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Polymorphs of VO(PO3)2: synthesis and crystal structure refinement revisited

  • Sven Umlauf , Markus Weber and Robert Glaum EMAIL logo
Published/Copyright: July 27, 2020
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 235 Issue 8-9

Abstract

The monoclinic α-polymorph of (VIVO)(PO3)2 is obtained reproducibly by reaction of V2O5 and H3PO4 (85%) (Au crucible, 380 °C, 4 d). Its crystal structure was refined from X-ray single-crystal data [C2/c, Z = 4, a = 15.1038(7) Å, b = 4.193(2) Å, c = 9.573(9) Å, β = 126.45(3), R1 = 0.052, wR2 = 0.189 for 976 unique reflections with Fo > 4σ(Fo), 48 variables]. A single-phase powder of the β-polymorph is obtained by the reaction of V2O5, H3PO4 (85%) and oxalic acid, evaporating the mixture, and subsequent annealing (porcelain crucible, 800 °C in air, 2 d). Single crystals of β-(VIVO)(PO3)2 were grown in a sealed silica ampoule with chlorine as mineralizer. The crystal structure of the orthorhombic (pseudo-tetragonal) β-polymorph was refined from X-ray single-crystal data [pseudo-merohedral twin, Fdd2, Z = 8, a = 15.536(2) Å, b = 15.586(2) Å, c = 4.2611(5) Å, R1 = 0.032, wR2 = 0.068 for 1072 unique reflections with Fo > 4σ(Fo), 50 variables]. Earlier reports on a tetragonal polymorph with unusual geometric structure of the [(V≡O)O5] polyhedron are corrected.

Keywords: group/subgroup relations; metaphosphate; polymorphic structures; pseudo-merohedral twinning; vanadyl(IV)

Dedicated to Professor Dr. Ulrich Müller on the occasion of his 80th birthday.

Corresponding author: Robert Glaum, Institute of Inorganic Chemistry, University of Bonn, 53113 Bonn, Germany, E-mail:

Acknowledgments

We thank Dr. Gregor Schnakenburg and Charlotte Rödde for the collection of the single crystal X-ray data and Dominik Offermanns (all University of Bonn) for the XRPD data of α- and β-VO(PO3)2.

  1. Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: None declared.

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/zkri-2020-0037).

Received: 2020-04-03
Accepted: 2020-05-28
Published Online: 2020-07-27
Published in Print: 2020-09-25

© 2020 Walter de Gruyter GmbH, Berlin/Boston

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  2. In this issue
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  4. Ulrich Müller zum 80. Geburtstag gewidmet
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https://doi.org/10.1515/zkri-2020-0037
Keywords for this article
group/subgroup relations; metaphosphate; polymorphic structures; pseudo-merohedral twinning; vanadyl(IV)

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Original papers
  4. Ulrich Müller zum 80. Geburtstag gewidmet
  5. Laboratory synthesis and characterization of Knasibfite K3Na4[SiF6]3[BF4] and the homologous Ge compound K3Na4[GeF6]3[BF4]
  6. The crystal structures of α-Rb7Sb3Br16, α- and β-Tl7Bi3Br16 and their relationship to close packings of spheres
  7. Beryllium triflates: synthesis and structure of BeL2(OTf)2 (L=H2O, THF, nBu2O)
  8. Synthesis and crystal structures of two layered Cu(I) and Ag(I) iodidometalates
  9. New mixed-valent alkali chain sulfido ferrates A1+x[FeS2] (A = K, Rb, Cs; x = 0.333–0.787)
  10. Structure solution of incommensurately modulated La6MnSb15
  11. Polymorphs of VO(PO3)2: synthesis and crystal structure refinement revisited
  12. On tungstates of divalent cations (III) – Pb5O2[WO6]
  13. Hydrogen order in hydrides of Laves phases
  14. High-pressure synthesis of SmGe3
  15. The complete series of sodium rare-earth metal(III) chloride oxotellurates(IV) Na2RE3Cl3[TeO3]4 (RE = Y, La–Nd, Sm–Lu)
  16. Structural diversity of salts of terpyridine derivatives with europium(III) located in both, cation and anion, in comparison to molecular complexes
  17. Elucidating structure–property relationships in imidazolium-based halide ionic liquids: crystal structures and thermal behavior
  18. Syntheses and crystal structures of the manganese hydroxide halides Mn5(OH)6Cl4, Mn5(OH)7I3, and Mn7(OH)10I4
  19. Site-preferential copper substitution for silicon leads to Cu-chains in the new ternary silicide Ir4−xCuSi2
  20. Syntheses and crystal structures of solvate complexes of alkaline earth and lanthanoid metal iodides with N,N-dimethylformamide
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