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

Journal logoCRYSTALLOGRAPHIC
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ISSN: 2056-9890
Volume 68| Part 4| April 2012| Pages m362-m363

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

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 VV ion is tetra­coordinated by four O atoms and the CuII 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[Cheetham, A. K., Férey, G. & Loiseau, T. (1999). Angew. Chem. Int. Ed. 38, 3268-3292.]); Hagrman et al. (2001[Hagrman, P. J., Finn, R. C. & Zubieta, J. (2001). Solid State Sci. 3, 745-774.]); Natarajan & Mandal (2008[Natarajan, S. & Mandal, S. (2008). Angew. Chem. Int. Ed. 47, 4798-4828.]); Zavalij & Whittingham (1999[Zavalij, P. Y. & Whittingham, M. S. (1999). Acta Cryst. B55, 627-663.]). For related structures, see: Chainok et al. (2011[Chainok, K., Haller, K. J., Rae, A. D., Willis, A. C. & Williams, I. D. (2011). Acta Cryst. B67, 41-52.]). For the bond valence sum calculation, see: Brown & Altermatt (1985[Brown, I. D. & Altermatt, D. (1985). Acta Cryst. B41, 244-247.]).

[Scheme 1]

Experimental

Crystal data
  • [Cu2V4O12(C3H4N2)8]

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.639, Tmax = 0.722

  • 11719 measured reflections

  • 4370 independent reflections

  • 3830 reflections with I > 2σ(I)

  • Rint = 0.025

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.073

  • S = 1.04

  • 4370 reflections

  • 262 parameters

  • H-atom parameters constrained

  • Δρmax = 0.51 e Å−3

  • Δρmin = −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 DA 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⋯O5iv 0.88 1.88 2.701 (2) 155
C24—H24⋯Cg1v 0.95 2.99 3.912 (2) 165
C12—H12⋯Cg2i 0.95 2.59 3.429 (2) 147
C22—H22⋯Cg3vi 0.95 2.66 3.332 (2) 128
C44—H44⋯Cg3vii 0.95 2.91 3.816 (2) 161
C32—H32⋯Cg4viii 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[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


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 MnII > CoII ~ NiII > CuII. 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 CuII 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 C2v 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 ππ 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%.

Refinement top

H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.95 and N—H = 0.88 Å and Uiso(H) = 1.2Ueq(C,N). In the final difference Fourier map, the maximum and minimum electron density of 0.51 and -0.30 eÅ-3 were located 0.77 and 0.33 Å from O2 and H45, respectively.

Structure description 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 MnII > CoII ~ NiII > CuII. 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 CuII 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 C2v 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 ππ stacking between adjacent imidazole rings in this compound.

