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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): m287–m288.
Published online 2008 January 4. doi:  10.1107/S1600536807067979
PMCID: PMC2960253

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

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 CuII 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 [triangle]); Kucsera et al. (2002 [triangle]); Lu et al. (2002 [triangle]); Yi et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0m287-scheme1.jpg

Experimental

Crystal data

  • [Cu2V4O12(C10H8N2)2]
  • M r = 417.60
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m287-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.53 e Å−3
  • Δρmin = −0.75 e Å−3

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

Table 1
Selected geometric parameters (Å, °)

Supplementary Material

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

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

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

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 CuII atom, one bipy molecule and a half of V4O12 unit (Fig. 1). The V4O12 units are linked through six square-pyramidal CuII 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 CuII 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.

Refinement

H atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93Å and Uiso(H) = 1.2Ueq(C).

Figures

Fig. 1.
The asymmetric unit of the title compound, extended to show the V4O12 unit. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) 1 - x, 1 - y, 1 - z; (ii) x, y - 1, z; (iii) 2 - x, 1 - y, 1 - z.]
Fig. 2.
A view of the copper–vanadate layer with C and H atoms of the bipy ligands omitted for clarity.

Crystal data

[Cu2V4O12(C10H8N2)2]Z = 2
Mr = 417.60F000 = 410
Triclinic, P1Dx = 2.137 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.1019 (4) ÅCell parameters from 3811 reflections
b = 8.3122 (5) Åθ = 2.1–28.3º
c = 10.3501 (4) ŵ = 3.06 mm1
α = 72.332 (3)ºT = 298 (2) K
β = 84.562 (3)ºBlock, green
γ = 77.878 (3)º0.33 × 0.31 × 0.25 mm
V = 648.98 (6) Å3

Data collection

Bruker SMART APEX CCD diffractometer3114 independent reflections
Radiation source: fine-focus sealed tube2553 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.055
T = 298(2) Kθmax = 28.3º
[var phi] and ω scansθmin = 2.1º
Absorption correction: multi-scan(SADABS; Bruker, 2002)h = −10→9
Tmin = 0.379, Tmax = 0.469k = −10→7
4603 measured reflectionsl = −13→12

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.084  w = 1/[σ2(Fo2) + (0.0438P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99(Δ/σ)max = 0.001
3114 reflectionsΔρmax = 0.53 e Å3
