Li6NCl3 crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to three equivalent N(1) and one Cl(1) atom. In the second Li site, Li(2) is bonded to one N(1) and three equivalent Cl(1) atoms to form distorted LiNCl3 tetrahedra that share corners with three equivalent Li(4)Cl4 tetrahedra and corners with six equivalent Li(2)NCl3 tetrahedra. In the third Li site, Li(3) is bonded in a distorted single-bond geometry to one N(1) and three equivalent Cl(3) atoms. In the fourth Li site, Li(4) is bonded to one Cl(1) and three equivalent Cl(2) atoms to form LiCl4 tetrahedra that share corners with three equivalent Li(5)Cl4 tetrahedra, corners with three equivalent Li(2)NCl3 tetrahedra, and corners with six equivalent Li(4)Cl4 tetrahedra. In the fifth Li site, Li(5) is bonded to one Cl(2) and three equivalent Cl(3) atoms to form corner-sharing LiCl4 tetrahedra. In the sixth Li site, Li(6) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. N(1) is bonded to one Li(2), one Li(3), three equivalent Li(1), and three equivalent Li(6) atoms to form NLi8 hexagonal bipyramids that share corners with three equivalent Cl(3)Li6 octahedra and edges with six equivalent N(1)Li8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 52-53°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), and three equivalent Li(2) atoms. In the second Cl site, Cl(2) is bonded to one Li(5) and three equivalent Li(4) atoms to form ClLi4 tetrahedra that share corners with three equivalent Cl(3)Li6 octahedra and corners with six equivalent Cl(2)Li4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-64°. In the third Cl site, Cl(3) is bonded to three equivalent Li(3) and three equivalent Li(5) atoms to form ClLi6 octahedra that share corners with three equivalent N(1)Li8 hexagonal bipyramids, corners with three equivalent Cl(2)Li4 tetrahedra, and edges with six equivalent Cl(3)Li6 octahedra.
Li6NCl3 crystallizes in the monoclinic Cm space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to three equivalent N(1) and one Cl(1) atom. There is one shorter (2.17 Å) and two longer (2.18 Å) Li(1)-N(1) bond lengths. The Li(1)-Cl(1) bond length is 2.81 Å. In the second Li site, Li(2) is bonded to one N(1) and three equivalent Cl(1) atoms to form distorted LiNCl3 tetrahedra that share corners with three equivalent Li(4)Cl4 tetrahedra and corners with six equivalent Li(2)NCl3 tetrahedra. The Li(2)-N(1) bond length is 1.99 Å. All Li(2)-Cl(1) bond lengths are 2.42 Å. In the third Li site, Li(3) is bonded in a distorted single-bond geometry to one N(1) and three equivalent Cl(3) atoms. The Li(3)-N(1) bond length is 1.87 Å. All Li(3)-Cl(3) bond lengths are 2.72 Å. In the fourth Li site, Li(4) is bonded to one Cl(1) and three equivalent Cl(2) atoms to form LiCl4 tetrahedra that share corners with three equivalent Li(5)Cl4 tetrahedra, corners with three equivalent Li(2)NCl3 tetrahedra, and corners with six equivalent Li(4)Cl4 tetrahedra. The Li(4)-Cl(1) bond length is 2.29 Å. All Li(4)-Cl(2) bond lengths are 2.40 Å. In the fifth Li site, Li(5) is bonded to one Cl(2) and three equivalent Cl(3) atoms to form corner-sharing LiCl4 tetrahedra. The Li(5)-Cl(2) bond length is 2.28 Å. All Li(5)-Cl(3) bond lengths are 2.42 Å. In the sixth Li site, Li(6) is bonded in a trigonal planar geometry to three equivalent N(1) atoms. All Li(6)-N(1) bond lengths are 2.16 Å. N(1) is bonded to one Li(2), one Li(3), three equivalent Li(1), and three equivalent Li(6) atoms to form NLi8 hexagonal bipyramids that share corners with three equivalent Cl(3)Li6 octahedra and edges with six equivalent N(1)Li8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 52-53°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), and three equivalent Li(2) atoms. In the second Cl site, Cl(2) is bonded to one Li(5) and three equivalent Li(4) atoms to form ClLi4 tetrahedra that share corners with three equivalent Cl(3)Li6 octahedra and corners with six equivalent Cl(2)Li4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-64°. In the third Cl site, Cl(3) is bonded to three equivalent Li(3) and three equivalent Li(5) atoms to form ClLi6 octahedra that share corners with three equivalent N(1)Li8 hexagonal bipyramids, corners with three equivalent Cl(2)Li4 tetrahedra, and edges with six equivalent Cl(3)Li6 octahedra.