Neue Thiophosphate: Die Verbindungen Li 6 Ln 3 (PS 4 ) 5 ( Ln : Y, Gd, Dy, Yb, Lu) und Ag 3 Y(PS 4 ) 2

New Thiophosphates: The Compounds Li 6 Ln 3 (PS 4 ) 5 ( Ln : Y, Gd, Dy, Yb, Lu) and Ag 3 Y(PS 4 ) 2 The new thiophosphates Li 6 Ln 3 (PS 4 ) 5 ( Ln : Y, Gd, Dy, Yb, Lu) were synthesized by heating mixtures of Ln , P, S, and Li 2 S 4 at 900 °C (100 h) and they were investigated by single crystal X‐ray methods. The compounds with Ln = Y ( a = 28.390(2), b = 10.068(1), c = 33.715(2) Å, β = 113.85(1)°), Gd ( a = 28.327(2), b = 10.074(1), c = 33.822(2) Å, β = 114.297(7)°), Dy ( a = 28.124(6), b = 10.003(2), c = 33.486(7) Å, β = 113.89(3)°), Yb ( a = 28.178(3), b = 9.977(1), c = 33.392(4) Å, β = 113.65(1)°), and Lu ( a = 28.169(6), b = 10.002(2), c = 33.432(7) Å, β = 113.54(3)°) are isotypic and crystallize in a new structure type ( C 2/ c ; Z = 12). Main feature are PS 4 tetrahedra isolated from each other surrounding the Ln and Li atoms via their S atoms. The coordination number of the five crystallographically independent Ln atoms is eight, but the polyhedra are quite different and they are interlinked to larger units extending in [010]. The environment of the Li atoms is irregular and formed by five to six S atoms. The crystal structure is compared with that of Li 9 Ln 2 (PS 4 ) 5 ( Ln : Nd, Gd). For the synthesis of Ag 3 Y(PS 4 ) 2 ( a = 16.874(3), b = 9.190(2), c = 9.312(2) Å, β = 123.17(3)°) a mixture of Y, P, S, and Ag 2 S was heated to 700 °C (50 h). The thiophosphate crystallizes in a new structure type ( C 2/ c ; Z = 4) composed of isolated PS 4 tetrahedra. The two crystallographically independent Ag atoms are surrounded by four S atoms in the shape of distorted tetrahedra. The Ag(1)S 4 polyhedra are cornershared to strands running along [001], which are linked together via Ag(2)S 4 tetrahedra. The environment of the Y atoms is composed of eight S atoms each building distorted square antiprisms. These polyhedra are connected with each other via common edges to a strand running along [001].