Li3Sb11S18 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(13), one S(15), one S(4), one S(5), one S(8), and one S(9) atom to form LiS6 octahedra that share  a cornercorner with one Sb(2)S6 octahedra, corners with two equivalent Sb(8)S5 square pyramids, corners with two equivalent Sb(9)S5 square pyramids, edges with two equivalent Li(3)S6 octahedra,  an edgeedge with one Sb(8)S5 square pyramid,  an edgeedge with one Sb(9)S5 square pyramid, edges with two equivalent Sb(3)S5 square pyramids, and edges with two equivalent Sb(4)S5 square pyramids. The corner-sharing octahedral tilt angles are 42°. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one S(11), one S(2), one S(6), one S(7), and one S(9) atom. In the third Li site, Li(3) is bonded to one S(12), one S(13), one S(15), one S(16), one S(5), and one S(8) atom to form LiS6 octahedra that share  a cornercorner with one Sb(10)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Sb(3)S5 square pyramids, corners with two equivalent Sb(4)S5 square pyramids, edges with two equivalent Li(1)S6 octahedra,  an edgeedge with one Sb(3)S5 square pyramid,  an edgeedge with one Sb(4)S5 square pyramid, edges with two equivalent Sb(8)S5 square pyramids, and edges with two equivalent Sb(9)S5 square pyramids. The corner-sharing octahedral tilt angles range from 42-48°. There are eleven inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one S(1), one S(11), one S(2), one S(3), and one S(6) atom to form distorted SbS5 square pyramids that share  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with three equivalent Sb(11)S6 octahedra, edges with two equivalent Sb(10)S6 octahedra,  an edgeedge with one Sb(6)S5 square pyramid, and edges with two equivalent Sb(5)S5 square pyramids. The corner-sharing octahedral tilt angles range from 5-89°. In the second Sb site, Sb(2) is bonded to one S(1), one S(10), one S(14), one S(17), one S(18), and one S(4) atom to form SbS6 octahedra that share  a cornercorner with one Li(1)S6 octahedra,  a cornercorner with one Sb(10)S6 octahedra,  a cornercorner with one Sb(1)S5 square pyramid,  a cornercorner with one Sb(4)S5 square pyramid,  a cornercorner with one Sb(5)S5 square pyramid,  a cornercorner with one Sb(9)S5 square pyramid, corners with two equivalent Sb(6)S5 square pyramids, edges with two equivalent Sb(11)S6 octahedra, edges with two equivalent Sb(7)S6 octahedra, and  an edgeedge with one Sb(6)S5 square pyramid. The corner-sharing octahedral tilt angles range from 6-42°. In the third Sb site, Sb(3) is bonded to one S(15), one S(16), one S(5), one S(8), and one S(9) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(10)S6 octahedra, corners with two equivalent Li(3)S6 octahedra,  an edgeedge with one Li(3)S6 octahedra, edges with two equivalent Li(1)S6 octahedra,  an edgeedge with one Sb(4)S5 square pyramid,  an edgeedge with one Sb(9)S5 square pyramid, and edges with two equivalent Sb(8)S5 square pyramids. The corner-sharing octahedral tilt angles range from 13-68°. In the fourth Sb site, Sb(4) is bonded to one S(12), one S(13), one S(4), one S(5), and one S(8) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Li(3)S6 octahedra,  an edgeedge with one Li(3)S6 octahedra, edges with two equivalent Li(1)S6 octahedra,  an edgeedge with one Sb(3)S5 square pyramid,  an edgeedge with one Sb(8)S5 square pyramid, and edges with two equivalent Sb(9)S5 square pyramids. The corner-sharing octahedral tilt angles range from 14-70°. In the fifth Sb site, Sb(5) is bonded to one S(1), one S(11), one S(3), one S(6), and one S(7) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(11)S6 octahedra,  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Sb(10)S6 octahedra, corners with two equivalent Sb(6)S5 square pyramids,  an edgeedge