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LiNiN crystallizes in the hexagonal P-6m2 space group. The structure is three-dimensional. Li1+ is bonded in a trigonal planar geometry to three equivalent N3- atoms. All Li–N bond lengths are 2.09 Å. Ni2+ is bonded in a linear geometry to two equivalent N3- atoms. Both Ni–N bond lengths are 1.71 Å. N3- is bonded to three equivalent Li1+ and two equivalent Ni2+ atoms to form corner-sharing NLi3Ni2 trigonal bipyramids.
Li5(NiN)3 crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. there are two inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in a trigonal planar geometry to three equivalent N3- atoms. All Li–N bond lengths are 2.08 Å. In the second Li1+ site, Li1+ is bonded in a 2-coordinate geometry to three equivalent N3- atoms. There are two shorter (2.13 Å) and one longer (2.42 Å) Li–N bond lengths. Ni+1.33+ is bonded in a linear geometry to two equivalent N3- atoms. Both Ni–N bond lengths are 1.74 Å. N3- is bonded to five Li1+ and two equivalent Ni+1.33+ atoms to form a mixture of distorted edge and corner-sharing NLi5Ni2 pentagonal bipyramids.