Inorganic Chemistry, Vol.48, No.17, 8227-8232, 2009
Reinvestigation of the Uranium(3.5+) Rare-Earth Oxysulfides "(UO)(2)LnS(3)" (Ln = Yb, Y)
Dark-red square plates of the previously reported compounds "(UO)(2)LnS(3)" (Ln = Yb, Y) have been synthesized by solid-state reactions of UOS and YbS or Y2S3 with Sb2S3 as a flux at 1273 K. The structure of these isotypic compounds was reinvestigated by single-crystal X-ray diffraction methods and an inductively coupled plasma experiment. The actual formula of "(UO)(2)LnS(3)" (Ln = Yb, Y) is (U(0.5)Ln(0.5)O)(2)LnS(3), that is, ULn(2)O(2)S(3), which can be charge-balanced with U4+ and Ln(3+). The layered structure comprises (U/Ln)O4S4 square antiprisms alternating with LnS(6) octahedra. U and Ln1 atoms disorder on the eight-coordinate metal position, but Ln2 atoms occupy the six-coordinate metal position exclusively. UYb2O2S3 is a modified Curie-Weiss paramagnet between 293 and 32 K, below which part of the paramagnetic moments go through a possible ferromagnetic transition. The band gaps of ULn(2)O(2)S(3) (Ln = Yb, Y) are around 2 eV.