Poly[octakis(1H-imidazole-κN3)octa-μ-oxido-tetra­oxidodicopper(II)tetra­vanadate(V)]

Chanthee, S.; Saesong, T.; Saphu, W.; Chainok, K.; Krachodnok, S.

doi:10.1107/S1600536812008252

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m362-m363

doi:10.1107/S1600536812008252

Open

access

Poly[octakis(1H-imidazole-κN³)octa-μ-oxido-tetraoxidodicopper(II)tetravanadate(V)]

Songwuit Chanthee,^a Tongchai Saesong,^a Watcharin Saphu,^a Kittipong Chainok ^a ^* and Samroeng Krachodnok ^b

^aDepartment of Chemistry, Faculty of Science, Naresuan University, Muang, Phitsanulok 65000, Thailand, and ^bDepartment of Applied Chemistry and Center for Innovation in Chemistry, Faculty of Science, Lampang Rajabhat University, Lampang 52100, Thailand
^*Correspondence e-mail: kittipongc@nu.ac.th

(Received 15 February 2012; accepted 24 February 2012; online 3 March 2012)

In the title inorganic–organic hybrid compound, [Cu₂V₄O₁₂(C₃H₄N₂)₈]_n, the V^V ion is tetracoordinated by four O atoms and the Cu^II ion is hexacoordinated by four N atoms from four imidazole ligands and two O atoms from two tetrahedral vanadate (VO₄) units in a distorted octahedral geometry. The structure consists of two-dimensional sheets constructed from centrosymmetric cyclic [V₄O₁₂]⁴⁻ anions covalently bound through O to [Cu(imidazole)₄]²⁺ cations. Adjacent sheets are linked by N—H⋯O hydrogen bonds and weak C—H⋯π interactions (H⋯centroid distances = 2.59, 2.66, 2.76, 2.91 and 2.98 Å into a three-dimensional supramolecular network.

Related literature

For background to inorganic–organic hybrids involving vanadium oxides, see: Cheetham et al. (1999 ); Hagrman et al. (2001 ); Natarajan & Mandal (2008 ); Zavalij & Whittingham (1999 ). For related structures, see: Chainok et al. (2011 ). For the bond valence sum calculation, see: Brown & Altermatt (1985 ).

Experimental

Crystal data

[Cu₂V₄O₁₂(C₃H₄N₂)₈]
M_r = 1067.52
Monoclinic, P 2₁ /n
a = 10.1761 (6) Å
b = 16.5092 (9) Å
c = 12.0372 (7) Å
β = 103.844 (1)°
V = 1963.50 (19) Å³
Z = 2
Mo Kα radiation
μ = 2.05 mm⁻¹
T = 100 K
0.24 × 0.20 × 0.18 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.639, T_max = 0.722
11719 measured reflections
4370 independent reflections
3830 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.073
S = 1.04
4370 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C11/C12/N13/C14/C15, C21/C22/N23/C24/C25, C31/C32/N33/C34/C35 and C41/C42/N43/C44/C45 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N13—H13⋯O3ⁱ	0.88	2.01	2.827 (2)	155
N23—H23⋯O5ⁱⁱ	0.88	1.95	2.779 (2)	155
N33—H33⋯O2ⁱⁱⁱ	0.88	1.90	2.694 (2)	149
N43—H43⋯O5^iv	0.88	1.88	2.701 (2)	155
C24—H24⋯Cg1^v	0.95	2.99	3.912 (2)	165
C12—H12⋯Cg2ⁱ	0.95	2.59	3.429 (2)	147
C22—H22⋯Cg3^vi	0.95	2.66	3.332 (2)	128
C44—H44⋯Cg3^vii	0.95	2.91	3.816 (2)	161
C32—H32⋯Cg4^viii	0.95	2.76	3.321 (2)	119
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) -x+2, -y+1, -z+2; (iv) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (v) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (vii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (viii) $[x+{\script{1\over 2}}, -y-{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812008252/hy2518sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812008252/hy2518Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812008252/hy2518Isup3.cdx