with one Sb(10)S6 octahedra,  an edgeedge with one Sb(11)S6 octahedra, and edges with two equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 8-88°. In the sixth Sb site, Sb(6) is bonded to one S(1), one S(10), one S(14), one S(17), and one S(6) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(10)S6 octahedra, corners with two equivalent Sb(2)S6 octahedra, corners with two equivalent Sb(5)S5 square pyramids,  an edgeedge with one Sb(2)S6 octahedra, edges with two equivalent Sb(11)S6 octahedra, edges with two equivalent Sb(7)S6 octahedra, and  an edgeedge with one Sb(1)S5 square pyramid. The corner-sharing octahedral tilt angles range from 3-83°. In the seventh Sb site, Sb(7) is bonded to one S(10), one S(12), one S(14), one S(17), one S(18), and one S(6) atom to form distorted SbS6 octahedra that share  a cornercorner with one Li(3)S6 octahedra, corners with two equivalent Sb(11)S6 octahedra,  a cornercorner with one Sb(1)S5 square pyramid,  a cornercorner with one Sb(4)S5 square pyramid,  a cornercorner with one Sb(5)S5 square pyramid,  a cornercorner with one Sb(9)S5 square pyramid,  an edgeedge with one Sb(11)S6 octahedra, edges with two equivalent Sb(2)S6 octahedra, and edges with two equivalent Sb(6)S5 square pyramids. The corner-sharing octahedral tilt angles range from 3-42°. In the eighth Sb site, Sb(8) is bonded to one S(13), one S(15), one S(16), one S(8), and one S(9) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(10)S6 octahedra, corners with two equivalent Li(1)S6 octahedra,  an edgeedge with one Li(1)S6 octahedra, edges with two equivalent Li(3)S6 octahedra,  an edgeedge with one Sb(4)S5 square pyramid,  an edgeedge with one Sb(9)S5 square pyramid, and edges with two equivalent Sb(3)S5 square pyramids. The corner-sharing octahedral tilt angles range from 16-69°. In the ninth Sb site, Sb(9) is bonded to one S(12), one S(13), one S(15), one S(4), and one S(5) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Li(1)S6 octahedra,  an edgeedge with one Li(1)S6 octahedra, edges with two equivalent Li(3)S6 octahedra,  an edgeedge with one Sb(3)S5 square pyramid,  an edgeedge with one Sb(8)S5 square pyramid, and edges with two equivalent Sb(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 11-69°. In the tenth Sb site, Sb(10) is bonded to one S(1), one S(11), one S(16), one S(2), one S(3), and one S(7) atom to form distorted SbS6 octahedra that share  a cornercorner with one Li(3)S6 octahedra,  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(3)S5 square pyramid,  a cornercorner with one Sb(6)S5 square pyramid,  a cornercorner with one Sb(8)S5 square pyramid, corners with two equivalent Sb(5)S5 square pyramids,  an edgeedge with one Sb(11)S6 octahedra,  an edgeedge with one Sb(5)S5 square pyramid, and edges with two equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 6-48°. In the eleventh Sb site, Sb(11) is bonded to one S(1), one S(10), one S(11), one S(17), one S(18), and one S(6) atom to form distorted SbS6 octahedra that share corners with two equivalent Sb(7)S6 octahedra,  a cornercorner with one Sb(5)S5 square pyramid, corners with three equivalent Sb(1)S5 square pyramids,  an edgeedge with one Sb(10)S6 octahedra,  an edgeedge with one Sb(7)S6 octahedra, edges with two equivalent Sb(2)S6 octahedra,  an edgeedge with one Sb(5)S5 square pyramid, and edges with two equivalent Sb(6)S5 square pyramids. The corner-sharing octahedral tilt angles range from 3-4°. There are eighteen inequivalent S sites. In the first S site, S(1) is bonded to one Sb(1), one Sb(10), one Sb(11), one Sb(2), one Sb(5), and one Sb(6) atom to form SSb6 octahedra that share  a cornercorner with one S(16)LiSb3 tetrahedra, edges with two equivalent S(6)LiSb5 octahedra, and edges with two equivalent S(11)LiSb4 square pyramids. