Structural refinement of köttigite-parasymplesite solid solution: Unique cation site occupancy and chemical bonding with water molecules

Akira Yoshiasa, Yumiko Miyano, Hiroshi Isobe, Kazumasa Sugiyama, Hiroshi Arima, Akihiko Nakatsuka, Koichi Momma, Ritsuro Miyawaki

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

Köttigite and parasymplesite form a solid solution of Zn3-x,Fex(AsO4)2 •8H2O. The compositional variations in the köttigite-parasymplesite solid-solution system were determined by SEM/EDS with specimens from Mitate Mine, Miyazaki, Japan, and Ojuela Mine, Mapimi Durango, Mexico. Variations were observed in the direction perpendicular to the (010) plane in the continuous solid-solution system. A refinement of the crystal structure of Zn1.62Fe1.38(AsO4)2 •8H2O [monoclinic, space group C2/m, a = 10.3417(13), b = 13.4837(16), c = 4.7756(5) Å, β =105. 306(4)°, V = 642.31(13) Å3, and Z = 4] converged into R = 0.0265 and S = 1.083 for 650 independent reflections in the single-crystal XRD data. The hydrogen bonds were described based on the hydrogen atom positions on the difference Fourier maps in reference to the bond valence calculations. The smaller Zn2+ ion prefers the larger M1 site and the larger Fe2+ ion prefers the smaller M2 site. This unique cation site preference reduces the structural distortions. The M2-O5 bond distance, where O5 is the oxygen of the H2O group, is shorter than that of M2-O2 and -O3, in which the oxygen atoms form edge-sharing M22O6(H2O)4 double octahedra. Only one hydrogen atom from the H2O group, H52, connects the respective complex sheets consisting of M22O6(H2O)4 double octahedra and AsO4 tetrahedra. The space between the respective complex sheets is filled with hydrogen. It is presumed that the movement of proton in this space is the fastest.

Original languageEnglish
Pages (from-to)363-369
Number of pages7
JournalJournal of Mineralogical and Petrological Sciences
Volume111
Issue number5
DOIs
Publication statusPublished - 2016 Jan 1

Keywords

  • Chemical bonding
  • Kottigite solid-solution
  • Parasymplesite solid-solution
  • Unique site occupancy
  • Water molecule

ASJC Scopus subject areas

  • Geophysics
  • Geology

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