DOE OSTI2020
NaPS3 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. Na1+ is bonded in a 6-coordinate geometry to six S2- atoms. There are a spread of Na–S bond distances ranging from 2.90–3.32 Å. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four S2- atoms to form edge-sharing PS4 tetrahedra. There are two shorter (2.00 Å) and two longer (2.14 Å) P–S bond lengths. In the second P5+ site, P5+ is bonded to four S2- atoms to form edge-sharing PS4 tetrahedra. There are a spread of P–S bond distances ranging from 1.98–2.18 Å. There are five inequivalent S2- sites. In the first S2- site, S2- is bonded in a 2-coordinate geometry to one Na1+ and two P5+ atoms. In the second S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Na1+ and one P5+ atom. In the third S2- site, S2- is bonded in a 5-coordinate geometry to four equivalent Na1+ and one P5+ atom. In the fourth S2- site, S2- is bonded in a trigonal non-coplanar geometry to two equivalent Na1+ and one P5+ atom. In the fifth S2- site, S2- is bonded in a 3-coordinate geometry to two equivalent Na1+ and one P5+ atom.