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Directed Dehydration of Na$_4$Sn$_2$S$_6$ ⋅ 5H$_2$O Generates the New Compound Na$_4$Sn$_2$S$_6$: Crystal Structure and Selected Properties

Benkada, Assma; Hartmann, Felix; Poschmann, Michael; Indris, Sylvio ORCID iD icon 1; Lühmann, Henning; Bensch, Wolfgang
1 Institut für Angewandte Materialien – Energiespeichersysteme (IAM-ESS), Karlsruher Institut für Technologie (KIT)


The new thiostannate Na$_4$Sn$_2$S$_6$ was prepared by directed crystal water removal from the hydrate Na$_4$Sn$_2$S$_6$ ⋅ 5H$_2$O at moderate temperatures. While the structure of the hydrate comprises isolated [Sn$_2$S$_6$]$^{4−}$ anions, that of the anhydrate contains linear chains composed of corner-sharing SnS4 tetrahedra, a structural motif not known in thiostannate chemistry. This structural rearrangement requires bond-breakage in the [Sn2S6]4− anion, movements of the fragments of the opened [Sn2S6]4− anion and Sn−S−Sn bond formation. Simultaneously, the coordination environment of the Na+ cations is significantly altered and the in situ formed NaS$_5$ polyhedra are joined by corner- and edge-sharing to form a six-membered ring. Time-dependent in situ X-ray powder diffraction evidences very fast rehydration into Na$_4$Sn$_2$S$_6$ ⋅ 5H$_2$O during storage in air atmosphere, but recovery of the initial crystallinity requires several days. Impedance spectroscopy demonstrates a mediocre room-temperature Na$^+$ ion conductivity of 0.31 μS cm$^{−1}$ and an activation energy for ionic transport of E$_a$=0.75 eV.

Verlagsausgabe §
DOI: 10.5445/IR/1000160450
Veröffentlicht am 12.07.2023
DOI: 10.1002/ejic.202200687
Zitationen: 3
Web of Science
Zitationen: 3
Zitationen: 3
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Angewandte Materialien – Energiespeichersysteme (IAM-ESS)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 03.04.2023
Sprache Englisch
Identifikator ISSN: 1434-1948, 1099-0682
KITopen-ID: 1000160450
HGF-Programm 38.02.02 (POF IV, LK 01) Components and Cells
Erschienen in European Journal of Inorganic Chemistry
Verlag Wiley-VCH Verlag
Band 26
Heft 10
Seiten Art.-Nr.: e202200687
Vorab online veröffentlicht am 27.01.2023
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