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Sb(1), and one Sb(10) atom. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Sb(1), one Sb(10), and one Sb(5) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Sb(2), one Sb(4), and one Sb(9) atom. In the fifth S site, S(5) is bonded to one Li(1), one Li(3), one Sb(3), one Sb(4), and one Sb(9) atom to form SLi2Sb3 square pyramids that share corners with two equivalent S(8)Li2Sb3 square pyramids,  an edgeedge with one S(8)Li2Sb3 square pyramid, edges with two equivalent S(13)Li2Sb3 square pyramids, edges with two equivalent S(15)Li2Sb3 square pyramids, and  an edgeedge with one S(16)LiSb3 tetrahedra. In the sixth S site, S(6) is bonded to one Li(2), one Sb(1), one Sb(11), one Sb(5), one Sb(6), and one Sb(7) atom to form distorted SLiSb5 octahedra that share corners with two equivalent S(11)LiSb4 square pyramids, edges with two equivalent S(1)Sb6 octahedra, and  an edgeedge with one S(11)LiSb4 square pyramid. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Sb(10), and one Sb(5) atom. In the eighth S site, S(8) is bonded to one Li(1), one Li(3), one Sb(3), one Sb(4), and one Sb(8) atom to form SLi2Sb3 square pyramids that share corners with two equivalent S(5)Li2Sb3 square pyramids, corners with three equivalent S(16)LiSb3 tetrahedra,  an edgeedge with one S(5)Li2Sb3 square pyramid, edges with two equivalent S(13)Li2Sb3 square pyramids, and edges with two equivalent S(15)Li2Sb3 square pyramids. In the ninth S site, S(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Sb(3), and one Sb(8) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Sb(11), one Sb(2), one Sb(6), and one Sb(7) atom. In the eleventh S site, S(11) is bonded to one Li(2), one Sb(1), one Sb(10), one Sb(11), and one Sb(5) atom to form distorted SLiSb4 square pyramids that share corners with two equivalent S(6)LiSb5 octahedra,  a cornercorner with one S(16)LiSb3 tetrahedra,  an edgeedge with one S(6)LiSb5 octahedra, and edges with two equivalent S(1)Sb6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. In the twelfth S site, S(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Sb(4), one Sb(7), and one Sb(9) atom. In the thirteenth S site, S(13) is bonded to one Li(1), one Li(3), one Sb(4), one Sb(8), and one Sb(9) atom to form SLi2Sb3 square pyramids that share corners with two equivalent S(15)Li2Sb3 square pyramids,  an edgeedge with one S(15)Li2Sb3 square pyramid, edges with two equivalent S(5)Li2Sb3 square pyramids, edges with two equivalent S(8)Li2Sb3 square pyramids, and  an edgeedge with one S(16)LiSb3 tetrahedra. In the fourteenth S site, S(14) is bonded in a distorted T-shaped geometry to one Sb(2), one Sb(6), and one Sb(7) atom. In the fifteenth S site, S(15) is bonded to one Li(1), one Li(3), one Sb(3), one Sb(8), and one Sb(9) atom to form distorted SLi2Sb3 square pyramids that share corners with two equivalent S(13)Li2Sb3 square pyramids,  a cornercorner with one S(16)LiSb3 tetrahedra,  an edgeedge with one S(13)Li2Sb3 square pyramid, edges with two equivalent S(5)Li2Sb3 square pyramids, edges with two equivalent S(8)Li2Sb3 square pyramids, and  an edgeedge with one S(16)LiSb3 tetrahedra. In the sixteenth S site, S(16) is bonded to one Li(3), one Sb(10), one Sb(3), and one Sb(8) atom to form distorted SLiSb3 tetrahedra that share  a cornercorner with one S(1)Sb6 octahedra,  a cornercorner with one S(15)Li2Sb3 square pyramid,  a cornercorner with one S(11)LiSb4 square pyramid, corners with three equivalent S(8)Li2Sb3 square pyramids,  an edgeedge with one S(13)Li2Sb3 square pyramid,  an edgeedge with one S(15)Li2Sb3 square pyramid, and  an edgeedge with one S(5)Li2Sb3 square pyramid. The corner-sharing octahedral tilt angles are 1°. In the seventeenth S site, S(17) is bonded in a rectangular see-saw-like geometry to one Sb(11), one Sb(2), one Sb(6), and one Sb(7) atom. In the eighteenth S site, S(18) is bonded in a distorted T-shaped geometry to one Sb(11), one Sb(2), and one Sb(7) atom.
