Synthesis and crystal structure of mercury-substituted type-I clathrates A8Hg4Sn42 (A = K, Rb, Cs)

Andreas Kaltzoglou, Siméon Ponou, Thomas F. Fässler

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Abstract

The mercury-substituted type-I clathrates A8Hg 4Sn42,with A = K, Rb or Cs, were obtained by fusion of the pure elements at high temperatures. The crystal structures of the compounds were refined from single-crystal X-ray diffraction data. They crystallize in the space group Pm3̄n (No. 223), Z = 1 with a = 12.1255(4) Å for K 8Hg4Sn42 (1), a = 12.1838(4) Å for Rb8Hg4Sn42 (2) and a = 12.2130(4) Å for Cs8Hg4Sn42 (3). The 3D framework of four-bonded atoms defines two types of polyhedral cages of different size that are fully occupied by the alkali-metal atoms. All three compounds are considered as formally charge-balanced Zintl phases without any homogeneity range. Differential thermal analysis (DTA) indicates that the stability of the clathrates significantly depends on the size of the encaged cations. The thermal stability of the title compounds and the binary phases A8Sn 44 (A = K, Rb, Cs) is discussed. Temperature-dependent magnetic measurements for compound 3 show also the expected diamagnetic behaviour.

Original languageEnglish
Pages (from-to)538-542
Number of pages5
JournalEuropean Journal of Inorganic Chemistry
Issue number4
DOIs
StatePublished - Feb 2008

Keywords

  • Clathrate
  • Crystal structure
  • Differential thermal analysis
  • Mercury
  • Stannides
  • Zintl phases

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