checkCIF report

Comment top

The synthesis of extended solids based on inorganic-organic hybrids involving vanadium oxides have received much attention due to their structural diversity and fascinating properties with applications in catalysis, ion exchange, magnetic materials (V⁴⁺, V³⁺), and the development of new cathode materials for Li batteries (Cheetham et al., 1999; Natarajan & Mandal, 2008). One approach for the design of such hybrid vanadium oxide frameworks is to introduce organic amine ligands to the secondary metal sites incorporating hydrothermal or solvothermal methods. Following this approach, numerous hybrid metal vanadium oxide framework structures involving edge- and corner-sharing VO₄ tetrahedra, VO₅ square-pyramids, or VO₆ octahedra and incorporating organic species such as diammonium cations have been successfully synthesized (Hagrman et al., 2001). Among the solid state polyhedra of vanadium oxide structures, the tetrahedral linking unit VO₄ is commonly observed (Zavalij & Whittingham, 1999). Recently, we have used the aromatic diamine planar geometry of imidazole and hydrothermal method to synthesize a new series of hybrid inorganic-organic metal vanadium oxide compounds with a general formula [M(imidazole)₄V₂O₆]_n (M = Mn, Co, Ni) (Chainok et al., 2011). The structures of these isostructural species contain two-dimensional polymeric sheets and display an interesting order-disorder crystallographic phase transition between the P4₂/n at 295 K and I4₁/a (Mn and Co) or P2/n (Ni) space groups at 100 K. As a continuation of this work, we report the title compound, (I), a new member of this family, which is isostructural to [M(imidazole)₄V₂O₆]_n.

Fig. 1 shows the asymmetric unit with atomic numbering and the detailed coordination environment for the metals ions in (I). It crystallizes in the monoclinic space group P2₁/n at 100 K. There are two crystallographically independent V atoms and one distinct Cu atom. The bond valence sum calculation (Brown & Altermatt, 1985) indicates that the oxidation state of all the V atoms are pentavalent and Cu is divalent. All the V atoms adopt a tetrahedral geometry involving one terminal and three bridging O atoms. The mean V—O bond lengths involving the O atoms bridging V and Cu atoms are 1.632 Å and significantly shorter than those involving the O atoms bridging V atoms only (mean 1.818 Å). The mean V—O bond lengths of those involving terminal O atoms are 1.648 Å. The bond lengths and angles around the V atoms are comparable to those observed in the ordered phases of [M(imidazole)₄V₂O₆]_n (Chainok et al., 2011). The Cu atom is in a distorted octahedral geometry with four equatorial N atoms from the imidazole ligands and two axial O atoms from VO₄ units. The mean M—N bond lengths in the [M(imidazole)₄V₂O₆]_n series are 2.251, 2.137, 2.137 and 2.008 Å for the Mn, Co, Ni and Cu complexes, respectively, showing that the M—N bond lengths systematically decrease with increasing atomic number in the order of Mn^II > Co^II ~ Ni^II > Cu^II. A similar trend, however, is not observed for the M—O bond lengths. The mean M—O bond lengths for the Mn, Co and Ni complexes are 2.154, 2.100 and 2.100 Å, respectively, while the Cu complex has the longest M—O bond lengths with a mean value of 2.413 Å. The latter case seems to be influenced by the distortion of Jahn-Teller effect on the Cu^II coordination polyhedra.

As shown in Fig. 2, the crystal structure consists of two-dimensional polymeric sheets constructed by centrosymmetric cyclic V₄O₁₂ tetramers (exhibiting an approximate C_2v symmetry) and CuN₄O₂ octahedra involving four separate imidazoles. The framework of sheet structure can be alternatively described as four corner-connected VO₄ tetrahedra forming eight-membered [V₄O₄] small rings, and four CuN₄O₂ octahedra and eight VO₄ tetrahedra further connected to form twenty four-membered [Cu₄V₈O₁₂] large rings. A packing view along the b axis (Fig. 3) shows the two-dimensional layer structure with the imidazole ligands decorating the layer on the periphery. The coordinated imidazole ligands on the Cu atoms form intermolecular N—H···O hydrogen bonds to the bridging oxido groups and the terminal vanadyl sites above and below adjacent layers (Fig. 4, Table 1). These layers are further stabilized by weak edge to face C—H···π interactions between the imidazole H atoms (H12, H24, H32, and H44) and the centroids (Cg) of the imidazole rings (Fig. 5). It should be noted that there is no π–π stacking between adjacent imidazole rings in this compound.

