Home Vanadium oxide bronzes – the double mixed valence phases Cu[unk]Cu[unk](1−t)V[unk](2−t)V[unk](2−t)O5 A joint XRD and ESCA investigation
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Vanadium oxide bronzes – the double mixed valence phases Cu[unk]Cu[unk](1−t)V[unk](2−t)V[unk](2−t)O5 A joint XRD and ESCA investigation

Published/Copyright: July 28, 2010
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 209 Issue 5

Abstract

In the scope of providing new chemical insight of the oxidation states of copper and vanadium, crystal structures of VOB's β′-CuxV2O5 with x = 0.29, 0.47 and 0.59, have been carefully investigated. The structures are monoclinic, space group C2/m, with a = 15.233(3) Å, 15.218(1) Å, 15.2007(7) Å, b = 3.6133(9) Å, 3.6271(6) Å, 3.6375(3) Å, c = 10.0927(9) Å, 10.087(8) Å, 10.0925(4) Å, β = 107.30(1) Å, 106.55(4) Å, 106.13(2)°, R = 0.0467, 0.0290, 0.0315.

A thorough examination of bond distances and angles allows to give a precise description of the structural evolution versus increasing values of copper insertion x in the tunnels of the [V2O5]n framework. The three independent vanadium atoms exhibit distorted oxygen coordination polyhedra, octahedra for V(1) and V(2), square pyramid for V(3). The copper, as revealed by successive Fourier map differences, is spreaded over a sort of toroidal section inserted in a huge oxygen trigonal bipyramid; more precisely the copper coordination changes, in its asymmetric site, from CN4 for Cu(1) (in the mirror plane) to CN3 for Cu(2) (apart the mirror plane, Δy ∼± 0.12) which rarely occurs in sulphides but, up to now never in oxides. The multiplication of Cu sites as well as their various coordination let us think that copper oxidation states could be not unique; such hypothesis is confirmed by ESCA measurements, which clearly indicate that simultaneously Cu(I) and Cu(II) are present. Such results establish that β′′-CuxV2O5 phases are doubly mixed valence vanadium oxide bronzes and can be formally written:

Cuxt+Cux(1−t)2+V2−x(2−t)5+Vx(2−t)4+O5 (t stands for Cu(I) rate).

Published Online: 2010-7-28
Published in Print: 1994-5-1

© 2015 Oldenbourg Wissenschaftsverlag GmbH, Rosenheimer Str. 145, 81671 München

Articles in the same Issue

  1. Crystallography with a pulsed neutron source
  2. Feasibility of phase determination in quasicrystals and microcrystals by means of multiple bragg scattering
  3. Physical properties and phase transition of tetragonal X2CuT4 · 2Q2O, X = K, Rb, NH4, ND4, T = C1, Br, Q = H, D
  4. Die Kristallstrukturen des (NH4)2Be4Cl10 und der analogen Alkalimetall-Verbindungen
  5. Vanadium oxide bronzes – the double mixed valence phases Cu[unk]Cu[unk](1−t)V[unk](2−t)V[unk](2−t)O5 A joint XRD and ESCA investigation
  6. Crystal structure of β′-Fe0.33V2O5
  7. Single crystal refinements of seven Sr1−xCaxCuO2 structures (x = 0–0.573) and of Ca2−ySryCuO3 (y = 0 and 0.134)
  8. Structure cristalline et moleculaire du thiophosphotris(enolpyruvate)
  9. Crystal structure of 4-hydroxy-4(3-methyl-5-oxo-4,5-dihydro-1H-pyrazo-4-yl)-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole
  10. Crystal and molecular structure of two Zn–Cu compounds: Zn(NH3)2Cu(CN)3 and [Zn(en)3]6[Cu5(CN)17] · nH2O (n = 8.4) containing novel [Cu2(CN)7]5− ion
  11. Crystal structure of lignocaine hydrochloride – palladium thiocyanate complex
  12. Crystal structure of lignocaine hydrochloride – nickel thiocyanate complex
  13. Crystal structure of diaquabissarcosinatocopper(II)
  14. Polysulphonylamines, XLVIII. Structure of N-trichloroacetyldimesylamine
  15. Neutron diffraction and 35Cl-NQR-T1 measurements of N-[2,6-dichlorophenyl]-2,2,2-trichloroacetamide, 2,6-Cl2C6H3NHCOCCl31
  16. Crystal structure of N-carbobenzoxy-glycine 1
  17. Crystal structure of barium dihydride, BaH2
  18. Crystal structure of [2.2]parabenzeno-(4,7)-1,5-dimethylisatinophane, C20H19NO2
  19. Crystal structure of (E,S)-(-)-(1-methoxyethyl)[(1,3,3-trimethyl-indoline-2-ylidene)-methyl]ketone, C16H21NO2
  20. Crystal structure of tricarbonyl(η6-syn-8,16-difluoro[2.2]-metacyclophane)chromium(0), C19H14CrF2O3
  21. Crystal structure of 6-chloro-5,5-bis(methylcarboxylato)-6-phospha-bicyclo[2.2.1]hept-2-ene, C6H6PCl(COOCH3)2
  22. Crystal structure of methylammonium citrate, C7H13NO7
  23. Crystal structure of 2,8,14,20-tetramethylpentacyclo-[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octol, C32H32O8
  24. Crystal structure of 2,8,14,20-tetramethylpentacyclo-[19.3.1.13,7.19,13.115,19]octacosa-1-(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octaethyl ether, C48H64O8
  25. Crystal structure of 2,8,14,20-tetramethylpentacyclo-[19.3.1.13,7.19,13.115,19]octacosa-1-(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octaethyl ether, C48H64O8
https://doi.org/10.1524/zkri.1994.209.5.405

