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The First Quinary Rare Earth Thiophosphates: Cs 5 Ln 3 X 3 (P 2 S 6 ) 2 (PS 4 ) ( Ln = La, Ce, X = Br, Cl) and the Quasi‐Quaternary Cs 10 Y 4 Cl 10 (P 2 S 6 ) 3
Author(s) -
Schoop Leslie Mareike,
Eger Roland,
Nuss Jürgen,
Pielnhofer Florian,
Lotsch Bettina Valeska
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201700309
Subject(s) - quinary , orthorhombic crystal system , monoclinic crystal system , crystallography , chemistry , thiophosphate , space group , crystal structure , group (periodic table) , stereochemistry , x ray crystallography , physics , alloy , organic chemistry , diffraction , optics
We report the first examples of quinary rare earth thiophosphates with a fully ordered cation and anion distribution, Cs 5 Ln 3 X 3 (P 2 S 6 ) 2 (PS 4 ), ( Ln = La, Ce and X = Br, Cl) as well as the quasi‐quaternary Cs 10 Y 4 Cl 10 (P 2 S 6 ) 3 . These four new compounds crystallize in three different, unknown structure types. The yellowish, transparent, brittle Cs 5 Ce 3 Br 3 (P 2 S 6 ) 2 (PS 4 ) 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) Å 3 in a novel structure type. Colorless crystals of Cs 5 La 3 Br 3 (P 2 S 6 ) 2 (PS 4 ) and Cs 5 La 3 Cl 3 (P 2 S 6 ) 2 (PS 4 ) are isotypic and were obtained in the monoclinic space group P 2 1 / 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) Å 3 and a = 9.513(2), b = 14.182(3), c = 13.699(3) Å, β = 99.39(3)° and V = 1823(1) Å 3 , respectively. Both structures contain isolated hexathiohypodiphosphate(IV) [P 2 S 6 ] 4– and thiophosphate [PS 4 ] 3– units that are arranged alternately in layers. Cs 10 Y 4 Cl 10 (P 2 S 6 ) 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) Å 3 . The structure is composed of isolated [P 4/2 S 6 ] 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.