190 parametersΔρmin = −0.75 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Cu10.59216 (4)0.14236 (4)0.28662 (3)0.01368 (10)
V10.87679 (6)0.39002 (6)0.34998 (5)0.01604 (12)
V20.73879 (6)0.72867 (6)0.47736 (5)0.01495 (12)
O10.7741 (3)0.2421 (3)0.3367 (2)0.0249 (5)
O20.9198 (3)0.5062 (3)0.1993 (2)0.0359 (6)
O30.7425 (3)0.5317 (3)0.4394 (2)0.0259 (5)
O40.5705 (3)0.7685 (3)0.5748 (2)0.0270 (5)
O50.9278 (3)0.7084 (3)0.5595 (2)0.0285 (5)
O60.7286 (3)0.8942 (3)0.3363 (2)0.0247 (5)
N10.5900 (3)0.2590 (3)0.0777 (2)0.0191 (5)
N20.3794 (3)0.0700 (3)0.2320 (2)0.0202 (5)
C10.7065 (4)0.3461 (4)0.0041 (3)0.0242 (6)
H10.79030.36710.04890.029*
C20.7057 (4)0.4056 (4)−0.1364 (3)0.0300 (7)
H20.78690.4667−0.18480.036*
C30.5828 (4)0.3731 (4)−0.2037 (3)0.0270 (7)
H30.58110.4107−0.29800.032*
C40.4620 (4)0.2835 (4)−0.1289 (3)0.0232 (6)
H40.37870.2594−0.17220.028*
C50.4675 (4)0.2303 (4)0.0120 (3)0.0192 (6)
C60.3397 (4)0.1390 (4)0.1003 (3)0.0187 (6)
C70.1878 (4)0.1270 (4)0.0534 (3)0.0288 (7)
H70.16100.1775−0.03720.035*
C80.0781 (4)0.0386 (4)0.1448 (4)0.0309 (7)
H8−0.02370.02900.11600.037*
C90.1209 (4)−0.0351 (4)0.2786 (3)0.0274 (7)
H90.0492−0.09620.34090.033*
C100.2718 (4)−0.0166 (4)0.3187 (3)0.0247 (6)
H100.3001−0.06600.40910.030*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cu10.01353 (17)0.01631 (18)0.01260 (17)−0.00306 (12)−0.00204 (12)−0.00563 (13)
V10.0140 (2)0.0172 (2)0.0183 (2)−0.00322 (18)−0.00335 (18)−0.00613 (19)
V20.0127 (2)0.0155 (2)0.0177 (2)−0.00107 (17)−0.00215 (18)−0.00696 (18)
O10.0202 (11)0.0282 (12)0.0335 (12)−0.0079 (9)−0.0034 (9)−0.0167 (10)
O20.0332 (14)0.0428 (14)0.0249 (12)−0.0122 (11)−0.0004 (10)0.0031 (11)
O30.0243 (12)0.0225 (11)0.0346 (13)−0.0036 (9)0.0016 (10)−0.0154 (10)
O40.0201 (11)0.0366 (13)0.0301 (12)−0.0050 (9)0.0047 (9)−0.0201 (10)
O50.0228 (12)0.0308 (12)0.0346 (13)−0.0013 (9)−0.0112 (10)−0.0128 (10)
O60.0245 (11)0.0204 (11)0.0266 (11)−0.0018 (9)−0.0051 (9)−0.0034 (9)
N10.0195 (12)0.0206 (12)0.0179 (12)−0.0040 (10)−0.0029 (10)−0.0059 (10)
N20.0225 (13)0.0233 (13)0.0178 (12)−0.0065 (10)−0.0011 (10)−0.0088 (10)
C10.0211 (15)0.0252 (16)0.0269 (16)−0.0057 (12)−0.0012 (12)−0.0077 (13)
C20.0264 (17)0.0326 (18)0.0299 (17)−0.0117 (14)0.0065 (14)−0.0058 (14)
C30.0328 (18)0.0269 (16)0.0177 (15)−0.0036 (13)−0.0008 (13)−0.0027 (12)
C40.0261 (16)0.0256 (16)0.0199 (15)−0.0037 (12)−0.0050 (12)−0.0090 (12)
C50.0181 (14)0.0190 (14)0.0211 (14)−0.0013 (11)−0.0044 (11)−0.0072 (11)
C60.0188 (14)0.0207 (14)0.0188 (14)−0.0048 (11)−0.0023 (11)−0.0078 (11)
C70.0270 (17)0.0350 (18)0.0252 (16)−0.0084 (14)−0.0101 (13)−0.0056 (14)
C80.0204 (16)0.0381 (19)0.0376 (19)−0.0095 (14)−0.0062 (14)−0.0118 (15)
C90.0242 (16)0.0299 (17)0.0318 (18)−0.0129 (13)0.0058 (13)−0.0110 (14)
C100.0263 (17)0.0295 (17)0.0192 (14)−0.0094 (13)0.0023 (12)−0.0065 (12)

