)	0.031 (2)	0.004 (2)	0.0090 (19)	−0.006 (2)
C11	0.033 (2)	0.023 (3)	0.039 (3)	−0.0059 (19)	0.0151 (19)	−0.0070 (19)
N6	0.029 (2)	0.054 (3)	0.042 (2)	0.0132 (19)	0.0003 (17)	−0.006 (2)
C20	0.035 (2)	0.035 (3)	0.027 (2)	−0.002 (2)	0.0065 (18)	0.004 (2)
C9	0.0205 (19)	0.024 (2)	0.021 (2)	0.0015 (17)	−0.0008 (15)	0.0011 (17)
N2	0.046 (2)	0.044 (3)	0.037 (2)	−0.0142 (19)	0.0242 (18)	−0.0041 (19)
C14	0.047 (3)	0.058 (4)	0.033 (3)	0.007 (2)	0.014 (2)	0.014 (2)
C19	0.039 (3)	0.041 (3)	0.030 (3)	0.009 (2)	−0.0005 (19)	−0.016 (2)
C22	0.043 (3)	0.065 (4)	0.026 (2)	−0.006 (3)	0.005 (2)	0.023 (2)
C21	0.034 (3)	0.081 (4)	0.036 (3)	0.001 (3)	0.002 (2)	0.031 (3)
C18	0.036 (3)	0.057 (4)	0.042 (3)	0.005 (2)	−0.004 (2)	−0.023 (3)
N4	0.055 (3)	0.064 (3)	0.058 (3)	0.011 (2)	0.034 (2)	−0.005 (2)
C16	0.037 (3)	0.051 (3)	0.049 (3)	0.008 (2)	0.022 (2)	0.006 (3)
C15	0.064 (4)	0.084 (5)	0.054 (4)	0.000 (3)	0.036 (3)	0.000 (3)
C12	0.059 (3)	0.069 (4)	0.036 (3)	−0.011 (3)	0.026 (2)	−0.008 (3)
O11	0.042 (2)	0.055 (3)	0.082 (3)	0.0004 (18)	0.0066 (19)	0.027 (2)
N9	0.042 (2)	0.043 (3)	0.076 (3)	0.006 (2)	0.014 (2)	−0.014 (2)
C24	0.083 (4)	0.071 (5)	0.078 (5)	−0.021 (4)	0.044 (4)	−0.027 (4)
C23	0.068 (4)	0.048 (4)	0.062 (4)	−0.014 (3)	0.008 (3)	−0.002 (3)
C25	0.091 (6)	0.083 (6)	0.173 (10)	0.048 (5)	−0.014 (6)	−0.025 (6)

