Na3N crystallizes in the hexagonal P6_3cm space group. There are four 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 trigonal planar geometry to three equivalent N(1) atoms. In the third Na site, Na(3) is bonded in a distorted trigonal planar geometry to three equivalent N(1) atoms. In the fourth Na site, Na(4) is bonded in a distorted bent 120 degrees geometry to two equivalent N(1) atoms. N(1) is bonded in a 8-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(4), and three equivalent Na(3) atoms.
Na3N crystallizes in the hexagonal P6_3cm space group. There are four 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 2.55 Å. In the second Na site, Na(2) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. All Na(2)-N(1) bond lengths are 2.60 Å. In the third Na site, Na(3) is bonded in a distorted trigonal planar geometry to three equivalent N(1) atoms. There is one shorter (2.54 Å) and two longer (2.75 Å) Na(3)-N(1) bond lengths. In the fourth Na site, Na(4) is bonded in a distorted bent 120 degrees geometry to two equivalent N(1) atoms. There is one shorter (2.52 Å) and one longer (2.66 Å) Na(4)-N(1) bond length. N(1) is bonded in a 8-coordinate geometry to one Na(1), two equivalent Na(2), two equivalent Na(4), and three equivalent Na(3) atoms.