Fe3Rh3S8 is Spinel-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(1) and three equivalent S(2) atoms to form FeS4 tetrahedra that share corners with three equivalent Fe(2)S6 octahedra and corners with nine equivalent Rh(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. In the second Fe site, Fe(2) is bonded to six equivalent S(2) atoms to form FeS6 octahedra that share corners with six equivalent Fe(1)S4 tetrahedra and edges with six equivalent Rh(1)S6 octahedra. Rh(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form RhS6 octahedra that share corners with six equivalent Fe(1)S4 tetrahedra, edges with two equivalent Fe(2)S6 octahedra, and edges with four equivalent Rh(1)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Fe(1) and three equivalent Rh(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(2), and two equivalent Rh(1) atoms.
Fe3Rh3S8 is Spinel-like structured and crystallizes in the trigonal R-3m space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one S(1) and three equivalent S(2) atoms to form FeS4 tetrahedra that share corners with three equivalent Fe(2)S6 octahedra and corners with nine equivalent Rh(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 52-58°. The Fe(1)-S(1) bond length is 2.09 Å. All Fe(1)-S(2) bond lengths are 2.14 Å. In the second Fe site, Fe(2) is bonded to six equivalent S(2) atoms to form FeS6 octahedra that share corners with six equivalent Fe(1)S4 tetrahedra and edges with six equivalent Rh(1)S6 octahedra. All Fe(2)-S(2) bond lengths are 2.31 Å. Rh(1) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form RhS6 octahedra that share corners with six equivalent Fe(1)S4 tetrahedra, edges with two equivalent Fe(2)S6 octahedra, and edges with four equivalent Rh(1)S6 octahedra. Both Rh(1)-S(1) bond lengths are 2.39 Å. All Rh(1)-S(2) bond lengths are 2.40 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a distorted rectangular see-saw-like geometry to one Fe(1) and three equivalent Rh(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(2), and two equivalent Rh(1) atoms.