Ce53Fe12S90X3 (X = Cl, Br, I): The first rare-earth transition-metal sulfide halides

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Abstract

The compounds Ce53Fe12S90X3 (X = Cl, Br, I), which represent the first examples of rare-earth transition-metal sulfide halides, were prepared using the reactive-flux method, through reaction of Ce2S3, FeS, or Fe and S in a CeX3 flux at 1320 K. Their structures were determined by single-crystal X-ray diffraction. The compounds are isostructural, crystallizing in the trigonal space group R3m with Z = 1 [Ce53Fe12S90Cl3, a = 13.9094(9) Å, c = 21.604(2) Å, V = 3619.7(4) Å3; Ce53Fe12S90Br3, a = 13.916(1) Å, c = 21.824(2) Å, V = 3660.0(5) Å3; Ce 53Fe12S90I3, a = 13.863(3) Å, c = 21.944(6) Å, V = 3652(2) Å3]. The structure adopted is a stuffed variant of the La52Fe12S90 structure type. Fe2S9 dimers of face-sharing octahedra are linked by face- and vertex-sharing capped CeS6 trigonal prisms, forming a three-dimensional framework containing cuboctahedral cavities of two sizes. The smaller cavities accommodate alternative sites for disordered cerium atoms. The larger cavities, which remain empty in the parent structure, are filled by halogen atoms in Ce53Fe12S90X 3. Alternatively, the structure can be described as a 9-fold superstructure of the Mn5Si3 structure type (P6 3/mcm), with a = √3a′ and c = 3c′. Temperature-dependent magnetic susceptibility measurements suggest that Ce 53Fe12S90I3 may order antiferromagnetically at low temperatures.

Details

Original languageEnglish
Pages (from-to)5172-5178
Number of pages7
JournalInorganic chemistry
Volume45
Issue number13
Publication statusPublished - 26 Jun 2006
Peer-reviewedYes

External IDs

ORCID /0000-0002-2391-6025/work/166325833