Abstract
The five quaternary compounds Ba3Gd2[P4S16] (1), Ba3Tb2[P4S16] (2), Ba3Dy2[P4S16] (3), Ba3Ho2[P4S16] (4), and Ba3Er2[P4S16] (5) were synthesized at elevated temperatures in carbon-coated quartz tubes. The isostructural compounds crystallize in the orthorhombic space group Pbcn (No. 60), Z = 4, with a = 19.127(3) A, b = 10.2795(5) A, and c = 12.648(2) A for 1; a = 19.113(2) A, b = 10.261(2) A, and c = 12.616(2) A for 2; a = 19.112(2) A, b = 10.2646(8) A, and c = 12.602(2) A for 3; a = 19.088(3) A, b = 10.248(2) A, and c = 12.565(2) A for 4; and a = 19.078(3) A, b = 10.241(2) A, and c = 12.568(2) A for 5.The structures are composed of one-dimensional infinite helical anionic [Ln2(PS4)4]n6n- chains and charge-compensating Ba2+ ions. The Ln atoms are surrounded by four [PS4]3- tetrahedra, leading to a strong distorted LnS8 rectangular antiprism. Three of the anions act as tetradentate ligands, and one is bidentate. Three Ln3+ centers are joined via one tetradentate [PS4]3- ligand, and this connection mode yie...
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