Related literature top

For background to inorganic–organic hybrids involving vanadium oxides, see: Cheetham et al. (1999); Hagrman et al. (2001); Natarajan & Mandal (2008); Zavalij & Whittingham (1999). For related structures, see: Chainok et al. (2011). For the bond valence sum calculation, see: Brown & Altermatt (1985).

Experimental top

A mixture of Cu(CH₃COO)₂.2H₂O (180 mg, 1.0 mmol), V₂O₅ (180 mg, 1.0 mmol), imidazole (410 mg, 6.0 mmol), and H₂O (500 mg, 278.0 mmol) in a mole ratio of 1:1:6:278 was sealed in a 23 ml Teflon-lined Parr reactor, which was placed in an oven and heated from room temperature to 393 K under autogenous pressure for 5 d. After cooling, the product was filtered off from the bright blue mother liquor, washed with distilled water and then dried overnight at room temperature. Dark-blue block-shaped crystals were easily separated from the residual uncharacterized brown-blue powder by hand under an optical microscope. The yield was 85% (0.15 g) based on V₂O₅. Analysis, calculated for C₁₂H₁₆CuN₈O₆V₂: C 27.00, H 3.02, N 21.07%; found: C 27.01, H 3.08, N 21.02%.

Structure description top

For background to inorganic–organic hybrids involving vanadium oxides, see: Cheetham et al. (1999); Hagrman et al. (2001); Natarajan & Mandal (2008); Zavalij & Whittingham (1999). For related structures, see: Chainok et al. (2011). For the bond valence sum calculation, see: Brown & Altermatt (1985).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The aymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
	Fig. 2. Polyhedral representation of the two-dimensional sheet structure of (I). H atoms have been omitted for clarity.
	Fig. 3. View of the layer structure of (I) along the b axis. H atoms have been omitted for clarity.
	Fig. 4. View of N—H···O hydrogen bonds (dashed lines) in (I). H atoms have been omitted for clarity.
	Fig. 5. View of weak intermolecular C—H···π interactions (dashed lines) in (I). (H12···Cg2 = 2.59, H22···Cg3 = 2.66, H44···Cg3 = 2.91, H32···Cg4 = 2.76 Å.)

Poly[octakis(1H-imidazole-κN³)octa-µ-oxido- tetraoxidodicopper(II)tetravanadate(V)] top

Crystal data top

[Cu₂V₄O₁₂(C₃H₄N₂)₈]	F(000) = 1068
M_r = 1067.52	D_x = 1.806 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3583 reflections
a = 10.1761 (6) Å	θ = 2.4–27.4°
b = 16.5092 (9) Å	µ = 2.05 mm⁻¹
c = 12.0372 (7) Å	T = 100 K
β = 103.844 (1)°	Block, dark blue
V = 1963.50 (19) Å³	0.24 × 0.20 × 0.18 mm
Z = 2

Data collection top

Bruker APEX CCD diffractometer	4370 independent reflections
Radiation source: sealed tube	3830 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ω and φ scans	θ_max = 28.2°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
T_min = 0.639, T_max = 0.722	k = −20→16
11719 measured reflections	l = −15→15

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0408P)² + 0.1105P] where P = (F_o² + 2F_c²)/3
4370 reflections	(Δ/σ)_max = 0.001
262 parameters	Δρ_max = 0.51 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³
0 constraints

Crystal data top

[Cu₂V₄O₁₂(C₃H₄N₂)₈]	V = 1963.50 (19) Å³
M_r = 1067.52	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1761 (6) Å	µ = 2.05 mm⁻¹
b = 16.5092 (9) Å	T = 100 K
c = 12.0372 (7) Å	0.24 × 0.20 × 0.18 mm
β = 103.844 (1)°