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
[Figure 1] Fig. 1. The aymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. Polyhedral representation of the two-dimensional sheet structure of (I). H atoms have been omitted for clarity.
[Figure 3] Fig. 3. View of the layer structure of (I) along the b axis. H atoms have been omitted for clarity.
[Figure 4] Fig. 4. View of N—H···O hydrogen bonds (dashed lines) in (I). H atoms have been omitted for clarity.
[Figure 5] 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
Mr = 1067.52Dx = 1.806 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3583 reflections
a = 10.1761 (6) Åθ = 2.4–27.4°
b = 16.5092 (9) ŵ = 2.05 mm1
c = 12.0372 (7) ÅT = 100 K
β = 103.844 (1)°Block, dark blue
V = 1963.50 (19) Å30.24 × 0.20 × 0.18 mm
Z = 2
Data collection top
Bruker APEX CCD
diffractometer
4370 independent reflections
Radiation source: sealed tube3830 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.025
ω and φ scansθmax = 28.2°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1212
Tmin = 0.639, Tmax = 0.722k = 2016
11719 measured reflectionsl = 1515
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0408P)2 + 0.1105P]
where P = (Fo2 + 2Fc2)/3
4370 reflections(Δ/σ)max = 0.001
262 parametersΔρmax = 0.51 e Å3
0 restraintsΔρmin = 0.30 e Å3
0 constraints
Crystal data top
[Cu2V4O12(C3H4N2)8]V = 1963.50 (19) Å3
Mr = 1067.52Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.1761 (6) ŵ = 2.05 mm1
b = 16.5092 (9) ÅT = 100 K
c = 12.0372 (7) Å0.24 × 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)
Tmin = 0.639, Tmax = 0.722Rint = 0.025
11719 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0280 restraints
wR(F2) = 0.073H-atom parameters constrained
S = 1.04Δρmax = 0.51 e Å3
4370 reflectionsΔρmin = 0.30 e Å3
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
xyzUiso*/Ueq
Cu10.80636 (2)0.241362 (13)0.801507 (19)0.00947 (8)
V10.61028 (3)0.417383 (18)0.91849 (3)0.00910 (9)
O10.64852 (14)0.33438 (8)0.85877 (11)0.0151 (3)
V20.46561 (3)0.585997 (19)0.82471 (3)0.00889 (9)
O20.75077 (14)0.46664 (8)0.97220 (12)0.0183 (3)
O30.50084 (14)0.47895 (8)0.80807 (11)0.0143 (3)
O40.47841 (14)0.60729 (8)0.97210 (11)0.0151 (3)
O50.31228 (14)0.60726 (9)0.74519 (12)0.0162 (3)
O60.92507 (14)0.14149 (8)0.71994 (12)0.0158 (3)
N110.82168 (16)0.18449 (10)0.95274 (13)0.0131 (3)
C120.9253 (2)0.14465 (12)1.01605 (17)0.0151 (4)
H121.01260.14241.00080.018*
N130.89173 (18)0.10785 (10)1.10445 (14)0.0167 (4)
H130.94540.07801.15690.020*
C140.7591 (2)0.12508 (13)1.09835 (18)0.0204 (5)
H140.70720.10751.14980.024*
C150.7157 (2)0.17227 (13)1.00442 (17)0.0199 (4)
H150.62680.19350.97840.024*
N210.78124 (16)0.31036 (10)0.66093 (13)0.0123 (3)
C220.77206 (19)0.28959 (12)0.55363 (16)0.0145 (4)
H220.77190.23530.52740.017*
N230.76290 (17)0.35500 (10)0.48635 (14)0.0167 (4)
H230.75560.35500.41200.020*
C240.7670 (2)0.42209 (13)0.55468 (18)0.0186 (4)
H240.76270.47720.53120.022*
C250.7783 (2)0.39402 (12)0.66188 (18)0.0169 (4)
H250.78350.42670.72770.020*
N310.97998 (16)0.30136 (10)0.86210 (13)0.0116 (3)
C321.0025 (2)0.35656 (12)0.94453 (16)0.0132 (4)
H320.94380.36740.99330.016*
N331.11982 (16)0.39489 (10)0.94927 (14)0.0140 (3)
H331.15520.43330.99790.017*
C341.1751 (2)0.36370 (12)0.86493 (17)0.0146 (4)
H341.25790.37930.84770.017*
C351.08746 (19)0.30603 (12)0.81122 (16)0.0139 (4)
H351.09850.27400.74850.017*
N410.64268 (16)0.17312 (9)0.73864 (13)0.0113 (3)
C420.51402 (19)0.19205 (12)0.72905 (16)0.0135 (4)
H420.48090.24570.73120.016*
N430.43677 (17)0.12534 (10)0.71599 (14)0.0151 (4)
H430.34850.12390.70760.018*
C440.5198 (2)0.06006 (12)0.71797 (17)0.0166 (4)
H440.49370.00470.71130.020*
