title: Endohedrally filled [Ni@Sn9](4-) and [Co@Sn9](5-) clusters in the neat solids Na12Ni(1-x)Sn17 and K(13-x)Co(1-x)Sn17: crystal structure and 119Sn solid-state NMR spectroscopy.
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 Na12Ni(1-x)Sn17 and K(13-x)Co(1-x)Sn17, 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 K(13-x)Co(1-x)Sn17 and K(5-x)Co(1-x)Sn9, and consequently, all compounds correspond to diamagnetic valence compounds. Owing to their diamagnetism, K(13-x)Co(1-x)Sn17, and K(5-x)Co(1-x)Sn9, as well as the d-block metal free binary compounds K12Sn17 and K4Sn9, were characterized for the first time by (119)Sn solid-state NMR spectroscopy.
authors: Department of Chemistry, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching (Germany), Fax: (+49) 8928913186.
authors: Viktor
authors: V
authors: Hlukhyy
authors: Saskia
authors: S
authors: Stegmaier
authors: Leo
authors: L
authors: van Wüllen
authors: Thomas F
authors: TF
authors: Fässler
keywords: NMR spectroscopy; cluster compounds; hierarchical relationship; intermetallic phases; intermetalloid cluster; stannides