Li2BiS3 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(2) and three equivalent S(3) atoms to form distorted LiS5 trigonal bipyramids that share corners with two equivalent Bi(1)S5 square pyramids, corners with three equivalent Li(2)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids, edges with four equivalent Bi(1)S5 square pyramids,  an edgeedge with one Li(2)S4 tetrahedra, and edges with three equivalent Li(1)S5 trigonal bipyramids. In the second Li site, Li(2) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with four equivalent Bi(1)S5 square pyramids, corners with three equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Bi(1)S5 square pyramid,  an edgeedge with one Li(2)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. Bi(1) is bonded to one S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(1)S5 square pyramids, corners with four equivalent Li(2)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Bi(1)S5 square pyramid,  an edgeedge with one Li(2)S4 tetrahedra, and edges with four equivalent Li(1)S5 trigonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Bi(1), and one S(1) atom. In the second S site, S(2) is bonded to one Li(2), two equivalent Li(1), and two equivalent Bi(1) atoms to form distorted SLi3Bi2 square pyramids that share  a cornercorner with one S(3)Li4Bi2 octahedra, corners with two equivalent S(2)Li3Bi2 square pyramids, edges with five equivalent S(3)Li4Bi2 octahedra, and  an edgeedge with one S(2)Li3Bi2 square pyramid. The corner-sharing octahedral tilt angles are 21°. In the third S site, S(3) is bonded to one Li(2), three equivalent Li(1), and two equivalent Bi(1) atoms to form distorted SLi4Bi2 octahedra that share corners with two equivalent S(3)Li4Bi2 octahedra,  a cornercorner with one S(2)Li3Bi2 square pyramid, edges with three equivalent S(3)Li4Bi2 octahedra, and edges with five equivalent S(2)Li3Bi2 square pyramids. The corner-sharing octahedral tilt angles are 12°.
Li2BiS3 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent S(2) and three equivalent S(3) atoms to form distorted LiS5 trigonal bipyramids that share corners with two equivalent Bi(1)S5 square pyramids, corners with three equivalent Li(2)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids, edges with four equivalent Bi(1)S5 square pyramids,  an edgeedge with one Li(2)S4 tetrahedra, and edges with three equivalent Li(1)S5 trigonal bipyramids. There is one shorter (2.48 Å) and one longer (2.58 Å) Li(1)-S(2) bond length. There are a spread of Li(1)-S(3) bond distances ranging from 2.70-2.86 Å. In the second Li site, Li(2) is bonded to one S(2), one S(3), and two equivalent S(1) atoms to form distorted LiS4 tetrahedra that share corners with four equivalent Bi(1)S5 square pyramids, corners with three equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Bi(1)S5 square pyramid,  an edgeedge with one Li(2)S4 tetrahedra, and  an edgeedge with one Li(1)S5 trigonal bipyramid. The Li(2)-S(2) bond length is 2.39 Å. The Li(2)-S(3) bond length is 2.46 Å. There is one shorter (2.46 Å) and one longer (2.64 Å) Li(2)-S(1) bond length. Bi(1) is bonded to one S(1), two equivalent S(2), and two equivalent S(3) atoms to form distorted BiS5 square pyramids that share corners with two equivalent Bi(1)S5 square pyramids, corners with four equivalent Li(2)S4 tetrahedra, corners with two equivalent Li(1)S5 trigonal bipyramids,  an edgeedge with one Bi(1)S5 square pyramid,  an edgeedge with one Li(2)S4 tetrahedra, and edges with four equivalent Li(1)S5 trigonal bipyramids. The Bi(1)-S(1) bond length is 3.04 Å. There is one shorter (2.69 Å) and one longer (2.81 Å) Bi(1)-S(2) bond length. There is one shorter (2.69 Å) and one longer (2.70 Å) Bi(1)-S(3) bond length. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to two equivalent Li(2), one Bi(1), and one S(1) atom. The S(1)-S(1) bond length is 2.09 Å. In the second S site, S(2) is bonded to one Li(2), two equivalent Li(1), and two equivalent Bi(1) atoms to form distorted SLi3Bi2 square pyramids that share  a cornercorner with one S(3)Li4Bi2 octahedra, corners with two equivalent S(2)Li3Bi2 square pyramids, edges with five equivalent S(3)Li4Bi2 octahedra, and  an edgeedge with one S(2)Li3Bi2 square pyramid. The corner-sharing octahedral tilt angles are 21°. In the third S site, S(3) is bonded to one Li(2), three equivalent Li(1), and two equivalent Bi(1) atoms to form distorted SLi4Bi2 octahedra that share corners with two equivalent S(3)Li4Bi2 octahedra,  a cornercorner with one S(2)Li3Bi2 square pyramid, edges with three equivalent S(3)Li4Bi2 octahedra, and edges with five equivalent S(2)Li3Bi2 square pyramids. The corner-sharing octahedral tilt angles are 12°.