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A microporous potassium vanadyl phosphate analogue of mahnertite: hydrothermal synthesis and crystal structure

  • Olga V. Yakubovich EMAIL logo , Ian M. Steele , Galina V. Kiriukhina and Olga V. Dimitrova
Published/Copyright: January 21, 2015
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Zeitschrift für Kristallographie - Crystalline Materials
From the journal Zeitschrift für Kristallographie - Crystalline Materials Volume 230 Issue 5

Abstract

The novel phase K2.5Cu5Cl(PO4)4(OH)0.5(VO2)•H2O was prepared by hydrothermal synthesis at 553 K. Its crystal structure was determined using low-temperature (100 K) single-crystal synchrotron diffraction data and refined against F2 to R = 0.035. The compound crystallizes in the tetragonal space group I4/mmm, with unit-cell parameters a =9.8120(8), c = 19.954(1) Å, V = 1921.1(2) Å3, and Z = 4. Both symmetrically independent Cu2+ sites show elongated square-pyramidal coordination. The V5+ ions reside in strongly distorted five-vertex VO5 polyhedra with 50% occupancy. The structure is based on a 3D anionic framework built from Cu- and V-centered five-vertex polyhedra and PO4 tetrahedra. Channels in the [100] and [010] directions accommodate large K atoms and H2O molecules. The compound is a new structural representative of the topology shown by the lavendulan group of copper arsenate and phosphate minerals. Their tetragonal or pseudotetragonal crystal structures are characterized by two types of 2D slabs alternating along one axis of their unit cells. One slab, described by the formula [Cu4X(TO4)4]∞ (where X = Cl, O and T = As, P), is common to all phases, whereas the slab content of the other set differs among the group members. We suggest interpreting this family of compounds in terms of the modular concept and also consider the synthetic phase Ba(VO)Cu4(PO4)4 as a simplest member of this polysomatic series.

Keywords: copper vanadyl phosphate chloride; crystal structure; hydrothermal synthesis; lavendulan group; low-temperature data; mahnertite; polysomatic series; synchrotron radiation
Corresponding author: Olga V. Yakubovich, Department of Crystallography and Crystal Chemistry Geological Faculty, M.V. Lomonosov Moscow State University, Vorob’evy Gory, 119992 Moscow, Russia, Tel.: +7 495 9393850, Fax: +7 495 9395575, E-mail: ; and Institute of Geology of Deposits, Petrography, Mineralogy and Geochemistry, Russian Academy of Science, Moscow, Russia

Acknowledgments

We thank ChemMatCARS Sector 15 that is principally supported by the National Science Foundation/Department of Energy under grant number NSF/CHE-0822838. Use of the Advanced Photon Source was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. We are grateful to V.O. Yapaskurt for the microprobe analysis of the crystal. This analysis was performed at the Laboratory of Local Methods for Studying Materials, Department of Petrology, Faculty of Geology, Moscow State University. We gratefully acknowledge the suggestions and corrections made by U. Kolitsch and an anonymous referee. We also thank W. Depmeier for his help in the reviewing process for the original manuscript.

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Received: 2014-9-29
Accepted: 2014-11-28
Published Online: 2015-1-21
Published in Print: 2015-5-1

©2015 by De Gruyter

Articles in the same Issue

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  2. Graphical Synopsis
  3. Preface
  4. Special Issue: Zeolites
  5. Original Articles
  6. The importance of T⋯T⋯T angles in the feasibility of zeolites
  7. On the relationship between unit cells and channel systems in high silica zeolites with the “butterfly” projection
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  10. A microporous potassium vanadyl phosphate analogue of mahnertite: hydrothermal synthesis and crystal structure
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https://doi.org/10.1515/zkri-2014-1806
Keywords for this article
copper vanadyl phosphate chloride; crystal structure; hydrothermal synthesis; lavendulan group; low-temperature data; mahnertite; polysomatic series; synchrotron radiation

Articles in the same Issue

  1. Frontmatter
  2. Graphical Synopsis
  3. Preface
  4. Special Issue: Zeolites
  5. Original Articles
  6. The importance of T⋯T⋯T angles in the feasibility of zeolites
  7. On the relationship between unit cells and channel systems in high silica zeolites with the “butterfly” projection
  8. A DFT-D study of the interaction of methane, carbon monoxide, and nitrogen with cation-exchanged SAPO-34
  9. Structure and bonding of water molecules in zeolite hosts: Benchmarking plane-wave DFT against crystal structure data
  10. A microporous potassium vanadyl phosphate analogue of mahnertite: hydrothermal synthesis and crystal structure
  11. Crystal chemical models for the cancrinite-sodalite supergroup: the structure of a new 18-layer phase
  12. Synthesis and structure of new microporous Nd(III) silicates of the rhodesite group
  13. Structures of dehydrated microporous copper silicate CuSH-6Na, an in situ single crystal X-ray study
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