Li3BiS3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form a mixture of distorted edge and corner-sharing LiS4 tetrahedra. In the second Li site, Li(2) is bonded to one S(3) and three equivalent S(2) atoms to form a mixture of distorted edge and corner-sharing LiS4 tetrahedra. In the third Li site, Li(3) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form a mixture of distorted edge and corner-sharing LiS4 tetrahedra. Bi(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(3), and one Bi(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Li(3), three equivalent Li(2), and one Bi(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), and one Bi(1) atom.
Li3BiS3 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form a mixture of distorted edge and corner-sharing LiS4 tetrahedra. There is one shorter (2.41 Å) and one longer (2.58 Å) Li(1)-S(1) bond length. There is one shorter (2.45 Å) and one longer (2.55 Å) Li(1)-S(3) bond length. In the second Li site, Li(2) is bonded to one S(3) and three equivalent S(2) atoms to form a mixture of distorted edge and corner-sharing LiS4 tetrahedra. The Li(2)-S(3) bond length is 2.47 Å. There are a spread of Li(2)-S(2) bond distances ranging from 2.49-2.61 Å. In the third Li site, Li(3) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form a mixture of distorted edge and corner-sharing LiS4 tetrahedra. The Li(3)-S(2) bond length is 2.51 Å. The Li(3)-S(3) bond length is 2.51 Å. There is one shorter (2.44 Å) and one longer (2.50 Å) Li(3)-S(1) bond length. Bi(1) is bonded in a 3-coordinate geometry to one S(1), one S(2), and one S(3) atom. The Bi(1)-S(1) bond length is 2.61 Å. The Bi(1)-S(2) bond length is 2.62 Å. The Bi(1)-S(3) bond length is 2.65 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Li(1), two equivalent Li(3), and one Bi(1) atom. In the second S site, S(2) is bonded in a 5-coordinate geometry to one Li(3), three equivalent Li(2), and one Bi(1) atom. In the third S site, S(3) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), two equivalent Li(1), and one Bi(1) atom.