Rh3Tl2S2 crystallizes in the trigonal R-3m space group. Rh(1) is bonded to two equivalent Tl(1), two equivalent Tl(2), and two equivalent S(1) atoms to form distorted RhTl4S2 octahedra that share corners with two equivalent Tl(2)Rh6S2 hexagonal bipyramids, corners with twelve equivalent Rh(1)Tl4S2 octahedra, and faces with four equivalent Rh(1)Tl4S2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted hexagonal planar geometry to six equivalent Rh(1) atoms. In the second Tl site, Tl(2) is bonded to six equivalent Rh(1) and two equivalent S(1) atoms to form TlRh6S2 hexagonal bipyramids that share corners with six equivalent Tl(2)Rh6S2 hexagonal bipyramids and corners with six equivalent Rh(1)Tl4S2 octahedra. The corner-sharing octahedral tilt angles are 46°. S(1) is bonded in a 4-coordinate geometry to three equivalent Rh(1) and one Tl(2) atom.
Rh3Tl2S2 crystallizes in the trigonal R-3m space group. Rh(1) is bonded to two equivalent Tl(1), two equivalent Tl(2), and two equivalent S(1) atoms to form distorted RhTl4S2 octahedra that share corners with two equivalent Tl(2)Rh6S2 hexagonal bipyramids, corners with twelve equivalent Rh(1)Tl4S2 octahedra, and faces with four equivalent Rh(1)Tl4S2 octahedra. The corner-sharing octahedral tilt angles range from 0-60°. Both Rh(1)-Tl(1) bond lengths are 2.87 Å. Both Rh(1)-Tl(2) bond lengths are 2.85 Å. Both Rh(1)-S(1) bond lengths are 2.30 Å. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted hexagonal planar geometry to six equivalent Rh(1) atoms. In the second Tl site, Tl(2) is bonded to six equivalent Rh(1) and two equivalent S(1) atoms to form TlRh6S2 hexagonal bipyramids that share corners with six equivalent Tl(2)Rh6S2 hexagonal bipyramids and corners with six equivalent Rh(1)Tl4S2 octahedra. The corner-sharing octahedral tilt angles are 46°. Both Tl(2)-S(1) bond lengths are 3.10 Å. S(1) is bonded in a 4-coordinate geometry to three equivalent Rh(1) and one Tl(2) atom.