Na3Li3N2 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted water-like geometry to one Na(2) and two equivalent N(1) atoms. In the second Na site, Na(2) is bonded to two equivalent Na(1) and four equivalent Li(1) atoms to form a mixture of corner and edge-sharing NaNa2Li4 octahedra. The corner-sharing octahedra are not tilted. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to four equivalent Na(2) atoms. In the second Li site, Li(2) is bonded to four equivalent N(1) atoms to form distorted corner-sharing LiN4 tetrahedra. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. N(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Li(2), and two equivalent Li(3) atoms.
Na3Li3N2 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted water-like geometry to one Na(2) and two equivalent N(1) atoms. The Na(1)-Na(2) bond length is 3.00 Å. Both Na(1)-N(1) bond lengths are 2.41 Å. In the second Na site, Na(2) is bonded to two equivalent Na(1) and four equivalent Li(1) atoms to form a mixture of corner and edge-sharing NaNa2Li4 octahedra. The corner-sharing octahedra are not tilted. All Na(2)-Li(1) bond lengths are 2.68 Å. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to four equivalent Na(2) atoms. In the second Li site, Li(2) is bonded to four equivalent N(1) atoms to form distorted corner-sharing LiN4 tetrahedra. All Li(2)-N(1) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to four equivalent N(1) atoms. All Li(3)-N(1) bond lengths are 2.11 Å. N(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Li(2), and two equivalent Li(3) atoms.