The First Quinary Rare Earth Thiophosphates: Cs5Ln3X3(P2S6)2(PS4) (Ln = La, Ce, X = Br, Cl) and the Quasi-Quaternary Cs10Y4Cl10(P2S6)3

Leslie Mareike Schoop, Roland Eger, Jürgen Nuss, Florian Pielnhofer, Bettina Valeska Lotsch

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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.

Original languageEnglish (US)
Pages (from-to)1818-1823
Number of pages6
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Issue number23
StatePublished - Dec 13 2017
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Inorganic Chemistry


  • Cesium
  • Quinary phases
  • Rare earths
  • Thiophosphates


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