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Syntheses, Crystal Structures, Vibrational Spectra and 31 P MAS NMR Spectra of the Thiophosphates Na M (PO 3 S)·9H 2 O ( M = Ca, Ba)
Author(s) -
Kazmierczak Karolina,
Heck Joachim G.,
Höppe Henning A.
Publication year - 2010
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.200900437
Subject(s) - crystallography , octahedron , crystal structure , chemistry , nmr spectra database , hydrate , crystal (programming language) , spectral line , crystallization , stereochemistry , physics , organic chemistry , astronomy , computer science , programming language
NaBa(PO 3 S)·9H 2 O was obtained as single‐phase crystalline powder starting from NaOH, PSCl 3 and BaCl 2 . Single‐crystals of NaCa(PO 3 S)·9H 2 O were grown by a gel crystallisation technique. The crystal structures of NaCa(PO 3 S)·9H 2 O ( P 2 1 3, Z = 4, a = 10.7845(12) Å, R 1 = 0.034, wR 2 = 0.083, 711 reflections, 64 parameters) and NaBa(PO 3 S)·9H 2 O ( P 2 1 3, Z = 4, a = 11.0216(2) Å, 754 reflections, 2 θ max = 70.0° R F 2 = 0.099, R p = 0.034, wR p = 0.047, χ 2 = 3.34) are isotypic with that of NaSr(PO 3 S)·9H 2 O and these three are homeotypic with Na M PO 4 ·9H 2 O ( M = Sr, Ba). The crystal structures of Na M (PO 3 S)·9H 2 O ( M = Ca, Ba) consist of isolated (PO 3 S) tetrahedra, [NaO 6 ] distorted octahedra and [ M O 9 ] polyhedra with the latter forming a network according to {}^3_\infty [{Na(H 2 O) 6/2 }{Ca(H 2 O) 6/2 (H 2 O) 3 }] 3+ . Nine crystal water molecules are situated in the voids of the resulting structure. The vibrational spectra of the title compounds have been measured and the relevant bands were assigned. Solid‐state 31 P MAS NMR spectra gave chemical shifts of 49 ppm for NaCa(PO 3 S)·9H 2 O, 34 ppm for NaBa(PO 3 S)·9H 2 O and 38 ppm for Na 3 (PO 3 S).