Na5LiN2 crystallizes in the monoclinic Pm space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted trigonal planar geometry to one N(1) and two equivalent N(2) atoms. In the second Na site, Na(2) is bonded in a distorted trigonal planar geometry to one N(2) and two equivalent N(1) atoms. In the third Na site, Na(3) is bonded in a distorted trigonal planar geometry to one N(1) and two equivalent N(2) atoms. In the fourth Na site, Na(4) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) atoms. In the fifth Na site, Na(5) is bonded in a linear geometry to two equivalent N(1) atoms. Li(1) is bonded in a linear geometry to two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Na(1), one Na(3), two equivalent Na(2), two equivalent Na(4), and two equivalent Na(5) atoms to form distorted NNa8 hexagonal bipyramids that share corners with two equivalent N(1)Na8 hexagonal bipyramids, edges with two equivalent N(1)Na8 hexagonal bipyramids, and edges with four equivalent N(2)Na6Li2 hexagonal bipyramids. In the second N site, N(2) is bonded to one Na(2), one Na(4), two equivalent Na(1), two equivalent Na(3), and two equivalent Li(1) atoms to form distorted NNa6Li2 hexagonal bipyramids that share corners with two equivalent N(2)Na6Li2 hexagonal bipyramids, edges with two equivalent N(2)Na6Li2 hexagonal bipyramids, and edges with four equivalent N(1)Na8 hexagonal bipyramids.
Na5LiN2 crystallizes in the monoclinic Pm space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted trigonal planar geometry to one N(1) and two equivalent N(2) atoms. The Na(1)-N(1) bond length is 2.59 Å. Both Na(1)-N(2) bond lengths are 2.60 Å. In the second Na site, Na(2) is bonded in a distorted trigonal planar geometry to one N(2) and two equivalent N(1) atoms. The Na(2)-N(2) bond length is 2.56 Å. Both Na(2)-N(1) bond lengths are 2.60 Å. In the third Na site, Na(3) is bonded in a distorted trigonal planar geometry to one N(1) and two equivalent N(2) atoms. The Na(3)-N(1) bond length is 2.63 Å. Both Na(3)-N(2) bond lengths are 2.57 Å. In the fourth Na site, Na(4) is bonded in a trigonal planar geometry to one N(2) and two equivalent N(1) atoms. The Na(4)-N(2) bond length is 2.57 Å. Both Na(4)-N(1) bond lengths are 2.59 Å. In the fifth Na site, Na(5) is bonded in a linear geometry to two equivalent N(1) atoms. Both Na(5)-N(1) bond lengths are 2.20 Å. Li(1) is bonded in a linear geometry to two equivalent N(2) atoms. There is one shorter (2.19 Å) and one longer (2.21 Å) Li(1)-N(2) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Na(1), one Na(3), two equivalent Na(2), two equivalent Na(4), and two equivalent Na(5) atoms to form distorted NNa8 hexagonal bipyramids that share corners with two equivalent N(1)Na8 hexagonal bipyramids, edges with two equivalent N(1)Na8 hexagonal bipyramids, and edges with four equivalent N(2)Na6Li2 hexagonal bipyramids. In the second N site, N(2) is bonded to one Na(2), one Na(4), two equivalent Na(1), two equivalent Na(3), and two equivalent Li(1) atoms to form distorted NNa6Li2 hexagonal bipyramids that share corners with two equivalent N(2)Na6Li2 hexagonal bipyramids, edges with two equivalent N(2)Na6Li2 hexagonal bipyramids, and edges with four equivalent N(1)Na8 hexagonal bipyramids.