Data collection top

Bruker APEX CCD diffractometer	4370 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3830 reflections with I > 2σ(I)
T_min = 0.639, T_max = 0.722	R_int = 0.025
11719 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.04	Δρ_max = 0.51 e Å⁻³
4370 reflections	Δρ_min = −0.30 e Å⁻³
262 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	0.80636 (2)	0.241362 (13)	0.801507 (19)	0.00947 (8)
V1	0.61028 (3)	0.417383 (18)	0.91849 (3)	0.00910 (9)
O1	0.64852 (14)	0.33438 (8)	0.85877 (11)	0.0151 (3)
V2	0.46561 (3)	0.585997 (19)	0.82471 (3)	0.00889 (9)
O2	0.75077 (14)	0.46664 (8)	0.97220 (12)	0.0183 (3)
O3	0.50084 (14)	0.47895 (8)	0.80807 (11)	0.0143 (3)
O4	0.47841 (14)	0.60729 (8)	0.97210 (11)	0.0151 (3)
O5	0.31228 (14)	0.60726 (9)	0.74519 (12)	0.0162 (3)
O6	0.92507 (14)	0.14149 (8)	0.71994 (12)	0.0158 (3)
N11	0.82168 (16)	0.18449 (10)	0.95274 (13)	0.0131 (3)
C12	0.9253 (2)	0.14465 (12)	1.01605 (17)	0.0151 (4)
H12	1.0126	0.1424	1.0008	0.018*
N13	0.89173 (18)	0.10785 (10)	1.10445 (14)	0.0167 (4)
H13	0.9454	0.0780	1.1569	0.020*
C14	0.7591 (2)	0.12508 (13)	1.09835 (18)	0.0204 (5)
H14	0.7072	0.1075	1.1498	0.024*
C15	0.7157 (2)	0.17227 (13)	1.00442 (17)	0.0199 (4)
H15	0.6268	0.1935	0.9784	0.024*
N21	0.78124 (16)	0.31036 (10)	0.66093 (13)	0.0123 (3)
C22	0.77206 (19)	0.28959 (12)	0.55363 (16)	0.0145 (4)
H22	0.7719	0.2353	0.5274	0.017*
N23	0.76290 (17)	0.35500 (10)	0.48635 (14)	0.0167 (4)
H23	0.7556	0.3550	0.4120	0.020*
C24	0.7670 (2)	0.42209 (13)	0.55468 (18)	0.0186 (4)
H24	0.7627	0.4772	0.5312	0.022*
C25	0.7783 (2)	0.39402 (12)	0.66188 (18)	0.0169 (4)
H25	0.7835	0.4267	0.7277	0.020*
N31	0.97998 (16)	0.30136 (10)	0.86210 (13)	0.0116 (3)
C32	1.0025 (2)	0.35656 (12)	0.94453 (16)	0.0132 (4)
H32	0.9438	0.3674	0.9933	0.016*
N33	1.11982 (16)	0.39489 (10)	0.94927 (14)	0.0140 (3)
H33	1.1552	0.4333	0.9979	0.017*
C34	1.1751 (2)	0.36370 (12)	0.86493 (17)	0.0146 (4)
H34	1.2579	0.3793	0.8477	0.017*
C35	1.08746 (19)	0.30603 (12)	0.81122 (16)	0.0139 (4)
H35	1.0985	0.2740	0.7485	0.017*
N41	0.64268 (16)	0.17312 (9)	0.73864 (13)	0.0113 (3)
C42	0.51402 (19)	0.19205 (12)	0.72905 (16)	0.0135 (4)
H42	0.4809	0.2457	0.7312	0.016*
N43	0.43677 (17)	0.12534 (10)	0.71599 (14)	0.0151 (4)
H43	0.3485	0.1239	0.7076	0.018*
C44	0.5198 (2)	0.06006 (12)	0.71797 (17)	0.0166 (4)
H44	0.4937	0.0047	0.7113	0.020*
C45	0.6465 (2)	0.08987 (11)	0.73137 (17)	0.0136 (4)
H45	0.7256	0.0584	0.7352	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01030 (13)	0.00903 (13)	0.00864 (13)	−0.00211 (8)	0.00144 (9)	0.00087 (8)
V1	0.01084 (17)	0.00739 (17)	0.00899 (16)	0.00014 (12)	0.00217 (12)	−0.00107 (11)
O1	0.0206 (7)	0.0109 (7)	0.0151 (7)	0.0012 (5)	0.0065 (6)	−0.0015 (5)
V2	0.00932 (16)	0.00903 (17)	0.00877 (16)	0.00116 (11)	0.00309 (12)	0.00181 (11)
O2	0.0156 (7)	0.0128 (7)	0.0247 (8)	−0.0018 (6)	0.0015 (6)	−0.0019 (6)
O3	0.0191 (7)	0.0112 (7)	0.0115 (7)	0.0019 (5)	0.0016 (5)	−0.0002 (5)
O4	0.0190 (7)	0.0147 (7)	0.0126 (7)	0.0012 (6)	0.0058 (6)	−0.0005 (5)
O5	0.0124 (7)	0.0221 (8)	0.0152 (7)	0.0040 (6)	0.0052 (6)	0.0041 (6)
O6	0.0156 (7)	0.0163 (7)	0.0176 (7)	−0.0010 (6)	0.0080 (6)	−0.0040 (6)
N11	0.0151 (8)	0.0135 (9)	0.0106 (8)	0.0002 (6)	0.0029 (7)	0.0005 (6)
C12	0.0160 (10)	0.0140 (10)	0.0133 (10)	−0.0005 (8)	−0.0002 (8)	0.0010 (7)
N13	0.0223 (9)	0.0130 (9)	0.0123 (8)	0.0001 (7)	−0.0011 (7)	0.0025 (6)
C14	0.0264 (12)	0.0220 (12)	0.0152 (10)	−0.0012 (9)	0.0101 (9)	0.0010 (8)
C15	0.0209 (11)	0.0247 (12)	0.0169 (10)	0.0034 (9)	0.0098 (9)	0.0041 (8)
N21	0.0137 (8)	0.0110 (8)	0.0120 (8)	−0.0019 (6)	0.0025 (6)	0.0004 (6)
C22	0.0144 (10)	0.0149 (10)	0.0139 (10)	−0.0012 (8)	0.0026 (8)	−0.0006 (8)
N23	0.0192 (9)	0.0206 (9)	0.0104 (8)	−0.0020 (7)	0.0038 (7)	0.0033 (7)
C24	0.0209 (11)	0.0140 (11)	0.0207 (11)	−0.0010 (8)	0.0048 (9)	0.0070 (8)
C25	0.0212 (11)	0.0102 (10)	0.0191 (10)	−0.0023 (8)	0.0041 (8)	0.0003 (8)
N31	0.0131 (8)	0.0116 (8)	0.0100 (8)	−0.0011 (6)	0.0024 (6)	0.0008 (6)
C32	0.0145 (10)	0.0128 (10)	0.0115 (9)	0.0000 (7)	0.0018 (8)	0.0008 (7)
N33	0.0158 (9)	0.0113 (8)	0.0135 (8)	−0.0030 (6)	0.0005 (7)	−0.0018 (6)
C34	0.0130 (10)	0.0152 (10)	0.0159 (10)	−0.0011 (8)	0.0044 (8)	0.0032 (8)
C35	0.0146 (10)	0.0165 (10)	0.0108 (9)	−0.0003 (8)	0.0031 (8)	−0.0007 (7)
N41	0.0125 (8)	0.0108 (8)	0.0105 (8)	−0.0009 (6)	0.0027 (6)	−0.0003 (6)
C42	0.0124 (9)	0.0143 (10)	0.0139 (10)	−0.0008 (8)	0.0032 (8)	−0.0012 (7)
N43	0.0109 (8)	0.0180 (9)	0.0169 (9)	−0.0020 (6)	0.0040 (7)	−0.0018 (7)
C44	0.0200 (10)	0.0117 (10)	0.0186 (10)	−0.0022 (8)	0.0056 (8)	−0.0003 (8)
C45	0.0167 (10)	0.0104 (9)	0.0142 (10)	0.0008 (7)	0.0047 (8)	−0.0001 (7)