Geometric parameters (Å, º) top

Cu1—N1	2.003 (4)	C3—C5	1.389 (5)
Cu1—N3	2.025 (4)	C6—C5	1.393 (5)
Cu1—O1	1.984 (3)	C6—C8	1.398 (5)
Cu1—O5ⁱ	1.985 (3)	C8—C9	1.506 (5)
Cu1—O9	2.344 (3)	C5—H5	0.9300
Cu2—N5	1.985 (3)	C13—C12	1.335 (7)
Cu2—N7	1.980 (3)	C13—H13	0.9300
Cu2—O3	2.243 (3)	C17—N6	1.327 (6)
Cu2—O7ⁱⁱ	2.003 (3)	C17—H17	0.9300
Cu2—O10	2.043 (3)	C11—N2	1.337 (6)
O3—C4	1.257 (5)	C11—H11	0.9300
O4—C4	1.245 (5)	N6—C18	1.358 (6)
O2—C1	1.240 (5)	N6—H6N	0.8600
O1—C1	1.282 (5)	C20—H20	0.9300
O5—C7	1.256 (5)	N2—C12	1.340 (6)
O5—Cu1ⁱⁱⁱ	1.985 (3)	N2—H2N	0.8600
O6—C7	1.247 (5)	C14—C15	1.339 (8)
O8—C9	1.228 (5)	C14—H14	0.9300
O7—C9	1.273 (5)	C19—C18	1.344 (6)
O7—Cu2^iv	2.003 (3)	C19—H19	0.9300
O10—H10A	0.8500	C22—C21	1.344 (7)
O10—H10B	0.8500	C22—H22	0.9300
O9—H9B	0.8499	C21—H21	0.9300
O9—H9C	0.8500	C18—H18	0.9300
N1—C11	1.312 (5)	N4—C16	1.335 (7)
N1—C13	1.367 (6)	N4—C15	1.335 (7)
N7—C20	1.323 (6)	N4—H4N	0.8600
N7—C22	1.380 (5)	C16—H16	0.9300
N3—C16	1.327 (6)	C15—H15	0.9300
N3—C14	1.348 (6)	C12—H12	0.9300
N5—C17	1.325 (6)	O11—C23	1.217 (7)
N5—C19	1.376 (5)	N9—C23	1.313 (8)
C7—C6	1.512 (5)	N9—C24	1.429 (8)
C2—C10	1.378 (5)	N9—C25	1.487 (8)
C2—C3	1.406 (5)	C24—H24A	0.9600
C2—C1	1.503 (5)	C24—H24B	0.9600
C4—C3	1.514 (5)	C24—H24C	0.9600
C10—C8	1.393 (5)	C23—H23	0.9300
C10—H10	0.9300	C25—H25A	0.9600
N8—C20	1.327 (6)	C25—H25B	0.9600
N8—C21	1.342 (6)	C25—H25C	0.9600
N8—H8N	0.8600

