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NaPN2 crystallizes in the tetragonal I-42d space group. The structure is three-dimensional. Na1+ is bonded in a 4-coordinate geometry to four equivalent N3- atoms. All Na–N bond lengths are 2.42 Å. P5+ is bonded to four equivalent N3- atoms to form corner-sharing PN4 tetrahedra. All P–N bond lengths are 1.65 Å. N3- is bonded in a 4-coordinate geometry to two equivalent Na1+ and two equivalent P5+ atoms.
NaP4N7 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Na1+ is bonded in a 5-coordinate geometry to five N3- atoms. There are a spread of Na–N bond distances ranging from 2.46–2.73 Å. There are two inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four N3- atoms to form corner-sharing PN4 tetrahedra. There are a spread of P–N bond distances ranging from 1.58–1.73 Å. In the second P5+ site, P5+ is bonded to four N3- atoms to form corner-sharing PN4 tetrahedra. There are a spread of P–N bond distances ranging from 1.60–1.75 Å. There are four inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to three P5+ atoms. In the second N3- site, N3- is bonded in a 3-coordinate geometry to one Na1+ and two P5+ atoms. In the third N3- site, N3- is bonded in a 3-coordinate geometry to one Na1+ and two equivalent P5+ atoms. In the fourth N3- site, N3- is bonded in a distorted bent 150 degrees geometry to one Na1+ and two equivalent P5+ atoms.