Li3Sb11S18 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one S(13), one S(15), one S(4), one S(5), one S(8), and one S(9) atom to form LiS6 octahedra that share  a cornercorner with one Sb(2)S6 octahedra, corners with two equivalent Sb(8)S5 square pyramids, corners with two equivalent Sb(9)S5 square pyramids, edges with two equivalent Li(3)S6 octahedra,  an edgeedge with one Sb(8)S5 square pyramid,  an edgeedge with one Sb(9)S5 square pyramid, edges with two equivalent Sb(3)S5 square pyramids, and edges with two equivalent Sb(4)S5 square pyramids. The corner-sharing octahedral tilt angles are 42°. The Li(1)-S(13) bond length is 2.89 Å. The Li(1)-S(15) bond length is 2.70 Å. The Li(1)-S(4) bond length is 2.57 Å. The Li(1)-S(5) bond length is 2.82 Å. The Li(1)-S(8) bond length is 2.85 Å. The Li(1)-S(9) bond length is 2.50 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one S(11), one S(2), one S(6), one S(7), and one S(9) atom. The Li(2)-S(11) bond length is 3.09 Å. The Li(2)-S(2) bond length is 2.59 Å. The Li(2)-S(6) bond length is 2.99 Å. The Li(2)-S(7) bond length is 2.58 Å. The Li(2)-S(9) bond length is 2.49 Å. In the third Li site, Li(3) is bonded to one S(12), one S(13), one S(15), one S(16), one S(5), and one S(8) atom to form LiS6 octahedra that share  a cornercorner with one Sb(10)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Sb(3)S5 square pyramids, corners with two equivalent Sb(4)S5 square pyramids, edges with two equivalent Li(1)S6 octahedra,  an edgeedge with one Sb(3)S5 square pyramid,  an edgeedge with one Sb(4)S5 square pyramid, edges with two equivalent Sb(8)S5 square pyramids, and edges with two equivalent Sb(9)S5 square pyramids. The corner-sharing octahedral tilt angles range from 42-48°. The Li(3)-S(12) bond length is 2.51 Å. The Li(3)-S(13) bond length is 2.90 Å. The Li(3)-S(15) bond length is 2.66 Å. The Li(3)-S(16) bond length is 2.48 Å. The Li(3)-S(5) bond length is 2.80 Å. The Li(3)-S(8) bond length is 2.80 Å. There are eleven inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one S(1), one S(11), one S(2), one S(3), and one S(6) atom to form distorted SbS5 square pyramids that share  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with three equivalent Sb(11)S6 octahedra, edges with two equivalent Sb(10)S6 octahedra,  an edgeedge with one Sb(6)S5 square pyramid, and edges with two equivalent Sb(5)S5 square pyramids. The corner-sharing octahedral tilt angles range from 5-89°. The Sb(1)-S(1) bond length is 2.91 Å. The Sb(1)-S(11) bond length is 2.63 Å. The Sb(1)-S(2) bond length is 2.54 Å. The Sb(1)-S(3) bond length is 2.67 Å. The Sb(1)-S(6) bond length is 3.02 Å. In the second Sb site, Sb(2) is bonded to one S(1), one S(10), one S(14), one S(17), one S(18), and one S(4) atom to form SbS6 octahedra that share  a cornercorner with one Li(1)S6 octahedra,  a cornercorner with one Sb(10)S6 octahedra,  a cornercorner with one Sb(1)S5 square pyramid,  a cornercorner with one Sb(4)S5 square pyramid,  a cornercorner with one Sb(5)S5 square pyramid,  a cornercorner with one Sb(9)S5 square pyramid, corners with two equivalent Sb(6)S5 square pyramids, edges with two equivalent Sb(11)S6 octahedra, edges with two equivalent Sb(7)S6 octahedra, and  an edgeedge with one Sb(6)S5 square pyramid. The corner-sharing octahedral tilt angles range from 6-42°. The Sb(2)-S(1) bond length is 3.01 Å. The Sb(2)-S(10) bond length is 2.87 Å. The Sb(2)-S(14) bond length is 2.72 Å. The Sb(2)-S(17) bond length is 2.86 Å. The