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Inorganics 2014, 2(1), 79-95; doi:10.3390/inorganics2010079
Article

New Type-I and Type-II Clathrates in the Systems Cs–Na–Ga–Si, Rb–Na–Ga–Si, and Rb–Na–Zn–Si

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Received: 14 January 2014 / Revised: 25 February 2014 / Accepted: 28 February 2014 / Published: 18 March 2014
(This article belongs to the Special Issue Energy Storage and Conversion)
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Abstract

Systematic studies in the systems Cs–Na–Ga–Si, Rb–Na–Ga–Si, and Rb–Na–Zn–Si yielded the novel type-I clathrates with refined compositions Cs6Na2Ga8.25Si37.75(3), Rb6.34Na1.66(2)Ga8.02Si37.98(3), and Rb5.20Na2.80(4)Zn3.85Si42.15(2) (cubic, ), as well as the type-II clathrates with formulae Cs8Na16Ga22.7Si113.3(1), Rb8.4Na15.6(1)Ga19.6Si116.4(1), and Rb8Na16Zn8.4Si127.6(1) (cubic, ). In each system, the type-I and -II compounds are always co-crystallizing, irrespective of the reaction conditions. The structures derived from single-crystal X-ray diffraction confirm complete ordering of Cs and Na atoms, and nearly complete ordering of the Rb and Na guest atoms. The framework-building Si atoms are randomly substituted by Ga or Zn atoms on all framework sites with notable difference in the substitution patterns between the type-I and type-II structure. This, and other details of the crystal chemistry are discussed in this paper.
Keywords: clathrates; type-I structure; type-II structure; silicon clathrates; type-I structure; type-II structure; silicon
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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Schäfer, M.C.; Bobev, S. New Type-I and Type-II Clathrates in the Systems Cs–Na–Ga–Si, Rb–Na–Ga–Si, and Rb–Na–Zn–Si. Inorganics 2014, 2, 79-95.

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