Geometric parameters (Å, º) top

Cu1—N41	2.0033 (16)	N21—C25	1.381 (2)
Cu1—N31	2.0045 (16)	C22—N23	1.340 (3)
Cu1—N21	2.0049 (16)	C22—H22	0.9500
Cu1—N11	2.0209 (16)	N23—C24	1.374 (3)
Cu1—O6	2.3894 (13)	N23—H23	0.8800
Cu1—O1	2.4379 (13)	C24—C25	1.350 (3)
V1—O1	1.6370 (13)	C24—H24	0.9500
V1—O2	1.6373 (14)	C25—H25	0.9500
V1—O4ⁱ	1.8121 (13)	N31—C32	1.326 (2)
V1—O3	1.8253 (13)	N31—C35	1.378 (2)
V2—O6ⁱⁱ	1.6285 (14)	C32—N33	1.340 (2)
V2—O5	1.6611 (14)	C32—H32	0.9500
V2—O4	1.7826 (14)	N33—C34	1.373 (3)
V2—O3	1.8237 (14)	N33—H33	0.8800
O4—V1ⁱ	1.8122 (13)	C34—C35	1.358 (3)
O6—V2ⁱⁱⁱ	1.6284 (14)	C34—H34	0.9500
N11—C12	1.319 (2)	C35—H35	0.9500
N11—C15	1.383 (3)	N41—C42	1.324 (2)
C12—N13	1.339 (3)	N41—C45	1.378 (2)
C12—H12	0.9500	C42—N43	1.340 (3)
N13—C14	1.364 (3)	C42—H42	0.9500
N13—H13	0.8800	N43—C44	1.366 (3)
C14—C15	1.357 (3)	N43—H43	0.8800
C14—H14	0.9500	C44—C45	1.354 (3)
C15—H15	0.9500	C44—H44	0.9500
N21—C22	1.318 (2)	C45—H45	0.9500

