Endohedrally Filled [Ni@Sn9]4− and [Co@Sn9]5− Clusters in the Neat Solids Na12Ni1−xSn17 and K13−xCo1−xSn17: Crystal Structure and 119Sn Solid‐State NMR Spectroscopy |
| |
| Authors: | Dr. Viktor Hlukhyy Dr. Saskia Stegmaier Prof. Dr. Leo van Wüllen Prof. Dr. Thomas F. Fässler |
| |
| Affiliation: | 1. Department of Chemistry, Technische Universit?t München, Lichtenbergstrasse 4, 85747 Garching (Germany), Fax: (+49)?8928913186;2. Department of Physics, University of Augsburg, Universit?tsstrasse 1, 86159 Augsburg (Germany) |
| |
| Abstract: | A systematic approach to the formation of endohedrally filled atom clusters by a high‐temperature route instead of the more frequent multistep syntheses in solution is presented. Zintl phases Na12Ni1?xSn17 and K13?xCo1?xSn17, containing endohedrally filled intermetalloid clusters [Ni@Sn9]4? or [Co@Sn9]5? beside [Sn4]4?, are obtained from high‐temperature reactions. The arrangement of [Ni@Sn9]4? or [Co@Sn9]5? and [Sn4]4? clusters, which are present in the ratio 1:2, can be regarded as a hierarchical replacement variant of the hexagonal Laves phase MgZn2 on the Mg and Zn positions, respectively. The alkali‐metal positions are considered for the first time in the hierarchical relationship, which leads to a comprehensive topological parallel and a better understanding of the composition of these compounds. The positions of the alkali‐metal atoms in the title compounds are related to the known inclusion of hydrogen atoms in the voids of Laves phases. The inclusion of Co atoms in the {Sn9} cages correlates strongly with the number of K vacancies in K13?xCo1?xSn17 and K5?xCo1?xSn9, and consequently, all compounds correspond to diamagnetic valence compounds. Owing to their diamagnetism, K13?xCo1?xSn17, and K5?xCo1?xSn9, as well as the d‐block metal free binary compounds K12Sn17 and K4Sn9, were characterized for the first time by 119Sn solid‐state NMR spectroscopy. |
| |
| Keywords: | cluster compounds hierarchical relationship intermetallic phases intermetalloid cluster NMR spectroscopy stannides |
|
|
