Poly[bis­(2,2′-bipyridine-κ2 N,N′)deca-μ-oxido-dioxidodicopper(II)tetra­vanadium(V)]

Xiao Zhang; Wujiong Xia; Xianzhu Xu; Zhihui Yi; Chao Yang

doi:10.1107/S1600536807067979

. 2008 Jan 4;64(Pt 2):m287–m288. doi: 10.1107/S1600536807067979

Poly[bis(2,2′-bipyridine-κ² N,N′)deca-μ-oxido-dioxidodicopper(II)tetravanadium(V)]

Xiao Zhang ^a,^b, Wujiong Xia ^a,^b,^*, Xianzhu Xu ^a,^b, Zhihui Yi ^c, Chao Yang ^a,^b

PMCID: PMC2960253 PMID: 21201266

Abstract

The title compound, [Cu₂V₄O₁₂(C₁₀H₈N₂)₂]_n, shows a two-dimensional copper–vanadate layer composed of eight-membered rings, each containing four corner-sharing VO₄ tetrahedra; these are linked through six pentacoordinated Cu^II atoms with the 2,2′-bipyridine ligands attached and pointing above and below the plane of the layer. The Cu atom is coordinated by two N donors from the 2,2′-bipyridine ligand and three O atoms from three adjacent VO₄ units to form a distorted tetragonal pyramid. These layers are further connected by π–π interactions between interleaving bipyridine ligands of adjacent layers [centroid–centroid distances = 3.63 (1) and 3.68 (1) Å] into a three-dimensional supramolecular structure.

Related literature

For related literature, see: DeBord et al. (1996 ▶); Kucsera et al. (2002 ▶); Lu et al. (2002 ▶); Yi et al. (2007 ▶).

Experimental

Crystal data

[Cu₂V₄O₁₂(C₁₀H₈N₂)₂]
M _r = 417.60
Triclinic,
a = 8.1019 (4) Å
b = 8.3122 (5) Å
c = 10.3501 (4) Å
α = 72.332 (3)°
β = 84.562 (3)°
γ = 77.878 (3)°
V = 648.98 (6) Å³
Z = 2
Mo Kα radiation
μ = 3.06 mm⁻¹
T = 298 (2) K
0.33 × 0.31 × 0.25 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.379, T _max = 0.469
4603 measured reflections
3114 independent reflections
2553 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.084
S = 0.99
3114 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.75 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807067979/hy2113sup1.cif

e-64-0m287-sup1.cif^{(18.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807067979/hy2113Isup2.hkl

e-64-0m287-Isup2.hkl^{(152.8KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Cu1—O1	2.012 (2)
Cu1—O4ⁱ	2.054 (2)
Cu1—O6ⁱⁱ	2.061 (2)
Cu1—N1	2.084 (2)
Cu1—N2	2.117 (2)
V1—O2	1.615 (2)
V1—O1	1.667 (2)
V1—O5ⁱⁱⁱ	1.824 (2)
V1—O3	1.833 (2)
V2—O4	1.655 (2)
V2—O6	1.670 (2)
V2—O5	1.774 (2)
V2—O3	1.790 (2)

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O1—Cu1—O4ⁱ	89.62 (9)
O1—Cu1—O6ⁱⁱ	94.53 (9)
O4ⁱ—Cu1—O6ⁱⁱ	121.32 (9)
O1—Cu1—N1	100.17 (9)
O4ⁱ—Cu1—N1	124.55 (9)
O6ⁱⁱ—Cu1—N1	112.18 (9)
O1—Cu1—N2	172.29 (9)
O4ⁱ—Cu1—N2	85.25 (9)
O6ⁱⁱ—Cu1—N2	93.05 (9)
N1—Cu1—N2	78.18 (10)
O2—V1—O1	108.65 (12)
O2—V1—O5ⁱⁱⁱ	109.43 (12)
O1—V1—O5ⁱⁱⁱ	111.53 (11)
O2—V1—O3	107.98 (12)
O1—V1—O3	110.08 (11)
O5ⁱⁱⁱ—V1—O3	109.09 (10)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This work was supported by the New Century Talent Program of the Chinese Ministry of Education and the Postdoctoral Foundation of Heilongjiang Province.

supplementary crystallographic information

Comment

Considerable efforts have been devoted to the hydrothermal synthesis of solid-state inorganic–organic hybrid vanadate(V) species based on discrete clusters, infinite chain and layer structures, such as [Zn(phen)₃][V₂O₆].10H₂O and [Cu(bipy)V₂O₆] (Yi et al., 2007), [Cu(bipy)][V₂O₆] and [Cu(bipy)₂][V₂O₆] (DeBord et al., 1996), [Mn(phen)₂]₂[V₄O₁₂].0.5H₂O (Lu et al., 2002), and [Co(phen)₂]₂[V₄O₁₂].H₂O (Kucsera et al., 2002), because of their diverse topologies and fascinating physical properties. We report here the crystal structure of a new complex, {[Cu(bipy)]₂V₄O₁₂}_n (bipy = 2,2'-bipyridine).

The asymmetric unit of the title compound consists of one Cu^II atom, one bipy molecule and a half of V₄O₁₂ unit (Fig. 1). The V₄O₁₂ units are linked through six square-pyramidal Cu^II atoms to six adjacent V₄O₁₂ rings (Fig. 2). Two of VO₄ units in the V₄O₁₂ unit each connect with one square-pyramidal Cu unit, while the other two VO₄ units each exhibit corner-sharing interactions with two Cu units. Each Cu unit links three V₄O₁₂ units through corner-sharing interactions. In this way, a two-dimensional layer is formed (Fig. 2). The Cu^II atom is coordinated by two pyridine N atoms and three tetravanadate O atoms (Fig. 1 and Table 1). The relative orientation of the bipy ligand with respect to the copper–vanadate layer is depicted by a dihedral angel of 84.6 (6)°. Furthermore, these bipy ligands interact with each other through π–π interactions between adjacent layers with centroid–centroid distances of 3.63 (1) and 3.68 (1) Å.

Experimental

The title compound was prepared hydrothermally from a mixture of V₂O₅ (0.73 g, 4.0 mmol), 2,2'-bipyridine dihydrate (0.38 g, 2.0 mmol), CuCl₂.2H₂O (0.34 g, 2.0 mmol) and water (18 ml) (molar ratio 2:1:1:500), adjusting pH to ca 6.1 with 4 M KOH, in a 25 ml Teflon-lined stainless steel reactor heated to 443 K for 7 d. After cooling to room temperature, green crystals were collected.