Complex Disorder in Type-I Clathrates: Synthesis and Structural Characterization of <i>A</i>₈Ga<i>_x</i>Sn_{46–<i>x</i>} (<i>A</i> = Rb, Cs; 6.9 < <i>x</i> < 7.5)

• Main Authors: Sviatoslav A. Baranets, Amanda B. Childs, Hua He, Svilen Bobev
• Format: Article
• Language: English
• Published: MDPI AG 2020-04-01
• Series: Crystals
• Subjects: clathrates; type-I structure; Zintl phases; crystal structures
• Online Access: https://www.mdpi.com/2073-4352/10/4/298
• ISSN: 2073-4352

Exploratory studies in the systems Rb–Ga–Sn and Cs–Ga–Sn yielded the cubic type-I clathrates with refined compositions Rb₈Ga<i>_x</i>Sn_{46–<i>x</i>} and Cs₈Ga<i>_x</i>Sn_46–x (6.9 < <i>x</i> < 7.5). Nearly single-phase materials with good crystallinity were obtained from stoichiometric reactions of the elements. The structures were characterized by means of single-crystal X-ray diffraction methods. Both Rb₈Ga<i>_x</i>Sn_{46–<i>x</i>} and Cs₈Ga<i>_x</i>Sn_{46–<i>x </i>}represents cases, where a Group 13 element randomly substitutes a Group 14 element in the structure. The extent of Ga/Sn mixing is apparently governed by the drive of the system to achieve an optimal valence electron count, and hence, Rb₈Ga<i>_x</i>Sn_{46–<i>x</i>} and Cs₈Ga<i>_x</i>Sn_{46–<i>x </i>}(<i>x</i> ≈ 8) can be regarded as Zintl phases. This notion is supported by structure refinements on a multitude of single-crystal X-ray diffraction data, which also confirm that both types of cages in the cubic type-I structure are fully occupied by Rb and Cs atoms. The open-framework, comprised of 46 nodes per formula unit, adapts to the incorporation of nearly eight Ga atoms within the matrix of Sn, whereby small, short-range distortions result. The exact nature of these effects is still unclear, as so far, the structural variations could only be modeled as both positional and occupational disorder at one of three framework sites. Since vacancies in the structures of the binary type-I clathrates <i>A</i>₈Sn_{46–<i>x</i>}¨<i>_x</i> (<i>A</i> = Rb, Cs; ¨ = missing Sn atom) are also known to cause local distortions, the latter were also synthesized with the same protocols used for the synthesis of <i>A</i>8Ga<i>x</i>Sn46–<i>x</i> and structurally re-analyzed. The results from the latter studies confirm that homogeneity issues abound, and that the final structures/compositions are an intricate function of the experimental conditions.