A new ternary phase has been synthesized and structurally characterized. BaLi x Cd 13– x ( x ≈ 2) adopts the cubic NaZn 13 structure type (space group Fm 3 ¯ c , Pearson symbol cF 112) with unit cell parameter a = 13.5548 (10) Å. Structure refinements from single-crystal X-ray diffraction data demonstrate that the Li atoms are exclusively found at the centers of the Cd 12 -icosahedra. Since a cubic BaCd 13 phase does not exist, and the tetragonal BaCd 11 is the most Cd-rich phase in the Ba–Cd system, BaLi x Cd 13– x ( x ≈ 2) has to be considered as a true ternary compound. As opposed to the typical electron count of ca. 27 e -per formula unit for many known compounds with the NaZn 13 structure type, BaLi x Cd 13– x ( x ≈ 2) only has ca. 26 e -, suggesting that both electronic and geometric factors are at play. Finally, the bonding characteristics of the cubic BaLi x Cd 13– x ( x ≈ 2) and tetragonal BaCd 11 are investigated using the TB-LMTO-ASA method, showing metallic-like behavior.
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The Synthesis and Crystal Structure of Six Quaternary Lithium-Alkaline Earth Metal Alumo-Silicides and Alumo-Germanides, A2LiAlTt2 (A = Mg, Ca, Sr, Ba; Tt = Si, Ge)
Reported are the synthesis and structural characterization of a series of quaternary lithium-alkaline earth metal alumo-silicides and alumo-germanides with the base formula A2LiAlTt2 (A = Ca, Sr, Ba; Tt = Si, Ge). To synthesize each compound, a mixture of the elements with the desired stoichiometric ratio was loaded into a niobium tube, arc welded shut, enclosed in a silica tube under vacuum, and heated in a tube furnace. Each sample was analyzed by powder and single-crystal X-ray diffraction, and the crystal structure of each compound was confirmed and refined from single-crystal X-ray diffraction data. The structures, despite the identical chemical formulae, are different, largely dependent on the nature of the alkaline earth metal. The differing cation determines the structure type—the calcium compounds are part of the TiNiSi family with the Pnma space group, the strontium compounds are isostructural with Na2LiAlP2 with the Cmce space group, and the barium compounds crystallize with the PbFCl structure type in the P4/nmm space group. The anion (silicon or germanium) only impacts the size of the unit cell, with the silicides having smaller unit cell volumes than the germanides.
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- Award ID(s):
- 2004579
- PAR ID:
- 10498892
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Inorganics
- Volume:
- 11
- Issue:
- 9
- ISSN:
- 2304-6740
- Page Range / eLocation ID:
- 351
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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