Na3N crystallizes in the hexagonal P6/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. In the second Na site, Na(2) is bonded in a linear geometry to two equivalent N(1) atoms. N(1) is bonded to two equivalent Na(2) and six equivalent Na(1) atoms to form a mixture of edge and corner-sharing NNa8 hexagonal bipyramids.
Na3N crystallizes in the hexagonal P6/mmm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. All Na(1)-N(1) bond lengths are 2.59 Å. In the second Na site, Na(2) is bonded in a linear geometry to two equivalent N(1) atoms. Both Na(2)-N(1) bond lengths are 2.38 Å. N(1) is bonded to two equivalent Na(2) and six equivalent Na(1) atoms to form a mixture of edge and corner-sharing NNa8 hexagonal bipyramids.