Fe2RhS4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form FeS4 tetrahedra that share corners with six equivalent Fe(2)S6 octahedra and corners with six equivalent Rh(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. In the second Fe site, Fe(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form FeS6 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. Rh(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form RhS6 octahedra that share corners with six equivalent Fe(1)S4 tetrahedra, edges with two equivalent Rh(1)S6 octahedra, and edges with four equivalent Fe(2)S6 octahedra. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(2), and two equivalent Rh(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Fe(1), two equivalent Fe(2), and one Rh(1) atom.
Fe2RhS4 is Spinel-like structured and crystallizes in the orthorhombic Imma space group. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent S(1) and two equivalent S(2) atoms to form FeS4 tetrahedra that share corners with six equivalent Fe(2)S6 octahedra and corners with six equivalent Rh(1)S6 octahedra. The corner-sharing octahedral tilt angles range from 53-60°. Both Fe(1)-S(1) bond lengths are 2.17 Å. Both Fe(1)-S(2) bond lengths are 2.21 Å. In the second Fe site, Fe(2) is bonded to two equivalent S(1) and four equivalent S(2) atoms to form FeS6 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 Fe(2)-S(1) bond lengths are 2.27 Å. All Fe(2)-S(2) bond lengths are 2.30 Å. Rh(1) is bonded to two equivalent S(2) and four equivalent S(1) atoms to form RhS6 octahedra that share corners with six equivalent Fe(1)S4 tetrahedra, edges with two equivalent Rh(1)S6 octahedra, and edges with four equivalent Fe(2)S6 octahedra. Both Rh(1)-S(2) bond lengths are 2.38 Å. All Rh(1)-S(1) bond lengths are 2.37 Å. There are two inequivalent S sites. In the first S site, S(1) is bonded in a rectangular see-saw-like geometry to one Fe(1), one Fe(2), and two equivalent Rh(1) atoms. In the second S site, S(2) is bonded in a rectangular see-saw-like geometry to one Fe(1), two equivalent Fe(2), and one Rh(1) atom.