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Inorganics 2014, 2(1), 79-95;

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

Department of Chemistry & Biochemistry, University of Delaware, Newark, DE 19716, USA
Author to whom correspondence should be addressed.
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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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. View Full-Text
Keywords: clathrates; type-I structure; type-II structure; silicon clathrates; type-I structure; type-II structure; silicon

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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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