Geometric parameters (Å, °)

Cu1—O12.012 (2)N2—C61.350 (4)
Cu1—O4i2.054 (2)C1—C21.387 (4)
Cu1—O6ii2.061 (2)C1—H10.9300
Cu1—N12.084 (2)C2—C31.381 (5)
Cu1—N22.117 (2)C2—H20.9300
V1—O21.615 (2)C3—C41.388 (5)
V1—O11.667 (2)C3—H30.9300
V1—O5iii1.824 (2)C4—C51.392 (4)
V1—O31.833 (2)C4—H40.9300
V2—O41.655 (2)C5—C61.488 (4)
V2—O61.670 (2)C6—C71.397 (4)
V2—O51.774 (2)C7—C81.384 (5)
V2—O31.790 (2)C7—H70.9300
O4—Cu1i2.054 (2)C8—C91.379 (5)
O5—V1iii1.824 (2)C8—H80.9300
O6—Cu1iv2.061 (2)C9—C101.379 (4)
N1—C11.346 (4)C9—H90.9300
N1—C51.352 (4)C10—H100.9300
N2—C101.344 (4)
O1—Cu1—O4i89.62 (9)C6—N2—Cu1114.9 (2)
O1—Cu1—O6ii94.53 (9)N1—C1—C2122.1 (3)
O4i—Cu1—O6ii121.32 (9)N1—C1—H1118.9
O1—Cu1—N1100.17 (9)C2—C1—H1118.9
O4i—Cu1—N1124.55 (9)C3—C2—C1119.2 (3)
O6ii—Cu1—N1112.18 (9)C3—C2—H2120.4
O1—Cu1—N2172.29 (9)C1—C2—H2120.4
O4i—Cu1—N285.25 (9)C2—C3—C4119.1 (3)
O6ii—Cu1—N293.05 (9)C2—C3—H3120.4
N1—Cu1—N278.18 (10)C4—C3—H3120.4
O2—V1—O1108.65 (12)C3—C4—C5118.9 (3)
O2—V1—O5iii109.43 (12)C3—C4—H4120.6
O1—V1—O5iii111.53 (11)C5—C4—H4120.6
O2—V1—O3107.98 (12)N1—C5—C4121.9 (3)
O1—V1—O3110.08 (11)N1—C5—C6115.6 (3)
O5iii—V1—O3109.09 (10)C4—C5—C6122.5 (3)
O4—V2—O6107.88 (11)N2—C6—C7121.6 (3)
O4—V2—O5111.20 (11)N2—C6—C5114.8 (2)
O6—V2—O5108.55 (11)C7—C6—C5123.6 (3)
O4—V2—O3109.63 (11)C8—C7—C6118.6 (3)
O6—V2—O3111.29 (11)C8—C7—H7120.7
O5—V2—O3108.30 (10)C6—C7—H7120.7
V1—O1—Cu1159.01 (14)C9—C8—C7119.6 (3)
V2—O3—V1139.64 (14)C9—C8—H8120.2
V2—O4—Cu1i162.64 (14)C7—C8—H8120.2
V2—O5—V1iii160.20 (14)C8—C9—C10118.9 (3)
V2—O6—Cu1iv133.16 (13)C8—C9—H9120.6
C1—N1—C5118.7 (3)C10—C9—H9120.6
C1—N1—Cu1125.5 (2)N2—C10—C9122.5 (3)
C5—N1—Cu1115.6 (2)N2—C10—H10118.7
C10—N2—C6118.8 (3)C9—C10—H10118.7
C10—N2—Cu1125.7 (2)
O2—V1—O1—Cu1−60.3 (4)N1—Cu1—N2—C10−175.0 (3)
O5iii—V1—O1—Cu1179.0 (4)O4i—Cu1—N2—C6122.4 (2)
O3—V1—O1—Cu157.8 (4)O6ii—Cu1—N2—C6−116.4 (2)
O4i—Cu1—O1—V1−68.8 (4)N1—Cu1—N2—C6−4.4 (2)
O6ii—Cu1—O1—V1169.8 (4)C5—N1—C1—C2−0.6 (5)
N1—Cu1—O1—V156.3 (4)Cu1—N1—C1—C2173.5 (2)
O4—V2—O3—V1−176.89 (19)N1—C1—C2—C3−0.8 (5)
O6—V2—O3—V163.8 (2)C1—C2—C3—C40.8 (5)
O5—V2—O3—V1−55.4 (2)C2—C3—C4—C50.5 (5)
O2—V1—O3—V2−51.5 (2)C1—N1—C5—C42.0 (4)
O1—V1—O3—V2−169.94 (19)Cu1—N1—C5—C4−172.6 (2)
O5iii—V1—O3—V267.4 (2)C1—N1—C5—C6−177.8 (3)
O6—V2—O4—Cu1i−84.8 (5)Cu1—N1—C5—C67.5 (3)
O5—V2—O4—Cu1i34.1 (5)C3—C4—C5—N1−2.0 (4)
O3—V2—O4—Cu1i153.8 (4)C3—C4—C5—C6177.9 (3)
O4—V2—O5—V1iii104.6 (4)C10—N2—C6—C72.1 (4)
O6—V2—O5—V1iii−136.9 (4)Cu1—N2—C6—C7−169.2 (2)
O3—V2—O5—V1iii−15.9 (5)C10—N2—C6—C5−179.3 (3)
O4—V2—O6—Cu1iv17.23 (19)Cu1—N2—C6—C59.5 (3)
O5—V2—O6—Cu1iv−103.38 (17)N1—C5—C6—N2−11.3 (4)
O3—V2—O6—Cu1iv137.53 (15)C4—C5—C6—N2168.8 (3)
O1—Cu1—N1—C111.4 (3)N1—C5—C6—C7167.3 (3)
O4i—Cu1—N1—C1108.1 (2)C4—C5—C6—C7−12.5 (5)
O6ii—Cu1—N1—C1−87.8 (3)N2—C6—C7—C8−1.5 (5)
N2—Cu1—N1—C1−176.2 (3)C5—C6—C7—C8180.0 (3)
O1—Cu1—N1—C5−174.30 (19)C6—C7—C8—C90.0 (5)
O4i—Cu1—N1—C5−77.7 (2)C7—C8—C9—C100.9 (5)
O6ii—Cu1—N1—C586.5 (2)C6—N2—C10—C9−1.2 (5)
N2—Cu1—N1—C5−1.97 (19)Cu1—N2—C10—C9169.1 (2)
O4i—Cu1—N2—C10−48.2 (3)C8—C9—C10—N2−0.3 (5)
O6ii—Cu1—N2—C1073.0 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2113).

References

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  • Kucsera, R., Gyepes, R. & Zurkvoa, L. (2002). Cryst. Res. Technol.37, 890–895.
  • Lu, Y., Wang, E. B., Yuan, M., Li, Y. G., Hu, C. W., Hu, N. H. & Jia, H. Q. (2002). Solid State Sci.4, 449–453.
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