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Abstract
The isostructural alkali thioferrate compounds CsFe2S3, RbFe2S3 and KFe2S3 have been synthesized by reacting Fe and S with their corresponding AFeS2 (A=K, Rb, Cs) precursors. The crystal structures of these and binary compounds of intermediate composition were determined by Rietveld analysis of laboratory powder X-ray diffraction patterns. All of the synthesized compounds adopt the space group Cmcm (#63), Z=4 with: a=9.5193(8) Å, b=11.5826(10) Å, c=5.4820(4) Å for CsFe2S3; a=9.2202(7) Å, b=11.2429(9) Å, c=5.4450(3) Å for RbFe2S3; and a=9.0415(13) Å, b=11.0298(17) Å, c=5.4177(6) Å for KFe2S3. These mixed valence alkali thioferrates show regular changes in cell dimensions, AS10 (A=K, Rb, Cs) polyhedron volumes, polyhedron distortion parameters, and calculated oxidation state of Fe with respect to increasing size of the alkali element cation. The calculated empirical oxidation state of iron varies from +2.618 (CsFe2S3), through +2.666 (RbFe2S3) to +2.77 (KFe2S3).
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