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K 2 NdP 2 S 7 : A Mixed‐Valent Neodymium(III) Thiophosphate According to K 4 Nd 2 [PS 4 ] 2 [P 2 S 6 ] with Discrete [PS 4 ] 3– and [S 3 P–PS 3 ] 4– Anions
Author(s) -
Schleid Thomas,
Hartenbach Ingo,
Komm Theresa
Publication year - 2002
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 - 10.1002/1521-3749(200201)628:1<7::aid-zaac7>3.0.co;2-s
Subject(s) - thiophosphate , monoclinic crystal system , chemistry , crystallography , tetrahedron , sulfur , potassium , crystal structure , inorganic chemistry , organic chemistry
Pale blue, lath‐shaped single crystals of K 2 NdP 2 S 7 (≡ K 4 Nd 2 [PS 4 ] 2 [P 2 S 6 ]; monoclinic, P2 1 /n, a = 904.76(8), b = 677.38(6), c = 1988.7(2) pm, β = 97.295(5)°, Z = 2) are obtained by the reaction of Nd, S and P 2 S 5 with an excess of KCl as a flux in evacuated silica tubes at 750 °C (7 d) which should produce Nd[PS 4 ] instead. Beside isolated [PS 4 ] 3– tetrahedra, the crystal structure contains discrete ethane‐analogous [P 2 S 6 ] 4– (≡ [S 3 P–PS 3 ] 4– ) units in staggered conformation with tetravalent phosphorus cations and a P–P distance of 219 pm. The two crystallographically different potassium cations show coordination numbers of nine and ten in the shape of distorted mono‐ and bicapped square antiprisms. Finally, the Nd 3+ cations are surrounded by eight sulfur atoms arranged as (uncapped) square antiprisms. The entire structure is dominated by (K1) + containing $^2_{\infty}$ {(Nd 2 [PS 4 ] 2 [P 2 S 6 ]) 4– } layers parallel (101) which are three‐dimensionally interconnected by (K2) + cations.