Li7NbS6 crystallizes in the monoclinic Pc space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(4), and one S(5) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one S(1), one S(4), and one S(6) atom. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), and one S(3) atom. In the fourth Li site, Li(4) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra, corners with two equivalent Li(7)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, and  an edgeedge with one Li(5)S4 tetrahedra. In the fifth Li site, Li(5) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(4)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra,  an edgeedge with one Li(4)S4 tetrahedra, and  an edgeedge with one Li(7)S4 tetrahedra. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(5), and one S(6) atom. In the seventh Li site, Li(7) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra, corners with two equivalent Li(4)S4 tetrahedra,  an edgeedge with one Li(5)S4 tetrahedra, and  an edgeedge with one Nb(1)S4 tetrahedra. Nb(1) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form NbS4 tetrahedra that share corners with two equivalent Li(4)S4 tetrahedra, corners with two equivalent Li(5)S4 tetrahedra, and  an edgeedge with one Li(7)S4 tetrahedra. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Li(7) atom to form a mixture of distorted corner and edge-sharing SLi7 pentagonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one Li(7) atom. In the third S site, S(3) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(5), one Li(7), and one Nb(1) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Nb(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one Li(6), and one Nb(1) atom. In the sixth S site, S(6) is bonded to one Li(2), one Li(6), one Li(7), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing SLi3Nb trigonal pyramids.
Li7NbS6 crystallizes in the monoclinic Pc space group. There are seven inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(4), and one S(5) atom. The Li(1)-S(1) bond length is 2.48 Å. The Li(1)-S(2) bond length is 2.43 Å. The Li(1)-S(4) bond length is 2.50 Å. The Li(1)-S(5) bond length is 2.85 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one S(1), one S(4), and one S(6) atom. The Li(2)-S(1) bond length is 2.49 Å. The Li(2)-S(4) bond length is 2.78 Å. The Li(2)-S(6) bond length is 2.61 Å. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to one S(1), one S(2), and one S(3) atom. The Li(3)-S(1) bond length is 2.52 Å. The Li(3)-S(2) bond length is 2.45 Å. The Li(3)-S(3) bond length is 2.45 Å. In the fourth Li site, Li(4) is bonded to one S(1), one S(2), one S(4), and one S(5) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra, corners with two equivalent Li(7)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, and  an edgeedge with one Li(5)S4 tetrahedra. The Li(4)-S(1) bond length is 2.57 Å. The Li(4)-S(2) bond length is 2.53 Å. The Li(4)-S(4) bond length is 2.54 Å. The Li(4)-S(5) bond length is 2.66 Å. In the fifth Li site, Li(5) is bonded to one S(1), one S(2), one S(3), and one S(5) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(4)S4 tetrahedra,  a cornercorner with one Li(7)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra,  an edgeedge with one Li(4)S4 tetrahedra, and  an edgeedge with one Li(7)S4 tetrahedra. The Li(5)-S(1) bond length is 2.50 Å. The Li(5)-S(2) bond length is 2.52 Å. The Li(5)-S(3) bond length is 2.51 Å. The Li(5)-S(5) bond length is 2.49 Å. In the sixth Li site, Li(6) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(5), and one S(6) atom. The Li(6)-S(1) bond length is 2.52 Å. The Li(6)-S(2) bond length is 2.44 Å. The Li(6)-S(5) bond length is 2.94 Å. The Li(6)-S(6) bond length is 2.47 Å. In the seventh Li site, Li(7) is bonded to one S(1), one S(2), one S(3), and one S(6) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(5)S4 tetrahedra, corners with two equivalent Li(4)S4 tetrahedra,  an edgeedge with one Li(5)S4 tetrahedra, and  an edgeedge with one Nb(1)S4 tetrahedra. The Li(7)-S(1) bond length is 2.49 Å. The Li(7)-S(2) bond length is 2.42 Å. The Li(7)-S(3) bond length is 2.51 Å. The Li(7)-S(6) bond length is 2.52 Å. Nb(1) is bonded to one S(3), one S(4), one S(5), and one S(6) atom to form NbS4 tetrahedra that share corners with two equivalent Li(4)S4 tetrahedra, corners with two equivalent Li(5)S4 tetrahedra, and  an edgeedge with one Li(7)S4 tetrahedra. The Nb(1)-S(3) bond length is 2.30 Å. The Nb(1)-S(4) bond length is 2.28 Å. The Nb(1)-S(5) bond length is 2.28 Å. The Nb(1)-S(6) bond length is 2.29 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), one Li(6), and one Li(7) atom to form a mixture of distorted corner and edge-sharing SLi7 pentagonal bipyramids. In the second S site, S(2) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one Li(6), and one Li(7) atom. In the third S site, S(3) is bonded in a distorted see-saw-like geometry to one Li(3), one Li(5), one Li(7), and one Nb(1) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Li(4), and one Nb(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Li(1), one Li(4), one Li(5), one Li(6), and one Nb(1) atom. In the sixth S site, S(6) is bonded to one Li(2), one Li(6), one Li(7), and one Nb(1) atom to form a mixture of distorted corner and edge-sharing SLi3Nb trigonal pyramids.