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(3), and one S(4) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(4), and one S(5) atom. In the third Li site, Li(3) 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(7)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, and  an edgeedge with one Li(7)S4 tetrahedra. In the fourth Li site, Li(4) is bonded in a distorted trigonal planar geometry to one S(1), one S(3), and one S(6) atom. In the fifth Li site, Li(5) is bonded in a 3-coordinate geometry to one S(2), one S(4), and one S(5) atom. In the sixth Li site, Li(6) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form distorted LiS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, and corners with three equivalent Li(7)S4 tetrahedra. In the seventh Li site, Li(7) is bonded to one S(1), one S(2), one S(5), and one S(6) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, corners with three equivalent Li(6)S4 tetrahedra, and  an edgeedge with one Li(3)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(3)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, and corners with two equivalent 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(6), and one Li(7) atom to form distorted SLi6 pentagonal pyramids that share corners with three equivalent S(2)Li6 pentagonal pyramids, corners with three equivalent S(6)Li3Nb trigonal pyramids, and  an edgeedge with one S(2)Li6 pentagonal pyramid. In the second S site, S(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Li(6), and one Li(7) atom to form distorted SLi6 pentagonal pyramids that share corners with three equivalent S(1)Li6 pentagonal pyramids, corners with two equivalent S(6)Li3Nb trigonal pyramids, and  an edgeedge with one S(1)Li6 pentagonal pyramid. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Nb(1) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(5), one Li(6), and one Nb(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Li(7), and one Nb(1) atom. In the sixth S site, S(6) is bonded to one Li(4), one Li(6), one Li(7), and one Nb(1) atom to form distorted corner-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(3), and one S(4) atom. The Li(1)-S(1) bond length is 2.54 Å. The Li(1)-S(2) bond length is 2.46 Å. The Li(1)-S(3) bond length is 2.54 Å. The Li(1)-S(4) bond length is 2.94 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one S(1), one S(2), one S(4), and one S(5) atom. The Li(2)-S(1) bond length is 2.53 Å. The Li(2)-S(2) bond length is 2.54 Å. The Li(2)-S(4) bond length is 2.60 Å. The Li(2)-S(5) bond length is 2.96 Å. In the third Li site, Li(3) 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(7)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, and  an edgeedge with one Li(7)S4 tetrahedra. The Li(3)-S(1) bond length is 2.54 Å. The Li(3)-S(2) bond length is 2.48 Å. The Li(3)-S(3) bond length is 2.50 Å. The Li(3)-S(5) bond length is 2.48 Å. In the fourth Li site, Li(4) is bonded in a distorted trigonal planar geometry to one S(1), one S(3), and one S(6) atom. The Li(4)-S(1) bond length is 2.39 Å. The Li(4)-S(3) bond length is 2.41 Å. The Li(4)-S(6) bond length is 2.47 Å. In the fifth Li site, Li(5) is bonded in a 3-coordinate geometry to one S(2), one S(4), and one S(5) atom. The Li(5)-S(2) bond length is 2.35 Å. The Li(5)-S(4) bond length is 2.47 Å. The Li(5)-S(5) bond length is 2.51 Å. In the sixth Li site, Li(6) is bonded to one S(1), one S(2), one S(4), and one S(6) atom to form distorted LiS4 tetrahedra that share corners with two equivalent Li(3)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, and corners with three equivalent Li(7)S4 tetrahedra. The Li(6)-S(1) bond length is 2.54 Å. The Li(6)-S(2) bond length is 2.54 Å. The Li(6)-S(4) bond length is 2.77 Å. The Li(6)-S(6) bond length is 2.52 Å. In the seventh Li site, Li(7) is bonded to one S(1), one S(2), one S(5), and one S(6) atom to form distorted LiS4 tetrahedra that share  a cornercorner with one Li(3)S4 tetrahedra, corners with two equivalent Nb(1)S4 tetrahedra, corners with three equivalent Li(6)S4 tetrahedra, and  an edgeedge with one Li(3)S4 tetrahedra. The Li(7)-S(1) bond length is 2.49 Å. The Li(7)-S(2) bond length is 2.53 Å. The Li(7)-S(5) bond length is 2.50 Å. The Li(7)-S(6) bond length is 2.45 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(3)S4 tetrahedra, corners with two equivalent Li(6)S4 tetrahedra, and corners with two equivalent Li(7)S4 tetrahedra. The Nb(1)-S(3) bond length is 2.28 Å. The Nb(1)-S(4) bond length is 2.28 Å. The Nb(1)-S(5) bond length is 2.29 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(6), and one Li(7) atom to form distorted SLi6 pentagonal pyramids that share corners with three equivalent S(2)Li6 pentagonal pyramids, corners with three equivalent S(6)Li3Nb trigonal pyramids, and  an edgeedge with one S(2)Li6 pentagonal pyramid. In the second S site, S(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Li(6), and one Li(7) atom to form distorted SLi6 pentagonal pyramids that share corners with three equivalent S(1)Li6 pentagonal pyramids, corners with two equivalent S(6)Li3Nb trigonal pyramids, and  an edgeedge with one S(1)Li6 pentagonal pyramid. In the third S site, S(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Li(4), and one Nb(1) atom. In the fourth S site, S(4) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(5), one Li(6), and one Nb(1) atom. In the fifth S site, S(5) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one Li(5), one Li(7), and one Nb(1) atom. In the sixth S site, S(6) is bonded to one Li(4), one Li(6), one Li(7), and one Nb(1) atom to form distorted corner-sharing SLi3Nb trigonal pyramids.