Semiclathrates of the Ge-P-Te system: Synthesis and crystal structures

Maria A. Kirsanova, Liudmila N. Reshetova, Andrei V. Olenev, Artem M. Abakumov, Andrei V. Shevelkov

Research output: Contribution to journalArticlepeer-review

17 Citations (Scopus)

Abstract

Novel compounds [Ge46-xPx]Tey (13.9≤15.6, 5.92≤7.75) with clathrate-like structures have been prepared and structurally characterized. They crystallize in the space group Fm$\bar 3$ with the unit cell parameter changing from 20.544(2) to 20.698(2) Å (Z=8) on going from x=13.9 to x=15.6. Their crystal structure is composed of a covalently bonded Geï P framework that hosts tellurium atoms in the guest positions and can be viewed as a peculiar variant of the type I clathrate superstructure. In contrast to the conventional type I clathrates, [Ge46-xPx]Tey contain tricoordinated (3b) atoms and no vacancies in the framework positions. As a consequence of the transformation of the framework, the majority of the guest tellurium atoms form a single covalent bond with the host framework and thus the title compounds are the first representative of semiclathrates with covalent bonding. A comparison is made with silicon clathrates and the evolution of the crystal structure upon changing the tellurium content is discussed.

Original language English 5719-5726 8 Chemistry - A European Journal 17 20 https://doi.org/10.1002/chem.201003553 Published - 9 May 2011

Keywords

• cage compounds
• clathrates
• germanium
• tellurium
• X-ray diffraction

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