Na3NiN2 is Pb(Zr_(1-x)Ti_x)O3-like structured and crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to two equivalent N(1) atoms. In the second Na site, Na(2) is bonded to four equivalent N(1) atoms to form a mixture of distorted edge and corner-sharing NaN4 tetrahedra. Ni(1) is bonded in a linear geometry to two equivalent N(1) atoms. N(1) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Na(2), and one Ni(1) atom.
Na3NiN2 is Pb(Zr_(1-x)Ti_x)O3-like structured and crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to two equivalent N(1) atoms. Both Na(1)-N(1) bond lengths are 2.34 Å. In the second Na site, Na(2) is bonded to four equivalent N(1) atoms to form a mixture of distorted edge and corner-sharing NaN4 tetrahedra. There are two shorter (2.56 Å) and two longer (2.65 Å) Na(2)-N(1) bond lengths. Ni(1) is bonded in a linear geometry to two equivalent N(1) atoms. Both Ni(1)-N(1) bond lengths are 1.69 Å. N(1) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Na(2), and one Ni(1) atom.