N41—Cu1—N31	174.98 (6)	C22—N21—C25	105.77 (16)
N41—Cu1—N21	94.25 (6)	C22—N21—Cu1	130.10 (14)
N31—Cu1—N21	87.11 (6)	C25—N21—Cu1	124.03 (13)
N41—Cu1—N11	87.53 (6)	N21—C22—N23	111.16 (18)
N31—Cu1—N11	91.75 (6)	N21—C22—H22	124.4
N21—Cu1—N11	172.34 (6)	N23—C22—H22	124.4
N41—Cu1—O6	85.01 (6)	C22—N23—C24	107.46 (17)
N31—Cu1—O6	90.13 (6)	C22—N23—H23	126.3
N21—Cu1—O6	91.15 (6)	C24—N23—H23	126.3
N11—Cu1—O6	96.43 (6)	C25—C24—N23	106.19 (18)
N41—Cu1—O1	85.21 (6)	C25—C24—H24	126.9
N31—Cu1—O1	99.72 (6)	N23—C24—H24	126.9
N21—Cu1—O1	85.48 (6)	C24—C25—N21	109.42 (18)
N11—Cu1—O1	87.25 (6)	C24—C25—H25	125.3
O6—Cu1—O1	169.40 (5)	N21—C25—H25	125.3
O1—V1—O2	108.20 (7)	C32—N31—C35	106.31 (16)
O1—V1—O4ⁱ	110.06 (7)	C32—N31—Cu1	126.24 (13)
O2—V1—O4ⁱ	111.36 (7)	C35—N31—Cu1	126.17 (13)
O1—V1—O3	108.31 (7)	N31—C32—N33	110.42 (17)
O2—V1—O3	109.51 (7)	N31—C32—H32	124.8
O4ⁱ—V1—O3	109.34 (6)	N33—C32—H32	124.8
V1—O1—Cu1	153.30 (8)	C32—N33—C34	108.05 (16)
O6ⁱⁱ—V2—O5	108.22 (7)	C32—N33—H33	126.0
O6ⁱⁱ—V2—O4	108.94 (7)	C34—N33—H33	126.0
O5—V2—O4	111.51 (7)	C35—C34—N33	106.05 (17)
O6ⁱⁱ—V2—O3	109.94 (7)	C35—C34—H34	127.0
O5—V2—O3	108.89 (7)	N33—C34—H34	127.0
O4—V2—O3	109.33 (6)	C34—C35—N31	109.17 (17)
V2—O3—V1	124.15 (7)	C34—C35—H35	125.4
V2—O4—V1ⁱ	138.46 (9)	N31—C35—H35	125.4
V2ⁱⁱⁱ—O6—Cu1	167.49 (8)	C42—N41—C45	105.79 (16)
C12—N11—C15	105.61 (17)	C42—N41—Cu1	128.00 (13)
C12—N11—Cu1	129.10 (14)	C45—N41—Cu1	123.45 (13)
C15—N11—Cu1	124.94 (13)	N41—C42—N43	110.87 (17)
N11—C12—N13	111.40 (18)	N41—C42—H42	124.6
N11—C12—H12	124.3	N43—C42—H42	124.6
N13—C12—H12	124.3	C42—N43—C44	107.67 (17)
C12—N13—C14	107.45 (17)	C42—N43—H43	126.2
C12—N13—H13	126.3	C44—N43—H43	126.2
C14—N13—H13	126.3	C45—C44—N43	106.43 (18)
C15—C14—N13	106.57 (18)	C45—C44—H44	126.8
C15—C14—H14	126.7	N43—C44—H44	126.8
N13—C14—H14	126.7	C44—C45—N41	109.24 (17)
C14—C15—N11	108.97 (19)	C44—C45—H45	125.4
C14—C15—H15	125.5	N41—C45—H45	125.4
N11—C15—H15	125.5

