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Li 12 P 3 N 9 with Non‐Condensed [P 3 N 9 ] 12− ‐Rings and its High‐Pressure Polymorph Li 4 PN 3 with Infinite Chains of PN 4 ‐Tetrahedra
Author(s) -
Bertschler EvaMaria,
Niklaus Robin,
Schnick Wolfgang
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201700979
Subject(s) - crystallography , chemistry , high pressure , crystal structure , rietveld refinement , lithium (medication) , spectroscopy , solid state , thermodynamics , physics , medicine , quantum mechanics , endocrinology
Abstract Li 12 P 3 N 9 was synthesized by solid‐state reaction of Li 3 N and P 3 N 5 at 790 °C. It is made up of non‐condensed [P 3 N 9 ] 12− dreier ‐rings of PN 4 ‐tetrahedra. The corresponding high‐pressure polymorph, Li 4 PN 3 , was synthesized under high‐pressure/high‐temperature conditions from Li 12 P 3 N 9 or LiPN 2 and Li 7 PN 4 at 6 or 7 GPa, respectively, using the multianvil technique. Li 4 PN 3 is the first lithium catena ‐nitridophosphate and contains PN 3 zweier ‐chains of corner sharing PN 4 ‐tetrahedra. To confirm the structure elucidated from single‐crystal X‐ray data, Rietveld refinement, 6 Li, 7 Li, and 31 P solid‐state NMR spectroscopy, FTIR spectroscopy and EDX measurements were carried out. To examine the phase transition of Li 12 P 3 N 9 to Li 4 PN 3 at 6 GPa and to corroborate the latter as the corresponding high‐pressure polymorph, DFT calculations were conducted. Electronic band gap and electron localization function (ELF) calculations were carried out to elucidate the electronic properties and bonding behavior of both polymorphs.