C450.6465 (2)0.08987 (11)0.73137 (17)0.0136 (4)
H450.72560.05840.73520.016*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01030 (13)0.00903 (13)0.00864 (13)0.00211 (8)0.00144 (9)0.00087 (8)
V10.01084 (17)0.00739 (17)0.00899 (16)0.00014 (12)0.00217 (12)0.00107 (11)
O10.0206 (7)0.0109 (7)0.0151 (7)0.0012 (5)0.0065 (6)0.0015 (5)
V20.00932 (16)0.00903 (17)0.00877 (16)0.00116 (11)0.00309 (12)0.00181 (11)
O20.0156 (7)0.0128 (7)0.0247 (8)0.0018 (6)0.0015 (6)0.0019 (6)
O30.0191 (7)0.0112 (7)0.0115 (7)0.0019 (5)0.0016 (5)0.0002 (5)
O40.0190 (7)0.0147 (7)0.0126 (7)0.0012 (6)0.0058 (6)0.0005 (5)
O50.0124 (7)0.0221 (8)0.0152 (7)0.0040 (6)0.0052 (6)0.0041 (6)
O60.0156 (7)0.0163 (7)0.0176 (7)0.0010 (6)0.0080 (6)0.0040 (6)
N110.0151 (8)0.0135 (9)0.0106 (8)0.0002 (6)0.0029 (7)0.0005 (6)
C120.0160 (10)0.0140 (10)0.0133 (10)0.0005 (8)0.0002 (8)0.0010 (7)
N130.0223 (9)0.0130 (9)0.0123 (8)0.0001 (7)0.0011 (7)0.0025 (6)
C140.0264 (12)0.0220 (12)0.0152 (10)0.0012 (9)0.0101 (9)0.0010 (8)
C150.0209 (11)0.0247 (12)0.0169 (10)0.0034 (9)0.0098 (9)0.0041 (8)
N210.0137 (8)0.0110 (8)0.0120 (8)0.0019 (6)0.0025 (6)0.0004 (6)
C220.0144 (10)0.0149 (10)0.0139 (10)0.0012 (8)0.0026 (8)0.0006 (8)
N230.0192 (9)0.0206 (9)0.0104 (8)0.0020 (7)0.0038 (7)0.0033 (7)
C240.0209 (11)0.0140 (11)0.0207 (11)0.0010 (8)0.0048 (9)0.0070 (8)
C250.0212 (11)0.0102 (10)0.0191 (10)0.0023 (8)0.0041 (8)0.0003 (8)
N310.0131 (8)0.0116 (8)0.0100 (8)0.0011 (6)0.0024 (6)0.0008 (6)
C320.0145 (10)0.0128 (10)0.0115 (9)0.0000 (7)0.0018 (8)0.0008 (7)
N330.0158 (9)0.0113 (8)0.0135 (8)0.0030 (6)0.0005 (7)0.0018 (6)
C340.0130 (10)0.0152 (10)0.0159 (10)0.0011 (8)0.0044 (8)0.0032 (8)
C350.0146 (10)0.0165 (10)0.0108 (9)0.0003 (8)0.0031 (8)0.0007 (7)
N410.0125 (8)0.0108 (8)0.0105 (8)0.0009 (6)0.0027 (6)0.0003 (6)
C420.0124 (9)0.0143 (10)0.0139 (10)0.0008 (8)0.0032 (8)0.0012 (7)
N430.0109 (8)0.0180 (9)0.0169 (9)0.0020 (6)0.0040 (7)0.0018 (7)
C440.0200 (10)0.0117 (10)0.0186 (10)0.0022 (8)0.0056 (8)0.0003 (8)
C450.0167 (10)0.0104 (9)0.0142 (10)0.0008 (7)0.0047 (8)0.0001 (7)
Geometric parameters (Å, º) top
Cu1—N412.0033 (16)N21—C251.381 (2)
Cu1—N312.0045 (16)C22—N231.340 (3)
Cu1—N212.0049 (16)C22—H220.9500
Cu1—N112.0209 (16)N23—C241.374 (3)
Cu1—O62.3894 (13)N23—H230.8800
Cu1—O12.4379 (13)C24—C251.350 (3)
V1—O11.6370 (13)C24—H240.9500
V1—O21.6373 (14)C25—H250.9500
V1—O4i1.8121 (13)N31—C321.326 (2)
V1—O31.8253 (13)N31—C351.378 (2)
V2—O6ii1.6285 (14)C32—N331.340 (2)
V2—O51.6611 (14)C32—H320.9500
V2—O41.7826 (14)N33—C341.373 (3)
V2—O31.8237 (14)N33—H330.8800
O4—V1i1.8122 (13)C34—C351.358 (3)
O6—V2iii1.6284 (14)C34—H340.9500
N11—C121.319 (2)C35—H350.9500
N11—C151.383 (3)N41—C421.324 (2)
C12—N131.339 (3)N41—C451.378 (2)
C12—H120.9500C42—N431.340 (3)
N13—C141.364 (3)C42—H420.9500
N13—H130.8800N43—C441.366 (3)
C14—C151.357 (3)N43—H430.8800
C14—H140.9500C44—C451.354 (3)
C15—H150.9500C44—H440.9500
N21—C221.318 (2)C45—H450.9500
N41—Cu1—N31174.98 (6)C22—N21—C25105.77 (16)
N41—Cu1—N2194.25 (6)C22—N21—Cu1130.10 (14)
N31—Cu1—N2187.11 (6)C25—N21—Cu1124.03 (13)
N41—Cu1—N1187.53 (6)N21—C22—N23111.16 (18)
N31—Cu1—N1191.75 (6)N21—C22—H22124.4
N21—Cu1—N11172.34 (6)N23—C22—H22124.4
N41—Cu1—O685.01 (6)C22—N23—C24107.46 (17)
N31—Cu1—O690.13 (6)C22—N23—H23126.3
N21—Cu1—O691.15 (6)C24—N23—H23126.3
N11—Cu1—O696.43 (6)C25—C24—N23106.19 (18)
N41—Cu1—O185.21 (6)C25—C24—H24126.9
N31—Cu1—O199.72 (6)N23—C24—H24126.9
N21—Cu1—O185.48 (6)C24—C25—N21109.42 (18)
N11—Cu1—O187.25 (6)C24—C25—H25125.3
O6—Cu1—O1169.40 (5)N21—C25—H25125.3
O1—V1—O2108.20 (7)C32—N31—C35106.31 (16)
O1—V1—O4i110.06 (7)C32—N31—Cu1126.24 (13)
O2—V1—O4i111.36 (7)C35—N31—Cu1126.17 (13)
O1—V1—O3108.31 (7)N31—C32—N33110.42 (17)
