Li5BiS4 crystallizes in the orthorhombic Cmc2_1 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 a mixture of distorted corner and edge-sharing LiS4 tetrahedra. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one S(2), one S(3), and two equivalent S(1) atoms. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to two equivalent S(1) and two equivalent S(2) atoms. Bi(1) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(1) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Bi(1) atom to form distorted corner-sharing SLi4Bi trigonal bipyramids. In the second S site, S(2) is bonded in a 8-coordinate geometry to two equivalent Li(2), two equivalent Li(3), and four equivalent Li(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one Bi(1) atom.
Li5BiS4 crystallizes in the orthorhombic Cmc2_1 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 a mixture of distorted corner and edge-sharing LiS4 tetrahedra. The Li(1)-S(1) bond length is 2.49 Å. The Li(1)-S(3) bond length is 2.60 Å. There is one shorter (2.46 Å) and one longer (2.58 Å) Li(1)-S(2) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Li(2)-S(2) bond length is 2.61 Å. The Li(2)-S(3) bond length is 2.59 Å. There is one shorter (2.44 Å) and one longer (2.55 Å) Li(2)-S(1) bond length. In the third Li site, Li(3) is bonded in a distorted trigonal planar geometry to two equivalent S(1) and two equivalent S(2) atoms. Both Li(3)-S(1) bond lengths are 2.42 Å. There is one shorter (2.45 Å) and one longer (2.99 Å) Li(3)-S(2) bond length. Bi(1) is bonded in a 3-coordinate geometry to one S(3) and two equivalent S(1) atoms. The Bi(1)-S(3) bond length is 2.59 Å. Both Bi(1)-S(1) bond lengths are 2.58 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one Li(1), one Li(3), two equivalent Li(2), and one Bi(1) atom to form distorted corner-sharing SLi4Bi trigonal bipyramids. In the second S site, S(2) is bonded in a 8-coordinate geometry to two equivalent Li(2), two equivalent Li(3), and four equivalent Li(1) atoms. In the third S site, S(3) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(2), and one Bi(1) atom.