Sb(2)-S(18) bond length is 2.67 Å. The Sb(2)-S(4) bond length is 2.57 Å. In the third Sb site, Sb(3) is bonded to one S(15), one S(16), one S(5), one S(8), and one S(9) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(10)S6 octahedra, corners with two equivalent Li(3)S6 octahedra,  an edgeedge with one Li(3)S6 octahedra, edges with two equivalent Li(1)S6 octahedra,  an edgeedge with one Sb(4)S5 square pyramid,  an edgeedge with one Sb(9)S5 square pyramid, and edges with two equivalent Sb(8)S5 square pyramids. The corner-sharing octahedral tilt angles range from 13-68°. The Sb(3)-S(15) bond length is 2.99 Å. The Sb(3)-S(16) bond length is 2.77 Å. The Sb(3)-S(5) bond length is 2.50 Å. The Sb(3)-S(8) bond length is 2.82 Å. The Sb(3)-S(9) bond length is 2.58 Å. In the fourth Sb site, Sb(4) is bonded to one S(12), one S(13), one S(4), one S(5), and one S(8) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Li(3)S6 octahedra,  an edgeedge with one Li(3)S6 octahedra, edges with two equivalent Li(1)S6 octahedra,  an edgeedge with one Sb(3)S5 square pyramid,  an edgeedge with one Sb(8)S5 square pyramid, and edges with two equivalent Sb(9)S5 square pyramids. The corner-sharing octahedral tilt angles range from 14-70°. The Sb(4)-S(12) bond length is 2.69 Å. The Sb(4)-S(13) bond length is 2.88 Å. The Sb(4)-S(4) bond length is 2.68 Å. The Sb(4)-S(5) bond length is 2.86 Å. The Sb(4)-S(8) bond length is 2.50 Å. In the fifth Sb site, Sb(5) is bonded to one S(1), one S(11), one S(3), one S(6), and one S(7) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(11)S6 octahedra,  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Sb(10)S6 octahedra, corners with two equivalent Sb(6)S5 square pyramids,  an edgeedge with one Sb(10)S6 octahedra,  an edgeedge with one Sb(11)S6 octahedra, and edges with two equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 8-88°. The Sb(5)-S(1) bond length is 2.97 Å. The Sb(5)-S(11) bond length is 2.61 Å. The Sb(5)-S(3) bond length is 2.60 Å. The Sb(5)-S(6) bond length is 3.00 Å. The Sb(5)-S(7) bond length is 2.53 Å. In the sixth Sb site, Sb(6) is bonded to one S(1), one S(10), one S(14), one S(17), and one S(6) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(10)S6 octahedra, corners with two equivalent Sb(2)S6 octahedra, corners with two equivalent Sb(5)S5 square pyramids,  an edgeedge with one Sb(2)S6 octahedra, edges with two equivalent Sb(11)S6 octahedra, edges with two equivalent Sb(7)S6 octahedra, and  an edgeedge with one Sb(1)S5 square pyramid. The corner-sharing octahedral tilt angles range from 3-83°. The Sb(6)-S(1) bond length is 2.77 Å. The Sb(6)-S(10) bond length is 2.77 Å. The Sb(6)-S(14) bond length is 2.61 Å. The Sb(6)-S(17) bond length is 2.75 Å. The Sb(6)-S(6) bond length is 2.72 Å. In the seventh Sb site, Sb(7) is bonded to one S(10), one S(12), one S(14), one S(17), one S(18), and one S(6) atom to form distorted SbS6 octahedra that share  a cornercorner with one Li(3)S6 octahedra, corners with two equivalent Sb(11)S6 octahedra,  a cornercorner with one Sb(1)S5 square pyramid,  a cornercorner with one Sb(4)S5 square pyramid,  a cornercorner with one Sb(5)S5 square pyramid,  a cornercorner with one Sb(9)S5 square pyramid,  an edgeedge with one Sb(11)S6 octahedra, edges with two equivalent Sb(2)S6 octahedra, and edges with two equivalent Sb(6)S5 square pyramids. The corner-sharing octahedral tilt angles range from 3-42°. The Sb(7)-S(10) bond length is 2.78 Å. The Sb(7)-S(12) bond length is 2.56 Å. The Sb(7)-S(14) bond length is 2.66 Å. The Sb(7)-S(17) bond length is 2.93 Å. The Sb(7)-S(18) bond length is 2.74 Å. The Sb(7)-S(6) bond length is 3.11 Å. In the eighth Sb site, Sb(8) is bonded to one S(13), one S(15), one S(16), one S(8), and one