O2—V1—O3109.51 (7)N31—C32—H32124.8
O4i—V1—O3109.34 (6)N33—C32—H32124.8
V1—O1—Cu1153.30 (8)C32—N33—C34108.05 (16)
O6ii—V2—O5108.22 (7)C32—N33—H33126.0
O6ii—V2—O4108.94 (7)C34—N33—H33126.0
O5—V2—O4111.51 (7)C35—C34—N33106.05 (17)
O6ii—V2—O3109.94 (7)C35—C34—H34127.0
O5—V2—O3108.89 (7)N33—C34—H34127.0
O4—V2—O3109.33 (6)C34—C35—N31109.17 (17)
V2—O3—V1124.15 (7)C34—C35—H35125.4
V2—O4—V1i138.46 (9)N31—C35—H35125.4
V2iii—O6—Cu1167.49 (8)C42—N41—C45105.79 (16)
C12—N11—C15105.61 (17)C42—N41—Cu1128.00 (13)
C12—N11—Cu1129.10 (14)C45—N41—Cu1123.45 (13)
C15—N11—Cu1124.94 (13)N41—C42—N43110.87 (17)
N11—C12—N13111.40 (18)N41—C42—H42124.6
N11—C12—H12124.3N43—C42—H42124.6
N13—C12—H12124.3C42—N43—C44107.67 (17)
C12—N13—C14107.45 (17)C42—N43—H43126.2
C12—N13—H13126.3C44—N43—H43126.2
C14—N13—H13126.3C45—C44—N43106.43 (18)
C15—C14—N13106.57 (18)C45—C44—H44126.8
C15—C14—H14126.7N43—C44—H44126.8
N13—C14—H14126.7C44—C45—N41109.24 (17)
C14—C15—N11108.97 (19)C44—C45—H45125.4
C14—C15—H15125.5N41—C45—H45125.4
N11—C15—H15125.5
O2—V1—O1—Cu11.75 (19)N41—Cu1—N21—C25127.77 (15)
O4i—V1—O1—Cu1123.65 (16)N31—Cu1—N21—C2557.07 (15)
O3—V1—O1—Cu1116.87 (16)O6—Cu1—N21—C25147.14 (15)
N41—Cu1—O1—V1179.21 (18)O1—Cu1—N21—C2542.92 (15)
N31—Cu1—O1—V10.15 (18)C25—N21—C22—N230.3 (2)
N21—Cu1—O1—V186.13 (17)Cu1—N21—C22—N23176.65 (13)
N11—Cu1—O1—V191.46 (17)N21—C22—N23—C240.2 (2)
O6—Cu1—O1—V1157.9 (2)C22—N23—C24—C250.1 (2)
O6ii—V2—O3—V191.19 (10)N23—C24—C25—N210.0 (2)
O5—V2—O3—V1150.41 (9)C22—N21—C25—C240.2 (2)
O4—V2—O3—V128.36 (11)Cu1—N21—C25—C24176.85 (14)
O1—V1—O3—V2164.38 (8)N21—Cu1—N31—C32106.98 (17)
O2—V1—O3—V246.59 (11)N11—Cu1—N31—C3265.43 (17)
O4i—V1—O3—V275.68 (10)O6—Cu1—N31—C32161.87 (16)
O6ii—V2—O4—V1i172.44 (11)O1—Cu1—N31—C3222.07 (17)
O5—V2—O4—V1i53.06 (14)N21—Cu1—N31—C3558.37 (16)
O3—V2—O4—V1i67.40 (13)N11—Cu1—N31—C35129.22 (16)
N41—Cu1—O6—V2iii179.0 (4)O6—Cu1—N31—C3532.78 (16)
N31—Cu1—O6—V2iii2.2 (4)O1—Cu1—N31—C35143.28 (15)
N21—Cu1—O6—V2iii84.9 (4)C35—N31—C32—N331.0 (2)
N11—Cu1—O6—V2iii94.0 (4)Cu1—N31—C32—N33168.67 (13)
O1—Cu1—O6—V2iii156.1 (3)N31—C32—N33—C340.8 (2)
N41—Cu1—N11—C12124.78 (18)C32—N33—C34—C350.2 (2)
N31—Cu1—N11—C1250.25 (18)N33—C34—C35—N310.3 (2)
O6—Cu1—N11—C1240.08 (18)C32—N31—C35—C340.8 (2)
O1—Cu1—N11—C12149.90 (17)Cu1—N31—C35—C34168.52 (13)
N41—Cu1—N11—C1547.34 (17)N21—Cu1—N41—C4276.98 (17)
N31—Cu1—N11—C15137.63 (17)N11—Cu1—N41—C4295.55 (16)
O6—Cu1—N11—C15132.04 (16)O6—Cu1—N41—C42167.77 (16)
O1—Cu1—N11—C1537.98 (16)O1—Cu1—N41—C428.11 (16)
C15—N11—C12—N130.1 (2)N21—Cu1—N41—C45124.56 (15)
Cu1—N11—C12—N13173.20 (13)N11—Cu1—N41—C4562.91 (15)
N11—C12—N13—C140.3 (2)O6—Cu1—N41—C4533.77 (14)
C12—N13—C14—C150.3 (2)O1—Cu1—N41—C45150.35 (15)
N13—C14—C15—N110.3 (2)C45—N41—C42—N430.1 (2)
C12—N11—C15—C140.1 (2)Cu1—N41—C42—N43161.54 (13)
Cu1—N11—C15—C14173.76 (14)N41—C42—N43—C440.4 (2)
N41—Cu1—N21—C2256.42 (17)C42—N43—C44—C450.5 (2)
N31—Cu1—N21—C22118.74 (17)N43—C44—C45—N410.5 (2)
O6—Cu1—N21—C2228.66 (17)C42—N41—C45—C440.3 (2)
O1—Cu1—N21—C22141.27 (17)Cu1—N41—C45—C44162.26 (13)
Symmetry codes: (i) x+1, y+1, z+2; (ii) x+3/2, y+1/2, z+3/2; (iii) x+3/2, y1/2, 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···AD—HH···AD···AD—H···A
N13—H13···O3iv0.882.012.827 (2)155
N23—H23···O5v0.881.952.779 (2)155
N33—H33···O2vi0.881.902.694 (2)149
N43—H43···O5vii0.881.882.701 (2)155
C24—H24···Cg1viii0.952.993.912 (2)165
C12—H12···Cg2iv0.952.593.429 (2)147
C22—H22···Cg3ix0.952.663.332 (2)128
C44—H44···Cg3iii0.952.913.816 (2)161
C32—H32···Cg4x0.952.763.321 (2)119
Symmetry codes: (iii) x+3/2, y1/2, 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, y1/2, z+3/2; (viii) x1/2, y+1/2, z+3/2; (ix) x1/2, y+1/2, z1/2; (x) x+1/2, y3/2, z+1/2.

