Ce₅₃Fe₁₂S₉₀X₃ (X = Cl, Br, I): The First Rare-Earth Transition-Metal Sulfide Halides

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 R3̄m 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; Ce53Fe12S90I3, 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 Ce53Fe12S90X3. Alternatively, the structure can be described as a 9-fold superstructure of the Mn5Si3 structure type (P63/mcm), with a = a‘ and c = 3c‘. Temperature-dependent magnetic susceptibility measurements suggest that Ce53Fe12S90I3 may order antiferromagnetically at low temperatures.