S(9) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(10)S6 octahedra, corners with two equivalent Li(1)S6 octahedra,  an edgeedge with one Li(1)S6 octahedra, edges with two equivalent Li(3)S6 octahedra,  an edgeedge with one Sb(4)S5 square pyramid,  an edgeedge with one Sb(9)S5 square pyramid, and edges with two equivalent Sb(3)S5 square pyramids. The corner-sharing octahedral tilt angles range from 16-69°. The Sb(8)-S(13) bond length is 2.50 Å. The Sb(8)-S(15) bond length is 2.94 Å. The Sb(8)-S(16) bond length is 2.77 Å. The Sb(8)-S(8) bond length is 2.81 Å. The Sb(8)-S(9) bond length is 2.62 Å. In the ninth Sb site, Sb(9) is bonded to one S(12), one S(13), one S(15), one S(4), and one S(5) atom to form SbS5 square pyramids that share  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(7)S6 octahedra, corners with two equivalent Li(1)S6 octahedra,  an edgeedge with one Li(1)S6 octahedra, edges with two equivalent Li(3)S6 octahedra,  an edgeedge with one Sb(3)S5 square pyramid,  an edgeedge with one Sb(8)S5 square pyramid, and edges with two equivalent Sb(4)S5 square pyramids. The corner-sharing octahedral tilt angles range from 11-69°. The Sb(9)-S(12) bond length is 2.80 Å. The Sb(9)-S(13) bond length is 2.75 Å. The Sb(9)-S(15) bond length is 2.46 Å. The Sb(9)-S(4) bond length is 2.81 Å. The Sb(9)-S(5) bond length is 2.76 Å. In the tenth Sb site, Sb(10) is bonded to one S(1), one S(11), one S(16), one S(2), one S(3), and one S(7) atom to form distorted SbS6 octahedra that share  a cornercorner with one Li(3)S6 octahedra,  a cornercorner with one Sb(2)S6 octahedra,  a cornercorner with one Sb(3)S5 square pyramid,  a cornercorner with one Sb(6)S5 square pyramid,  a cornercorner with one Sb(8)S5 square pyramid, corners with two equivalent Sb(5)S5 square pyramids,  an edgeedge with one Sb(11)S6 octahedra,  an edgeedge with one Sb(5)S5 square pyramid, and edges with two equivalent Sb(1)S5 square pyramids. The corner-sharing octahedral tilt angles range from 6-48°. The Sb(10)-S(1) bond length is 3.05 Å. The Sb(10)-S(11) bond length is 3.13 Å. The Sb(10)-S(16) bond length is 2.55 Å. The Sb(10)-S(2) bond length is 2.54 Å. The Sb(10)-S(3) bond length is 3.10 Å. The Sb(10)-S(7) bond length is 2.56 Å. In the eleventh Sb site, Sb(11) is bonded to one S(1), one S(10), one S(11), one S(17), one S(18), and one S(6) atom to form distorted SbS6 octahedra that share corners with two equivalent Sb(7)S6 octahedra,  a cornercorner with one Sb(5)S5 square pyramid, corners with three equivalent Sb(1)S5 square pyramids,  an edgeedge with one Sb(10)S6 octahedra,  an edgeedge with one Sb(7)S6 octahedra, edges with two equivalent Sb(2)S6 octahedra,  an edgeedge with one Sb(5)S5 square pyramid, and edges with two equivalent Sb(6)S5 square pyramids. The corner-sharing octahedral tilt angles range from 3-4°. The Sb(11)-S(1) bond length is 2.84 Å. The Sb(11)-S(10) bond length is 2.83 Å. The Sb(11)-S(11) bond length is 3.12 Å. The Sb(11)-S(17) bond length is 2.69 Å. The Sb(11)-S(18) bond length is 2.61 Å. The Sb(11)-S(6) bond length is 2.69 Å. There are eighteen inequivalent S sites. In the first S site, S(1) is bonded to one Sb(1), one Sb(10), one Sb(11), one Sb(2), one Sb(5), and one Sb(6) atom to form SSb6 octahedra that share  a cornercorner with one S(16)LiSb3 tetrahedra, edges with two equivalent S(6)LiSb5 octahedra, and edges with two equivalent S(11)LiSb4 square pyramids. In the second S site, S(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Sb(1), and one Sb(10) atom. In the third S site, S(3) is bonded in a 2-coordinate geometry to one Sb(1), one Sb(10), and one Sb(5) atom. In the fourth S site, S(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Sb(2), one Sb(4), and one Sb(9) atom. In the fifth S site, S(5) is bonded to