Experimental details

Crystal data
Chemical formula[Cu2V4O12(C3H4N2)8]
Mr1067.52
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)10.1761 (6), 16.5092 (9), 12.0372 (7)
β (°) 103.844 (1)
V3)1963.50 (19)
Z2
Radiation typeMo Kα
µ (mm1)2.05
Crystal size (mm)0.24 × 0.20 × 0.18
Data collection
DiffractometerBruker APEX CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.639, 0.722
No. of measured, independent and
observed [I > 2σ(I)] reflections
11719, 4370, 3830
Rint0.025
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.073, 1.04
No. of reflections4370
No. of parameters262
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N13—H13···O3i0.882.012.827 (2)155
N23—H23···O5ii0.881.952.779 (2)155
N33—H33···O2iii0.881.902.694 (2)149
N43—H43···O5iv0.881.882.701 (2)155
C24—H24···Cg1v0.952.9853.912 (2)165.3
C12—H12···Cg2i0.952.5923.429 (2)147.1
C22—H22···Cg3vi0.952.6593.332 (2)128.2
C44—H44···Cg3vii0.952.9073.816 (2)160.5
C32—H32···Cg4viii0.952.7613.321 (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, y1/2, z+3/2; (v) x1/2, y+1/2, z+3/2; (vi) x1/2, y+1/2, z1/2; (vii) x+3/2, y1/2, z+3/2; (viii) x+1/2, y3/2, 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

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