The First Quinary Rare Earth Thiophosphates: Cs₅<i>Ln</i>₃<i>X</i>₃(P₂S₆)₂(PS₄) (<i>Ln</i> = La, Ce, <i>X</i> = Br, Cl) and the Quasi‐Quaternary Cs₁₀Y₄Cl₁₀(P₂S₆)₃

We report the first examples of quinary rare earth thiophosphates with a fully ordered cation and anion distribution, Cs5Ln3X3(P2S6)2(PS4), (Ln = La, Ce and X = Br, Cl) as well as the quasi‐quaternary Cs10Y4Cl10(P2S6)3. These four new compounds crystallize in three different, unknown structure types. The yellowish, transparent, brittle Cs5Ce3Br3(P2S6)2(PS4) crystallizes in the orthorhombic space group Pnma (no. 62) with a = 13.276(3), b = 14.891(3), c = 19.593(4) Å, and V = 3873(1) Å3 in a novel structure type. Colorless crystals of Cs5La3Br3(P2S6)2(PS4) and Cs5La3Cl3(P2S6)2(PS4) are isotypic and were obtained in the monoclinic space group P21/m (no. 11) with a = 9.715(2), b = 14.310(3), c = 13.685(3) Å, β = 100.16(3)° and V = 1873(1) Å3 and a = 9.513(2), b = 14.182(3), c = 13.699(3) Å, β = 99.39(3)° and V = 1823(1) Å3, respectively. Both structures contain isolated hexathiohypodiphosphate(IV) [P2S6]4– and thiophosphate [PS4]3– units that are arranged alternately in layers. Cs10Y4Cl10(P2S6)3 crystallizes in colorless transparent platelets in the orthorhombic space group Pnnm (no. 58) with a = 13.153(3), b = 28.964(6), c = 7.780(2) Å, and V = 2964(1) Å3. The structure is composed of isolated [P4/2S6]4– octahedra containing four half occupied P positions surrounded octahedrally by sulfur. We show with Raman scattering that this disordered thiophosphate anion shows a Raman spectrum that is distinct from spectra published for other literature‐known thiophosphate anions.