Articles in the same Issue

  1. Crystallography with a pulsed neutron source
  2. Feasibility of phase determination in quasicrystals and microcrystals by means of multiple bragg scattering
  3. Physical properties and phase transition of tetragonal X2CuT4 · 2Q2O, X = K, Rb, NH4, ND4, T = C1, Br, Q = H, D
  4. Die Kristallstrukturen des (NH4)2Be4Cl10 und der analogen Alkalimetall-Verbindungen
  5. Vanadium oxide bronzes – the double mixed valence phases Cu[unk]Cu[unk](1−t)V[unk](2−t)V[unk](2−t)O5 A joint XRD and ESCA investigation
  6. Crystal structure of β′-Fe0.33V2O5
  7. Single crystal refinements of seven Sr1−xCaxCuO2 structures (x = 0–0.573) and of Ca2−ySryCuO3 (y = 0 and 0.134)
  8. Structure cristalline et moleculaire du thiophosphotris(enolpyruvate)
  9. Crystal structure of 4-hydroxy-4(3-methyl-5-oxo-4,5-dihydro-1H-pyrazo-4-yl)-3-methyl-5-oxo-4,5-dihydro-1H-pyrazole
  10. Crystal and molecular structure of two Zn–Cu compounds: Zn(NH3)2Cu(CN)3 and [Zn(en)3]6[Cu5(CN)17] · nH2O (n = 8.4) containing novel [Cu2(CN)7]5− ion
  11. Crystal structure of lignocaine hydrochloride – palladium thiocyanate complex
  12. Crystal structure of lignocaine hydrochloride – nickel thiocyanate complex
  13. Crystal structure of diaquabissarcosinatocopper(II)
  14. Polysulphonylamines, XLVIII. Structure of N-trichloroacetyldimesylamine
  15. Neutron diffraction and 35Cl-NQR-T1 measurements of N-[2,6-dichlorophenyl]-2,2,2-trichloroacetamide, 2,6-Cl2C6H3NHCOCCl31
  16. Crystal structure of N-carbobenzoxy-glycine 1
  17. Crystal structure of barium dihydride, BaH2
  18. Crystal structure of [2.2]parabenzeno-(4,7)-1,5-dimethylisatinophane, C20H19NO2
  19. Crystal structure of (E,S)-(-)-(1-methoxyethyl)[(1,3,3-trimethyl-indoline-2-ylidene)-methyl]ketone, C16H21NO2
  20. Crystal structure of tricarbonyl(η6-syn-8,16-difluoro[2.2]-metacyclophane)chromium(0), C19H14CrF2O3
  21. Crystal structure of 6-chloro-5,5-bis(methylcarboxylato)-6-phospha-bicyclo[2.2.1]hept-2-ene, C6H6PCl(COOCH3)2
  22. Crystal structure of methylammonium citrate, C7H13NO7
  23. Crystal structure of 2,8,14,20-tetramethylpentacyclo-[19.3.1.13,7.19,13.115,19]octacosa-1(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octol, C32H32O8
  24. Crystal structure of 2,8,14,20-tetramethylpentacyclo-[19.3.1.13,7.19,13.115,19]octacosa-1-(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octaethyl ether, C48H64O8
  25. Crystal structure of 2,8,14,20-tetramethylpentacyclo-[19.3.1.13,7.19,13.115,19]octacosa-1-(25),3,5,7(28),9,11,13(27),15,17,19(26),21,23-dodecaene-4,6,10,12,16,18,22,24-octaethyl ether, C48H64O8
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