Li5NCl2 crystallizes in the trigonal R-3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Cl(1) atoms to form edge-sharing LiCl6 octahedra. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one N(1) and three equivalent Cl(1) atoms. In the third Li site, Li(3) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. N(1) is bonded to two equivalent Li(2) and six equivalent Li(3) atoms to form NLi8 hexagonal bipyramids that share corners with six equivalent Cl(1)Li6 octahedra and edges with six equivalent N(1)Li8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 57°. Cl(1) is bonded to three equivalent Li(1) and three equivalent Li(2) atoms to form ClLi6 octahedra that share corners with three equivalent N(1)Li8 hexagonal bipyramids, corners with three equivalent Cl(1)Li6 octahedra, and edges with nine equivalent Cl(1)Li6 octahedra. The corner-sharing octahedra are not tilted.
Li5NCl2 crystallizes in the trigonal R-3m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to six equivalent Cl(1) atoms to form edge-sharing LiCl6 octahedra. All Li(1)-Cl(1) bond lengths are 2.55 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one N(1) and three equivalent Cl(1) atoms. The Li(2)-N(1) bond length is 1.91 Å. All Li(2)-Cl(1) bond lengths are 2.49 Å. In the third Li site, Li(3) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. All Li(3)-N(1) bond lengths are 2.10 Å. N(1) is bonded to two equivalent Li(2) and six equivalent Li(3) atoms to form NLi8 hexagonal bipyramids that share corners with six equivalent Cl(1)Li6 octahedra and edges with six equivalent N(1)Li8 hexagonal bipyramids. The corner-sharing octahedral tilt angles are 57°. Cl(1) is bonded to three equivalent Li(1) and three equivalent Li(2) atoms to form ClLi6 octahedra that share corners with three equivalent N(1)Li8 hexagonal bipyramids, corners with three equivalent Cl(1)Li6 octahedra, and edges with nine equivalent Cl(1)Li6 octahedra. The corner-sharing octahedra are not tilted.