NaLi5N2 crystallizes in the monoclinic Pm space group. Na(1) is bonded in a 2-coordinate geometry to one N(1) and two equivalent N(2) atoms. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a linear geometry to two equivalent N(2) atoms. In the second Li site, Li(2) is bonded in a distorted linear geometry to two equivalent N(1) atoms. In the third Li site, Li(3) is bonded in a 2-coordinate geometry to one N(1) and two equivalent N(2) atoms. In the fourth Li site, Li(4) is bonded in a distorted trigonal planar geometry to one N(2) and two equivalent N(1) atoms. In the fifth Li site, Li(5) is bonded in a bent 120 degrees geometry to two equivalent N(1) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 8-coordinate geometry to one Na(1), one Li(3), two equivalent Li(2), two equivalent Li(4), and two equivalent Li(5) atoms. In the second N site, N(2) is bonded to two equivalent Na(1), one Li(4), two equivalent Li(1), and two equivalent Li(3) atoms to form a mixture of distorted edge and corner-sharing NNa2Li5 pentagonal bipyramids.
NaLi5N2 crystallizes in the monoclinic Pm space group. Na(1) is bonded in a 2-coordinate geometry to one N(1) and two equivalent N(2) atoms. The Na(1)-N(1) bond length is 2.72 Å. Both Na(1)-N(2) bond lengths are 2.49 Å. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded in a linear geometry to two equivalent N(2) atoms. Both Li(1)-N(2) bond lengths are 1.93 Å. In the second Li site, Li(2) is bonded in a distorted linear geometry to two equivalent N(1) atoms. There is one shorter (1.95 Å) and one longer (1.96 Å) Li(2)-N(1) bond length. In the third Li site, Li(3) is bonded in a 2-coordinate geometry to one N(1) and two equivalent N(2) atoms. The Li(3)-N(1) bond length is 2.43 Å. Both Li(3)-N(2) bond lengths are 1.98 Å. In the fourth Li site, Li(4) is bonded in a distorted trigonal planar geometry to one N(2) and two equivalent N(1) atoms. The Li(4)-N(2) bond length is 2.03 Å. Both Li(4)-N(1) bond lengths are 2.16 Å. In the fifth Li site, Li(5) is bonded in a bent 120 degrees geometry to two equivalent N(1) atoms. Both Li(5)-N(1) bond lengths are 2.06 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a 8-coordinate geometry to one Na(1), one Li(3), two equivalent Li(2), two equivalent Li(4), and two equivalent Li(5) atoms. In the second N site, N(2) is bonded to two equivalent Na(1), one Li(4), two equivalent Li(1), and two equivalent Li(3) atoms to form a mixture of distorted edge and corner-sharing NNa2Li5 pentagonal bipyramids.