The first rubidium rare-earth(III) thiophosphates: Rb3M3[PS4]4 (M=Pr, Er)

The two non-isotypical rubidium rare-earth(III) thiophosphates Rb3M3[PS4]4 of praseodymium and erbium can easily be obtained by the stoichiometric reaction of the respective rare-earth metal, red phosphorus and sulfur with an excess of rubidium bromide (RbBr) as flux and rubidium source at 950°C for 14 days in evacuated silica tubes. The pale green platelet-shaped single crystals of Rb3Pr3[PS4]4 as well as the pink rods of Rb3Er3[PS4]4 are moisture sensitive. Rb3Pr3[PS4]4 crystallizes triclinically in the space group image (image, image, image, image, image, image; image), Rb3Er3[PS4]4 monoclinically in the space group image (image, image, image, image; image). In both structures, there are three crystallographically different rare-earth cations present. (M1)3+ is eightfold coordinated in the shape of a square antiprism, (M2)3+ and (M3)3+ are both surrounded by eight sulfur atoms as bicapped trigonal prisms each with a coordination number of eight as well as for the praseodymium, but better described as image in the case of the erbium compound. These [MS8]13− polyhedra form a layer according to image by sharing edges with the isolated [PS4]3− tetrahedra (d(P–S)=200–209 pm, ∢(S–P–S)=102–116°). These layers are stacked with a repetition period of three in the case of the praseodymium compound, but of only two for the erbium analog. The rubidium cation (Rb1)+ is located in cavities of these layers and tenfold coordinated in the shape of a tetracapped trigonal antiprism. The also tenfold but more irregularly coordinated rubidium cations (Rb2)+ and (Rb3)+ reside between the layers.