TlBiS2 crystallizes in the tetragonal I4_1/amd space group. Tl(1) is bonded in a square co-planar geometry to four equivalent S(1) atoms. Bi(1) is bonded to six equivalent S(1) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles are 10°. S(1) is bonded to two equivalent Tl(1) and three equivalent Bi(1) atoms to form a mixture of corner and edge-sharing STl2Bi3 square pyramids.
TlBiS2 crystallizes in the tetragonal I4_1/amd space group. Tl(1) is bonded in a square co-planar geometry to four equivalent S(1) atoms. All Tl(1)-S(1) bond lengths are 2.99 Å. Bi(1) is bonded to six equivalent S(1) atoms to form a mixture of corner and edge-sharing BiS6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are two shorter (2.80 Å) and four longer (2.99 Å) Bi(1)-S(1) bond lengths. S(1) is bonded to two equivalent Tl(1) and three equivalent Bi(1) atoms to form a mixture of corner and edge-sharing STl2Bi3 square pyramids.