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Na3N is alpha Rhenium trioxide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Na1+ is bonded in a linear geometry to two equivalent N3- atoms. Both Na–N bond lengths are 2.37 Å. N3- is bonded to six equivalent Na1+ atoms to form corner-sharing NNa6 octahedra. The corner-sharing octahedral tilt angles are 0°.
Na3N is alpha bismuth trifluoride structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 8-coordinate geometry to eight equivalent Na1+ and six equivalent N3- atoms. All Na–Na bond lengths are 2.73 Å. All Na–N bond lengths are 3.15 Å. In the second Na1+ site, Na1+ is bonded to four equivalent Na1+ and four equivalent N3- atoms to form a mixture of edge, corner, and face-sharing NaNa4N4 tetrahedra. All Na–N bond lengths are 2.73 Å. N3- is bonded in a body-centered cubic geometry to fourteen Na1+ atoms.
Na3N crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. there are two inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a trigonal planar geometry to three equivalent N3- atoms. All Na–N bond lengths are 2.59 Å. In the second Na1+ site, Na1+ is bonded in a linear geometry to two equivalent N3- atoms. Both Na–N bond lengths are 2.38 Å. N3- is bonded to eight Na1+ atoms to form a mixture of corner and edge-sharing NNa8 hexagonal bipyramids.