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Synthesis and Crystal Structure of Mercury‐Substituted Type‐I Clathrates A 8 Hg 4 Sn 42 (A = K, Rb, Cs)
Author(s) -
Kaltzoglou Andreas,
Ponou Siméon,
Fässler Thomas F.
Publication year - 2008
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200700854
Subject(s) - chemistry , crystallography , diamagnetism , alkali metal , crystal structure , thermal stability , metal , differential thermal analysis , mercury (programming language) , single crystal , paramagnetism , melting point , diffraction , magnetic field , condensed matter physics , programming language , physics , organic chemistry , quantum mechanics , computer science , optics
The mercury‐substituted type‐I clathrates A 8 Hg 4 Sn 42 ,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 Pm $\bar {3}$ n (No. 223), Z = 1 with a = 12.1255(4) Å for K 8 Hg 4 Sn 42 ( 1 ), a = 12.1838(4) Å for Rb 8 Hg 4 Sn 42 ( 2 ) and a = 12.2130(4) Å for Cs 8 Hg 4 Sn 42 ( 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 A 8 Sn 44 (A = K, Rb, Cs) is discussed. Temperature‐dependent magnetic measurements for compound 3 show also the expected diamagnetic behaviour. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)