Li8NbS6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with two equivalent Nb(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with six equivalent Li(1)S4 tetrahedra, edges with two equivalent Li(3)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. In the second Li site, Li(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 tetrahedra that share corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(3)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra,  an edgeedge with one Nb(1)S4 tetrahedra, and edges with three equivalent Li(1)S4 tetrahedra. In the third Li site, Li(3) is bonded to one S(2) and three equivalent S(1) atoms to form LiS4 tetrahedra that share corners with three equivalent Li(3)S4 tetrahedra, corners with three equivalent Nb(1)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra, and edges with three equivalent Li(1)S4 tetrahedra. Nb(1) is bonded to one S(3) and three equivalent S(1) atoms to form NbS4 tetrahedra that share corners with six equivalent Li(1)S4 tetrahedra, corners with six equivalent Li(3)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Nb(1) atom to form corner-sharing SLi4Nb trigonal bipyramids. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent Li(2) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and one Nb(1) atom.
Li8NbS6 crystallizes in the hexagonal P6_3cm space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with two equivalent Nb(1)S4 tetrahedra, corners with four equivalent Li(2)S4 tetrahedra, corners with six equivalent Li(1)S4 tetrahedra, edges with two equivalent Li(3)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. The Li(1)-S(1) bond length is 2.48 Å. The Li(1)-S(3) bond length is 2.53 Å. Both Li(1)-S(2) bond lengths are 2.47 Å. In the second Li site, Li(2) is bonded to one S(1), one S(3), and two equivalent S(2) atoms to form distorted LiS4 tetrahedra that share corners with four equivalent Li(1)S4 tetrahedra, corners with four equivalent Li(3)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra,  an edgeedge with one Nb(1)S4 tetrahedra, and edges with three equivalent Li(1)S4 tetrahedra. The Li(2)-S(1) bond length is 2.48 Å. The Li(2)-S(3) bond length is 2.69 Å. Both Li(2)-S(2) bond lengths are 2.46 Å. In the third Li site, Li(3) is bonded to one S(2) and three equivalent S(1) atoms to form LiS4 tetrahedra that share corners with three equivalent Li(3)S4 tetrahedra, corners with three equivalent Nb(1)S4 tetrahedra, corners with six equivalent Li(2)S4 tetrahedra, and edges with three equivalent Li(1)S4 tetrahedra. The Li(3)-S(2) bond length is 2.48 Å. All Li(3)-S(1) bond lengths are 2.46 Å. Nb(1) is bonded to one S(3) and three equivalent S(1) atoms to form NbS4 tetrahedra that share corners with six equivalent Li(1)S4 tetrahedra, corners with six equivalent Li(3)S4 tetrahedra, and edges with three equivalent Li(2)S4 tetrahedra. The Nb(1)-S(3) bond length is 2.39 Å. All Nb(1)-S(1) bond lengths are 2.33 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), two equivalent Li(3), and one Nb(1) atom to form corner-sharing SLi4Nb trigonal bipyramids. In the second S site, S(2) is bonded in a 7-coordinate geometry to one Li(3), three equivalent Li(1), and three equivalent Li(2) atoms. In the third S site, S(3) is bonded in a 7-coordinate geometry to three equivalent Li(1), three equivalent Li(2), and one Nb(1) atom.