O1—Cu1—O5ⁱ	176.77 (12)	C3—C5—C6	120.8 (4)
O1—Cu1—N1	88.65 (13)	C3—C5—H5	119.6
O5ⁱ—Cu1—N1	89.92 (13)	C6—C5—H5	119.6
O1—Cu1—N3	90.46 (13)	C12—C13—N1	109.2 (4)
O5ⁱ—Cu1—N3	90.31 (13)	C12—C13—H13	125.4
N1—Cu1—N3	167.36 (15)	N1—C13—H13	125.4
O1—Cu1—O9	98.32 (12)	N5—C17—N6	111.0 (4)
O5ⁱ—Cu1—O9	84.71 (12)	N5—C17—H17	124.5
N1—Cu1—O9	96.07 (13)	N6—C17—H17	124.5
N3—Cu1—O9	96.53 (14)	N1—C11—N2	111.8 (4)
N7—Cu2—N5	172.01 (15)	N1—C11—H11	124.1
N7—Cu2—O7ⁱⁱ	94.38 (13)	N2—C11—H11	124.1
N5—Cu2—O7ⁱⁱ	88.09 (13)	C17—N6—C18	107.6 (4)
N7—Cu2—O10	87.98 (13)	C17—N6—H6N	126.2
N5—Cu2—O10	88.73 (13)	C18—N6—H6N	126.2
O7ⁱⁱ—Cu2—O10	173.16 (12)	N7—C20—N8	111.2 (4)
N7—Cu2—O3	91.92 (13)	N7—C20—H20	124.4
N5—Cu2—O3	95.39 (13)	N8—C20—H20	124.4
O7ⁱⁱ—Cu2—O3	95.99 (11)	O8—C9—O7	124.6 (4)
O10—Cu2—O3	90.34 (12)	O8—C9—C8	120.6 (4)
C4—O3—Cu2	125.3 (3)	O7—C9—C8	114.6 (4)
C1—O1—Cu1	106.6 (2)	C11—N2—C12	106.3 (4)
C7—O5—Cu1ⁱⁱⁱ	113.6 (2)	C11—N2—H2N	126.8
C9—O7—Cu2^iv	114.2 (3)	C12—N2—H2N	126.8
Cu2—O10—H10A	109.2	C15—C14—N3	110.8 (5)
Cu2—O10—H10B	109.3	C15—C14—H14	124.6
H10A—O10—H10B	109.5	N3—C14—H14	124.6
Cu1—O9—H9B	109.2	C18—C19—N5	108.8 (4)
Cu1—O9—H9C	109.3	C18—C19—H19	125.6
H9B—O9—H9C	109.5	N5—C19—H19	125.6
C11—N1—C13	104.8 (4)	C21—C22—N7	109.6 (4)
C11—N1—Cu1	124.3 (3)	C21—C22—H22	125.2
C13—N1—Cu1	129.3 (3)	N7—C22—H22	125.2
C20—N7—C22	104.5 (4)	N8—C21—C22	106.4 (4)
C20—N7—Cu2	128.8 (3)	N8—C21—H21	126.8
C22—N7—Cu2	126.5 (3)	C22—C21—H21	126.8
C16—N3—C14	103.6 (4)	C19—C18—N6	107.0 (4)
C16—N3—Cu1	124.9 (3)	C19—C18—H18	126.5
C14—N3—Cu1	129.4 (3)	N6—C18—H18	126.5
C17—N5—C19	105.7 (4)	C16—N4—C15	106.2 (5)
C17—N5—Cu2	126.0 (3)	C16—N4—H4N	126.9
C19—N5—Cu2	128.3 (3)	C15—N4—H4N	126.9
O6—C7—O5	125.6 (3)	N3—C16—N4	112.3 (5)
O6—C7—C6	117.8 (4)	N3—C16—H16	123.9
O5—C7—C6	116.7 (3)	N4—C16—H16	123.9
C10—C2—C3	119.5 (3)	N4—C15—C14	107.1 (5)
C10—C2—C1	121.4 (4)	N4—C15—H15	126.4
C3—C2—C1	119.0 (3)	C14—C15—H15	126.4
O4—C4—O3	127.1 (4)	C13—C12—N2	107.8 (5)
O4—C4—C3	119.1 (4)	C13—C12—H12	126.1
O3—C4—C3	113.6 (3)	N2—C12—H12	126.1
O2—C1—O1	124.0 (3)	C23—N9—C24	123.4 (5)
O2—C1—C2	119.0 (4)	C23—N9—C25	120.7 (7)
O1—C1—C2	116.9 (3)	C24—N9—C25	115.0 (6)
C2—C10—C8	121.6 (4)	N9—C24—H24A	109.5
C2—C10—H10	119.2	N9—C24—H24B	109.5
C8—C10—H10	119.2	H24A—C24—H24B	109.5
C20—N8—C21	108.2 (4)	N9—C24—H24C	109.5
C20—N8—H8N	125.9	H24A—C24—H24C	109.5
C21—N8—H8N	125.9	H24B—C24—H24C	109.5
C5—C3—C2	119.3 (3)	O11—C23—N9	125.4 (6)
C5—C3—C4	118.6 (3)	O11—C23—H23	117.3
C2—C3—C4	121.9 (3)	N9—C23—H23	117.3
C5—C6—C8	119.9 (3)	N9—C25—H25A	109.5
C5—C6—C7	119.6 (3)	N9—C25—H25B	109.5
C8—C6—C7	120.4 (3)	H25A—C25—H25B	109.5
C10—C8—C6	118.8 (3)	N9—C25—H25C	109.5
C10—C8—C9	119.3 (3)	H25A—C25—H25C	109.5
C6—C8—C9	121.7 (3)	H25B—C25—H25C	109.5

