Li5SbS4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal non-coplanar geometry to one S(2) and two equivalent S(1) atoms. In the second Li site, Li(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with four equivalent Sb(1)S4 trigonal pyramids. Sb(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form distorted SbS4 trigonal pyramids that share corners with four equivalent Li(2)S4 tetrahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Li(2), four equivalent Li(1), and one Sb(1) atom to form distorted SLi5Sb octahedra that share corners with two equivalent S(1)Li5Sb octahedra, corners with eight equivalent S(2)Li3Sb tetrahedra, and edges with two equivalent S(1)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 36-69°. In the second S site, S(2) is bonded to one Li(2), two equivalent Li(1), and one Sb(1) atom to form distorted SLi3Sb tetrahedra that share corners with eight equivalent S(1)Li5Sb octahedra and corners with two equivalent S(2)Li3Sb tetrahedra. The corner-sharing octahedral tilt angles range from 49-78°.
Li5SbS4 crystallizes in the orthorhombic Pmmn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal non-coplanar geometry to one S(2) and two equivalent S(1) atoms. The Li(1)-S(2) bond length is 2.48 Å. There is one shorter (2.41 Å) and one longer (2.46 Å) Li(1)-S(1) bond length. In the second Li site, Li(2) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form LiS4 tetrahedra that share corners with four equivalent Sb(1)S4 trigonal pyramids. Both Li(2)-S(1) bond lengths are 2.44 Å. Both Li(2)-S(2) bond lengths are 2.45 Å. Sb(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form distorted SbS4 trigonal pyramids that share corners with four equivalent Li(2)S4 tetrahedra. Both Sb(1)-S(1) bond lengths are 2.77 Å. Both Sb(1)-S(2) bond lengths are 2.48 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded to one Li(2), four equivalent Li(1), and one Sb(1) atom to form distorted SLi5Sb octahedra that share corners with two equivalent S(1)Li5Sb octahedra, corners with eight equivalent S(2)Li3Sb tetrahedra, and edges with two equivalent S(1)Li5Sb octahedra. The corner-sharing octahedral tilt angles range from 36-69°. In the second S site, S(2) is bonded to one Li(2), two equivalent Li(1), and one Sb(1) atom to form distorted SLi3Sb tetrahedra that share corners with eight equivalent S(1)Li5Sb octahedra and corners with two equivalent S(2)Li3Sb tetrahedra. The corner-sharing octahedral tilt angles range from 49-78°.