O2—V1—O1—Cu1	−1.75 (19)	N41—Cu1—N21—C25	127.77 (15)
O4ⁱ—V1—O1—Cu1	−123.65 (16)	N31—Cu1—N21—C25	−57.07 (15)
O3—V1—O1—Cu1	116.87 (16)	O6—Cu1—N21—C25	−147.14 (15)
N41—Cu1—O1—V1	179.21 (18)	O1—Cu1—N21—C25	42.92 (15)
N31—Cu1—O1—V1	0.15 (18)	C25—N21—C22—N23	−0.3 (2)
N21—Cu1—O1—V1	−86.13 (17)	Cu1—N21—C22—N23	−176.65 (13)
N11—Cu1—O1—V1	91.46 (17)	N21—C22—N23—C24	0.2 (2)
O6—Cu1—O1—V1	−157.9 (2)	C22—N23—C24—C25	−0.1 (2)
O6ⁱⁱ—V2—O3—V1	91.19 (10)	N23—C24—C25—N21	0.0 (2)
O5—V2—O3—V1	−150.41 (9)	C22—N21—C25—C24	0.2 (2)
O4—V2—O3—V1	−28.36 (11)	Cu1—N21—C25—C24	176.85 (14)
O1—V1—O3—V2	−164.38 (8)	N21—Cu1—N31—C32	106.98 (17)
O2—V1—O3—V2	−46.59 (11)	N11—Cu1—N31—C32	−65.43 (17)
O4ⁱ—V1—O3—V2	75.68 (10)	O6—Cu1—N31—C32	−161.87 (16)
O6ⁱⁱ—V2—O4—V1ⁱ	172.44 (11)	O1—Cu1—N31—C32	22.07 (17)
O5—V2—O4—V1ⁱ	53.06 (14)	N21—Cu1—N31—C35	−58.37 (16)
O3—V2—O4—V1ⁱ	−67.40 (13)	N11—Cu1—N31—C35	129.22 (16)
N41—Cu1—O6—V2ⁱⁱⁱ	179.0 (4)	O6—Cu1—N31—C35	32.78 (16)
N31—Cu1—O6—V2ⁱⁱⁱ	−2.2 (4)	O1—Cu1—N31—C35	−143.28 (15)
N21—Cu1—O6—V2ⁱⁱⁱ	84.9 (4)	C35—N31—C32—N33	−1.0 (2)
N11—Cu1—O6—V2ⁱⁱⁱ	−94.0 (4)	Cu1—N31—C32—N33	−168.67 (13)
O1—Cu1—O6—V2ⁱⁱⁱ	156.1 (3)	N31—C32—N33—C34	0.8 (2)
N41—Cu1—N11—C12	124.78 (18)	C32—N33—C34—C35	−0.2 (2)
N31—Cu1—N11—C12	−50.25 (18)	N33—C34—C35—N31	−0.3 (2)
O6—Cu1—N11—C12	40.08 (18)	C32—N31—C35—C34	0.8 (2)
O1—Cu1—N11—C12	−149.90 (17)	Cu1—N31—C35—C34	168.52 (13)
N41—Cu1—N11—C15	−47.34 (17)	N21—Cu1—N41—C42	−76.98 (17)
N31—Cu1—N11—C15	137.63 (17)	N11—Cu1—N41—C42	95.55 (16)
O6—Cu1—N11—C15	−132.04 (16)	O6—Cu1—N41—C42	−167.77 (16)
O1—Cu1—N11—C15	37.98 (16)	O1—Cu1—N41—C42	8.11 (16)
C15—N11—C12—N13	0.1 (2)	N21—Cu1—N41—C45	124.56 (15)
Cu1—N11—C12—N13	−173.20 (13)	N11—Cu1—N41—C45	−62.91 (15)
N11—C12—N13—C14	−0.3 (2)	O6—Cu1—N41—C45	33.77 (14)
C12—N13—C14—C15	0.3 (2)	O1—Cu1—N41—C45	−150.35 (15)
N13—C14—C15—N11	−0.3 (2)	C45—N41—C42—N43	−0.1 (2)
C12—N11—C15—C14	0.1 (2)	Cu1—N41—C42—N43	−161.54 (13)
Cu1—N11—C15—C14	173.76 (14)	N41—C42—N43—C44	0.4 (2)
N41—Cu1—N21—C22	−56.42 (17)	C42—N43—C44—C45	−0.5 (2)
N31—Cu1—N21—C22	118.74 (17)	N43—C44—C45—N41	0.5 (2)
O6—Cu1—N21—C22	28.66 (17)	C42—N41—C45—C44	−0.3 (2)
O1—Cu1—N21—C22	−141.27 (17)	Cu1—N41—C45—C44	162.26 (13)

