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Structural features in Tutton’s salts K2[M2+(H2O)6](SO4)2, with M2+ = Mg, Fe, Co, Ni, Cu, and Zn

  • Ferdinando Bosi EMAIL logo , Girolamo Belardi and Paolo Ballirano
Published/Copyright: April 1, 2015
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American Mineralogist
From the journal American Mineralogist Volume 94 Issue 1

Abstract

The crystal chemistry of six crystals of general formula K2[M2+(H2O)6](SO4)2, with M2+ = Mg, Fe, Co, Ni, Cu, and Zn, was investigated by single-crystal structure analysis to determine the effects of the chemical variation of M2+ on the structural environment surrounding K, M, and S sites. Results indicate that the distortion in the SO4 tetrahedron and the MO6 octahedron is very small, except for CuO6 where it is pronounced because of the Jahn-Teller effect. The KO8-octacoordinate polyhedron has the highest degree of distortion, and its idealized shape may be referred to as a bicapped trigonal prism. The SO4 size is not affected by changes in cation occupancies at the adjacent M site. In contrast, changes in the KO8 size, which are accompanied by changes in the bond valence sum at K, depend on interaction with the first and second coordination sphere of M. This interaction results by changes in M-O individual lengths, by expansion of the second coordination sphere of M, and by changes in the distribution of the bond strengths over the O atoms coordinated to K. The MO6 size follows the expected trend from the increased ionic radius at the M site. The latter is also correlated with the unit-cell volume except for the Cu- and Mg-phase, which show a larger cell volume with respect to that expected. Although the relevant octahedral distortion around the Cu2+ cation explains the volume excess in the Cu-phase, an expansion of the second coordination sphere of Mg2+, compared to those of cations of larger ionic radius (such as Zn and Co), explains the excess of the unit-cell volume in the Mg-phase. As the CuO6 distortion can be caused by the Jahn-Teller effect, the higher ionicity of the Mg atom could be the cause for its anomalous behavior observed in Tutton’s salts. This stereochemical behavior of the Mg atom seems to be consistent with the weakening of the hydrogen bonds in the structure connected to differences in the bonding character of Mg and transition metals when coordinated by water molecules.

Keywords : Crystal synthesis; Tutton’s salts; crystal structure; bond valence
Received: 2007-12-17
Accepted: 2008-7-15
Published Online: 2015-4-1
Published in Print: 2009-1-1

© 2015 by Walter de Gruyter Berlin/Boston

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  1. Amorphous materials: Properties, structure, and durability. The viscosity of hydrous NaAlSi3O8 and granitic melts: Configurational entropy models
  2. Alteration mineralogy and the effect of acid-leaching on the Pb-isotope systematics of ocean-island basalts
  3. Color origin and heat evidence of paleontological bones: Case study of blue and gray bones from San Josecito Cave, Mexico
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  5. Amphibole equilibria in mantle rocks: Determining values of mantle aH2O and implications for mantle H2O contents
  6. Experimental fluoridation of nanocrystalline apatite
  7. Dehydration dynamics of barrerite: An in situ synchrotron XRPD study
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https://doi.org/10.2138/am.2009.2898
Keywords for this article
Crystal synthesis; Tutton’s salts; crystal structure; bond valence

Articles in the same Issue

  1. Amorphous materials: Properties, structure, and durability. The viscosity of hydrous NaAlSi3O8 and granitic melts: Configurational entropy models
  2. Alteration mineralogy and the effect of acid-leaching on the Pb-isotope systematics of ocean-island basalts
  3. Color origin and heat evidence of paleontological bones: Case study of blue and gray bones from San Josecito Cave, Mexico
  4. Coexistence of pyroxenes jadeite, omphacite, and diopside/hedenbergite in an albite-omphacite rock from a serpentinite mélange in the Kurosegawa Zone of Central Kyushu, Japan
  5. Amphibole equilibria in mantle rocks: Determining values of mantle aH2O and implications for mantle H2O contents
  6. Experimental fluoridation of nanocrystalline apatite
  7. Dehydration dynamics of barrerite: An in situ synchrotron XRPD study
  8. Structural features in Tutton’s salts K2[M2+(H2O)6](SO4)2, with M2+ = Mg, Fe, Co, Ni, Cu, and Zn
  9. Incorporation of water in iron-free ringwoodite: A first-principles study
  10. Temperature dependence of reflectance spectra and color values of hematite by in situ, high-temperature visible micro-spectroscopy
  11. Lattice thermal expansion of zircon-type LuPO4 and LuVO4: A comparative study
  12. Solubility of H2O and CO2 in ultrapotassic melts at 1200 and 1250 °C and pressure from 50 to 500 MPa
  13. Multi-analytical approach to solve the puzzle of an allanite-subgroup mineral from Kesebol, Västra Götaland, Sweden
  14. Dislocation modeling in calcium silicate perovskite based on the Peierls-Nabarro model
  15. Molecular dynamics insight into the cointercalation of hexadecyltrimethyl-ammonium and acetate ions into smectites
  16. Adding further complexity to the polybasite structure: The role of Ag in the B layer of the -M2a2b2c polytype
  17. Structural position of H2O molecules and hydrogen bonding in anomalous 11 Å tobermorite
  18. Electronic structures of siderite (FeCO3) and rhodochrosite (MnCO3): Oxygen K-edge spectroscopy and hybrid density functional theory
  19. Crystal growth and the fast reaction paradox: Mathematical resolution and implications for habit and compositional zoning
  20. The composition of KLB-1 peridotite
  21. Crystal chemistry of the magnetite-ulvöspinel series
  22. New insights into the crystal structure and crystal chemistry of the zeolite phillipsite
  23. Letter: Octahedral cation distribution in palygorskite
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