N7—Cu2—O3—C4	98.4 (3)	C1—C2—C3—C4	−7.1 (5)
N5—Cu2—O3—C4	−78.3 (3)	O4—C4—C3—C5	−78.2 (5)
O7ⁱⁱ—Cu2—O3—C4	−167.0 (3)	O3—C4—C3—C5	98.4 (4)
O10—Cu2—O3—C4	10.4 (3)	O4—C4—C3—C2	107.7 (4)
O5ⁱ—Cu1—O1—C1	−13 (2)	O3—C4—C3—C2	−75.7 (5)
N1—Cu1—O1—C1	−76.3 (3)	O6—C7—C6—C5	−141.6 (4)
N3—Cu1—O1—C1	91.1 (3)	O5—C7—C6—C5	38.7 (5)
O9—Cu1—O1—C1	−172.2 (3)	O6—C7—C6—C8	33.9 (5)
O1—Cu1—N1—C11	142.5 (4)	O5—C7—C6—C8	−145.8 (4)
O5ⁱ—Cu1—N1—C11	−34.6 (3)	C2—C10—C8—C6	−3.0 (6)
N3—Cu1—N1—C11	56.4 (7)	C2—C10—C8—C9	172.2 (4)
O9—Cu1—N1—C11	−119.3 (3)	C5—C6—C8—C10	2.0 (6)
O1—Cu1—N1—C13	−20.6 (4)	C7—C6—C8—C10	−173.5 (3)
O5ⁱ—Cu1—N1—C13	162.3 (4)	C5—C6—C8—C9	−173.0 (4)
N3—Cu1—N1—C13	−106.6 (7)	C7—C6—C8—C9	11.5 (6)
O9—Cu1—N1—C13	77.7 (4)	C2—C3—C5—C6	−1.3 (6)
N5—Cu2—N7—C20	−105.7 (10)	C4—C3—C5—C6	−175.5 (4)
O7ⁱⁱ—Cu2—N7—C20	2.1 (4)	C8—C6—C5—C3	0.1 (6)
O10—Cu2—N7—C20	−171.5 (4)	C7—C6—C5—C3	175.6 (3)
O3—Cu2—N7—C20	98.3 (4)	C11—N1—C13—C12	−0.1 (6)
N5—Cu2—N7—C22	79.8 (11)	Cu1—N1—C13—C12	165.4 (4)
O7ⁱⁱ—Cu2—N7—C22	−172.4 (4)	C19—N5—C17—N6	−0.8 (5)
O10—Cu2—N7—C22	14.0 (4)	Cu2—N5—C17—N6	−178.3 (3)
O3—Cu2—N7—C22	−76.2 (4)	C13—N1—C11—N2	0.2 (5)
O1—Cu1—N3—C16	−39.4 (4)	Cu1—N1—C11—N2	−166.3 (3)
O5ⁱ—Cu1—N3—C16	137.5 (4)	N5—C17—N6—C18	0.2 (6)
N1—Cu1—N3—C16	46.5 (8)	C22—N7—C20—N8	0.7 (5)
O9—Cu1—N3—C16	−137.8 (4)	Cu2—N7—C20—N8	−174.8 (3)
O1—Cu1—N3—C14	160.2 (4)	C21—N8—C20—N7	−0.7 (6)
O5ⁱ—Cu1—N3—C14	−23.0 (4)	Cu2^iv—O7—C9—O8	−14.0 (5)
N1—Cu1—N3—C14	−114.0 (6)	Cu2^iv—O7—C9—C8	160.5 (2)
O9—Cu1—N3—C14	61.7 (4)	C10—C8—C9—O8	58.3 (5)
N7—Cu2—N5—C17	−156.0 (9)	C6—C8—C9—O8	−126.6 (4)
O7ⁱⁱ—Cu2—N5—C17	95.8 (4)	C10—C8—C9—O7	−116.4 (4)
O10—Cu2—N5—C17	−90.3 (4)	C6—C8—C9—O7	58.6 (5)
O3—Cu2—N5—C17	−0.1 (4)	N1—C11—N2—C12	−0.2 (6)
N7—Cu2—N5—C19	27.0 (12)	C16—N3—C14—C15	0.3 (6)
O7ⁱⁱ—Cu2—N5—C19	−81.2 (4)	Cu1—N3—C14—C15	163.9 (4)
O10—Cu2—N5—C19	92.8 (4)	C17—N5—C19—C18	1.1 (6)
O3—Cu2—N5—C19	−177.0 (4)	Cu2—N5—C19—C18	178.6 (4)
Cu1ⁱⁱⁱ—O5—C7—O6	3.3 (5)	C20—N7—C22—C21	−0.4 (6)
Cu1ⁱⁱⁱ—O5—C7—C6	−177.1 (2)	Cu2—N7—C22—C21	175.2 (4)
Cu2—O3—C4—O4	13.8 (5)	C20—N8—C21—C22	0.4 (7)
Cu2—O3—C4—C3	−162.4 (2)	N7—C22—C21—N8	0.0 (7)
Cu1—O1—C1—O2	−6.3 (5)	N5—C19—C18—N6	−1.1 (7)
Cu1—O1—C1—C2	175.1 (3)	C17—N6—C18—C19	0.5 (6)
C10—C2—C1—O2	152.4 (4)	C14—N3—C16—N4	0.2 (6)
C3—C2—C1—O2	−26.0 (6)	Cu1—N3—C16—N4	−164.4 (3)
C10—C2—C1—O1	−28.9 (6)	C15—N4—C16—N3	−0.6 (7)
C3—C2—C1—O1	152.7 (4)	C16—N4—C15—C14	0.8 (7)
C3—C2—C10—C8	1.8 (6)	N3—C14—C15—N4	−0.7 (7)
C1—C2—C10—C8	−176.7 (4)	N1—C13—C12—N2	0.0 (7)
C10—C2—C3—C5	0.3 (6)	C11—N2—C12—C13	0.1 (6)
C1—C2—C3—C5	178.8 (3)	C24—N9—C23—O11	−5.1 (10)
C10—C2—C3—C4	174.4 (4)	C25—N9—C23—O11	−173.7 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3^v	0.86	2.01	2.807 (5)	153
N4—H4N···O7ⁱⁱ	0.86	2.35	3.099 (5)	146
N6—H6N···O6ⁱ	0.86	2.03	2.733 (5)	138
N8—H8N···O2^vi	0.86	2.35	2.952 (5)	127
N8—H8N···O4^vi	0.86	2.26	3.033 (6)	149
O9—H9B···O11^vii	0.85	2.06	2.909 (5)	177
O9—H9C···O11^vi	0.85	2.02	2.805 (6)	153
O10—H10A···O8^viii	0.85	1.90	2.655 (4)	147
O10—H10B···O4	0.85	2.24	2.703 (5)	114