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

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C11/C12/N13/C14/C15, C21/C22/N23/C24/C25, C31/C32/N33/C34/C35 and C41/C42/N43/C44/C45 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13···O3^iv	0.88	2.01	2.827 (2)	155
N23—H23···O5^v	0.88	1.95	2.779 (2)	155
N33—H33···O2^vi	0.88	1.90	2.694 (2)	149
N43—H43···O5^vii	0.88	1.88	2.701 (2)	155
C24—H24···Cg1^viii	0.95	2.99	3.912 (2)	165
C12—H12···Cg2^iv	0.95	2.59	3.429 (2)	147
C22—H22···Cg3^ix	0.95	2.66	3.332 (2)	128
C44—H44···Cg3ⁱⁱⁱ	0.95	2.91	3.816 (2)	161
C32—H32···Cg4^x	0.95	2.76	3.321 (2)	119

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

Experimental details

Crystal data
Chemical formula	[Cu₂V₄O₁₂(C₃H₄N₂)₈]
M_r	1067.52
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	10.1761 (6), 16.5092 (9), 12.0372 (7)
β (°)	103.844 (1)
V (Å³)	1963.50 (19)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.05
Crystal size (mm)	0.24 × 0.20 × 0.18

Data collection
Diffractometer	Bruker APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.639, 0.722
No. of measured, independent and observed [I > 2σ(I)] reflections	11719, 4370, 3830
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.073, 1.04
No. of reflections	4370
No. of parameters	262
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.30

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg1, Cg2, Cg3 and Cg4 are the centroids of the C11/C12/N13/C14/C15, C21/C22/N23/C24/C25, C31/C32/N33/C34/C35 and C41/C42/N43/C44/C45 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N13—H13···O3ⁱ	0.88	2.01	2.827 (2)	155
N23—H23···O5ⁱⁱ	0.88	1.95	2.779 (2)	155
N33—H33···O2ⁱⁱⁱ	0.88	1.90	2.694 (2)	149
N43—H43···O5^iv	0.88	1.88	2.701 (2)	155
C24—H24···Cg1^v	0.95	2.985	3.912 (2)	165.3
C12—H12···Cg2ⁱ	0.95	2.592	3.429 (2)	147.1
C22—H22···Cg3^vi	0.95	2.659	3.332 (2)	128.2
C44—H44···Cg3^vii	0.95	2.907	3.816 (2)	160.5
C32—H32···Cg4^viii	0.95	2.761	3.321 (2)	118.5

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

Acknowledgements

The authors thank Professor Ian D. Williams and Dr Herman H.-Y. Sung of the Department of Chemistry, The Hong Kong University of Science and Technology, for their kind help during the X-ray study and for valuable discussions. The authors also thank Associate Professor David J. Harding for valuable discussions. This work was supported financially by Naresuan University (grant No. R2554C034).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244–247. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chainok, K., Haller, K. J., Rae, A. D., Willis, A. C. & Williams, I. D. (2011). Acta Cryst. B67, 41–52. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268–3292. Web of Science CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hagrman, P. J., Finn, R. C. & Zubieta, J. (2001). Solid State Sci. 3, 745–774. Web of Science CrossRef CAS Google Scholar
Natarajan, S. & Mandal, S. (2008). Angew. Chem. Int. Ed. 47, 4798–4828. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zavalij, P. Y. & Whittingham, M. S. (1999). Acta Cryst. B55, 627–663. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 4| April 2012| Pages m362-m363

doi:10.1107/S1600536812008252

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)