Na5LiN2 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted bent 150 degrees geometry to two equivalent N(1) atoms. In the second Na site, Na(2) is bonded in a linear geometry to two equivalent N(1) atoms. In the third Na site, Na(3) is bonded in a bent 150 degrees geometry to two equivalent N(1) atoms. In the fourth Na site, Na(4) is bonded in a bent 150 degrees geometry to two equivalent N(1) atoms. Li(1) is bonded in a bent 150 degrees geometry to two equivalent N(1) atoms. N(1) is bonded to one Na(1), one Na(3), one Na(4), two equivalent Na(2), and one Li(1) atom to form distorted corner-sharing NNa5Li octahedra. The corner-sharing octahedral tilt angles range from 4-40°.
Na5LiN2 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted bent 150 degrees geometry to two equivalent N(1) atoms. Both Na(1)-N(1) bond lengths are 2.40 Å. In the second Na site, Na(2) is bonded in a linear geometry to two equivalent N(1) atoms. There is one shorter (2.48 Å) and one longer (2.53 Å) Na(2)-N(1) bond length. In the third Na site, Na(3) is bonded in a bent 150 degrees geometry to two equivalent N(1) atoms. Both Na(3)-N(1) bond lengths are 2.35 Å. In the fourth Na site, Na(4) is bonded in a bent 150 degrees geometry to two equivalent N(1) atoms. Both Na(4)-N(1) bond lengths are 2.37 Å. Li(1) is bonded in a bent 150 degrees geometry to two equivalent N(1) atoms. Both Li(1)-N(1) bond lengths are 1.95 Å. N(1) is bonded to one Na(1), one Na(3), one Na(4), two equivalent Na(2), and one Li(1) atom to form distorted corner-sharing NNa5Li octahedra. The corner-sharing octahedral tilt angles range from 4-40°.