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

Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₀H₂O₈)(C₃H₄N₂)₄(H₂O)₂]·C₃H₇NO
M_r	758.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	8.999 (4), 19.296 (8), 18.926 (7)
β (°)	110.590 (18)
V (Å³)	3076 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.46
Crystal size (mm)	0.23 × 0.21 × 0.15

Data collection
Diffractometer	Bruker APEXII area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.731, 0.811
No. of measured, independent and observed [I > 2σ(I)] reflections	17289, 5445, 4149
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.153, 1.11
No. of reflections	5445
No. of parameters	426
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.60

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—N1	2.003 (4)	Cu2—N5	1.985 (3)
Cu1—N3	2.025 (4)	Cu2—N7	1.980 (3)
Cu1—O1	1.984 (3)	Cu2—O3	2.243 (3)
Cu1—O5ⁱ	1.985 (3)	Cu2—O7ⁱⁱ	2.003 (3)
Cu1—O9	2.344 (3)	Cu2—O10	2.043 (3)

Symmetry codes: (i) x+1, −y+3/2, z+1/2; (ii) x, −y+3/2, z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3ⁱⁱⁱ	0.86	2.01	2.807 (5)	153
N4—H4N···O7ⁱⁱ	0.86	2.35	3.099 (5)	146
N6—H6N···O6ⁱ	0.86	2.03	2.733 (5)	138
N8—H8N···O2^iv	0.86	2.35	2.952 (5)	127
N8—H8N···O4^iv	0.86	2.26	3.033 (6)	149
O9—H9B···O11^v	0.85	2.06	2.909 (5)	177
O9—H9C···O11^iv	0.85	2.02	2.805 (6)	153
O10—H10A···O8^vi	0.85	1.90	2.655 (4)	147
O10—H10B···O4	0.85	2.24	2.703 (5)	114

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

Acknowledgements

The work was supported by the National Natural Science Foundation of China (grant Nos. 21171133 and 21271143) and the Opening Foundation of Zhejiang Provincial Top Key Discipline (20121112).

References

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