Lithium metal atoms fill vacancies in the germanium network of a type-I clathrate: synthesis and structural characterization of Ba 8 Li 5 Ge 41

• Published in: Dalton transactions : an international journal of inorganic chemistry 2023-08, Vol.52 (30), p.10310-10322
• Main Authors: Ghosh, Kowsik, Ovchinnikov, Alexander, Baitinger, Michael, Krnel, Mitja, Burkhardt, Ulrich, Grin, Yuri, Bobev, Svilen
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/D3DT01168B

Clathrate phases with crystal structures exhibiting complex disorder have been the subject of many prior studies. Here we report syntheses, crystal and electronic structure, and chemical bonding analysis of a Li-substituted Ge-based clathrate phase with the refined chemical formula Ba Li Ge , which is a rare example of ternary clathrate-I where alkali metal atoms substitute framework Ge atoms. Two different synthesis methods to grow single crystals of the new clathrate phase are presented, in addition to the classical approach towards polycrystalline materials by combining pure elements in desired stoichiometric ratios. Structure elucidations for samples from different batches were carried out by single-crystal and powder X-ray diffraction methods. The ternary Ba Li Ge phase crystallizes in the cubic type-I clathrate structure (space group 3̄ no. 223, ≈ 10.80 Å), with the unit cell being substantially larger compared to the binary phase Ba Ge (Ba □ Ge , ≈ 10.63 Å). The expansion of the unit cell is the result of the Li atoms filling vacancies and substituting atoms in the Ge framework, with Li and Ge co-occupying one crystallographic (6 ) site. As such, the Li atoms are situated in four-fold coordination environment surrounded by equidistant Ge atoms. Analysis of chemical bonding applying the electron density/electron localizability approach reveals ionic interaction of barium with the Li-Ge framework, while the lithium-germanium bonds are strongly polar covalent.