TlBiS2 is Caswellsilverite structured and crystallizes in the trigonal R-3m space group. Tl(1) is bonded to six equivalent S(1) atoms to form distorted TlS6 octahedra that share corners with six equivalent Bi(1)S6 octahedra, edges with six equivalent Tl(1)S6 octahedra, and edges with six equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 9°. Bi(1) is bonded to six equivalent S(1) atoms to form BiS6 octahedra that share corners with six equivalent Tl(1)S6 octahedra, edges with six equivalent Tl(1)S6 octahedra, and edges with six equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 9°. S(1) is bonded to three equivalent Tl(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing STl3Bi3 octahedra. The corner-sharing octahedra are not tilted.
TlBiS2 is Caswellsilverite structured and crystallizes in the trigonal R-3m space group. Tl(1) is bonded to six equivalent S(1) atoms to form distorted TlS6 octahedra that share corners with six equivalent Bi(1)S6 octahedra, edges with six equivalent Tl(1)S6 octahedra, and edges with six equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 9°. All Tl(1)-S(1) bond lengths are 3.20 Å. Bi(1) is bonded to six equivalent S(1) atoms to form BiS6 octahedra that share corners with six equivalent Tl(1)S6 octahedra, edges with six equivalent Tl(1)S6 octahedra, and edges with six equivalent Bi(1)S6 octahedra. The corner-sharing octahedral tilt angles are 9°. All Bi(1)-S(1) bond lengths are 2.85 Å. S(1) is bonded to three equivalent Tl(1) and three equivalent Bi(1) atoms to form a mixture of edge and corner-sharing STl3Bi3 octahedra. The corner-sharing octahedra are not tilted.