LiBiS2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Li(1) is bonded to six S(1,1,1) atoms to form LiS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, and edges with eight equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. Bi(1) is bonded to six S(1,1) atoms to form BiS6 octahedra that share corners with two equivalent Li(1)S6 octahedra, corners with four equivalent Bi(1)S6 octahedra, edges with four equivalent Bi(1)S6 octahedra, and edges with eight equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
LiBiS2 is Caswellsilverite-like structured and crystallizes in the tetragonal I4_1/amd space group. Li(1) is bonded to six S(1,1,1) atoms to form LiS6 octahedra that share corners with two equivalent Bi(1)S6 octahedra, corners with four equivalent Li(1)S6 octahedra, edges with four equivalent Li(1)S6 octahedra, and edges with eight equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two shorter (2.77 Å) and four longer (2.78 Å) Li(1)-S(1,1,1) bond lengths. Bi(1) is bonded to six S(1,1) atoms to form BiS6 octahedra that share corners with two equivalent Li(1)S6 octahedra, corners with four equivalent Bi(1)S6 octahedra, edges with four equivalent Bi(1)S6 octahedra, and edges with eight equivalent Li(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are four shorter (2.78 Å) and two longer (2.81 Å) Bi(1)-S(1,1) bond lengths. There are four inequivalent S sites. In the first S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There is one shorter (2.77 Å) and two longer (2.78 Å) S(1)-Li(1) bond lengths. There are two shorter (2.78 Å) and one longer (2.81 Å) S(1)-Bi(1) bond length. In the second S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two shorter (2.78 Å) and one longer (2.81 Å) S(1)-Bi(1) bond length. In the fourth S site, S(1) is bonded to three equivalent Li(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing SLi3Bi3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.