NaN3 crystallizes in the trigonal R-3m space group. Na(1) is bonded to six equivalent N(1) atoms to form edge-sharing NaN6 octahedra. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Na(1) and one N(2) atom. In the second N site, N(2) is bonded in a linear geometry to two equivalent N(1) atoms.
NaN3 crystallizes in the trigonal R-3m space group. Na(1) is bonded to six equivalent N(1) atoms to form edge-sharing NaN6 octahedra. All Na(1)-N(1) bond lengths are 2.48 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted rectangular see-saw-like geometry to three equivalent Na(1) and one N(2) atom. The N(1)-N(2) bond length is 1.18 Å. In the second N site, N(2) is bonded in a linear geometry to two equivalent N(1) atoms.