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Metastable Ge( cF 136) with empty clathrate-II crystal structure was successfully used for the preparation of otherwise hardly accessible germanium clathrate phases. On reaction of Ge( cF 136) with potassium vapour at 280 °C for 6 days, the new clathrate-II phase K 24 Ge 136  was formed, in which the cages of the germanium framework are completely filled by potassium atoms. The crystal structure of K  x  Ge 136  is discussed for different potassium contents ( x =0, 8.6, 24).

Preparation of anionic clathrate-II K 24- x Ge 136 by filling of Ge( cF 136)