Li6NCl3 crystallizes in the triclinic P1 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) atoms. 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 3-coordinate geometry to one N(1) and two 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 distorted corner-sharing LiCl4 tetrahedra. In the sixth Li site, Li(6) is bonded in a distorted 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 distorted edge-sharing NLi8 hexagonal bipyramids. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to 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 corner-sharing ClLi4 tetrahedra. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent Li(3) and three equivalent Li(5) atoms.
Li6NCl3 crystallizes in the triclinic P1 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) atoms. There are a spread of Li(1)-N(1) bond distances ranging from 2.11-2.25 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 2.07 Å. There are a spread of Li(2)-Cl(1) bond distances ranging from 2.19-2.66 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one N(1) and two equivalent Cl(3) atoms. The Li(3)-N(1) bond length is 1.95 Å. There is one shorter (2.41 Å) and one longer (2.76 Å) Li(3)-Cl(3) bond length. 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 2.36 Å. There are a spread of Li(4)-Cl(2) bond distances ranging from 2.18-2.64 Å. In the fifth Li site, Li(5) is bonded to one Cl(2) and three equivalent Cl(3) atoms to form distorted corner-sharing LiCl4 tetrahedra. The Li(5)-Cl(2) bond length is 2.37 Å. There are a spread of Li(5)-Cl(3) bond distances ranging from 2.20-2.67 Å. In the sixth Li site, Li(6) is bonded in a distorted trigonal planar geometry to three equivalent N(1) atoms. There are a spread of Li(6)-N(1) bond distances ranging from 2.13-2.20 Å. N(1) is bonded to one Li(2), one Li(3), three equivalent Li(1), and three equivalent Li(6) atoms to form distorted edge-sharing NLi8 hexagonal bipyramids. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 4-coordinate geometry to 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 corner-sharing ClLi4 tetrahedra. In the third Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent Li(3) and three equivalent Li(5) atoms.