one Li(1), one Li(3), one Sb(3), one Sb(4), and one Sb(9) atom to form SLi2Sb3 square pyramids that share corners with two equivalent S(8)Li2Sb3 square pyramids,  an edgeedge with one S(8)Li2Sb3 square pyramid, edges with two equivalent S(13)Li2Sb3 square pyramids, edges with two equivalent S(15)Li2Sb3 square pyramids, and  an edgeedge with one S(16)LiSb3 tetrahedra. In the sixth S site, S(6) is bonded to one Li(2), one Sb(1), one Sb(11), one Sb(5), one Sb(6), and one Sb(7) atom to form distorted SLiSb5 octahedra that share corners with two equivalent S(11)LiSb4 square pyramids, edges with two equivalent S(1)Sb6 octahedra, and  an edgeedge with one S(11)LiSb4 square pyramid. In the seventh S site, S(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Sb(10), and one Sb(5) atom. In the eighth S site, S(8) is bonded to one Li(1), one Li(3), one Sb(3), one Sb(4), and one Sb(8) atom to form SLi2Sb3 square pyramids that share corners with two equivalent S(5)Li2Sb3 square pyramids, corners with three equivalent S(16)LiSb3 tetrahedra,  an edgeedge with one S(5)Li2Sb3 square pyramid, edges with two equivalent S(13)Li2Sb3 square pyramids, and edges with two equivalent S(15)Li2Sb3 square pyramids. In the ninth S site, S(9) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Sb(3), and one Sb(8) atom. In the tenth S site, S(10) is bonded in a rectangular see-saw-like geometry to one Sb(11), one Sb(2), one Sb(6), and one Sb(7) atom. In the eleventh S site, S(11) is bonded to one Li(2), one Sb(1), one Sb(10), one Sb(11), and one Sb(5) atom to form distorted SLiSb4 square pyramids that share corners with two equivalent S(6)LiSb5 octahedra,  a cornercorner with one S(16)LiSb3 tetrahedra,  an edgeedge with one S(6)LiSb5 octahedra, and edges with two equivalent S(1)Sb6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. In the twelfth S site, S(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Sb(4), one Sb(7), and one Sb(9) atom. In the thirteenth S site, S(13) is bonded to one Li(1), one Li(3), one Sb(4), one Sb(8), and one Sb(9) atom to form SLi2Sb3 square pyramids that share corners with two equivalent S(15)Li2Sb3 square pyramids,  an edgeedge with one S(15)Li2Sb3 square pyramid, edges with two equivalent S(5)Li2Sb3 square pyramids, edges with two equivalent S(8)Li2Sb3 square pyramids, and  an edgeedge with one S(16)LiSb3 tetrahedra. In the fourteenth S site, S(14) is bonded in a distorted T-shaped geometry to one Sb(2), one Sb(6), and one Sb(7) atom. In the fifteenth S site, S(15) is bonded to one Li(1), one Li(3), one Sb(3), one Sb(8), and one Sb(9) atom to form distorted SLi2Sb3 square pyramids that share corners with two equivalent S(13)Li2Sb3 square pyramids,  a cornercorner with one S(16)LiSb3 tetrahedra,  an edgeedge with one S(13)Li2Sb3 square pyramid, edges with two equivalent S(5)Li2Sb3 square pyramids, edges with two equivalent S(8)Li2Sb3 square pyramids, and  an edgeedge with one S(16)LiSb3 tetrahedra. In the sixteenth S site, S(16) is bonded to one Li(3), one Sb(10), one Sb(3), and one Sb(8) atom to form distorted SLiSb3 tetrahedra that share  a cornercorner with one S(1)Sb6 octahedra,  a cornercorner with one S(15)Li2Sb3 square pyramid,  a cornercorner with one S(11)LiSb4 square pyramid, corners with three equivalent S(8)Li2Sb3 square pyramids,  an edgeedge with one S(13)Li2Sb3 square pyramid,  an edgeedge with one S(15)Li2Sb3 square pyramid, and  an edgeedge with one S(5)Li2Sb3 square pyramid. The corner-sharing octahedral tilt angles are 1°. In the seventeenth S site, S(17) is bonded in a rectangular see-saw-like geometry to one Sb(11), one Sb(2), one Sb(6), and one Sb(7) atom. In the eighteenth S site, S(18) is bonded in a distorted T-shaped geometry to one Sb(11), one Sb(2), and one Sb(7) atom.