Rh3S4 is Aluminum carbonitride-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form RhS6 octahedra that share corners with four equivalent Rh(3)S5 square pyramids, corners with two equivalent S(1)Rh3S tetrahedra,  an edgeedge with one Rh(1)S6 octahedra, and edges with two equivalent Rh(2)S6 octahedra. In the second Rh site, Rh(2) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form RhS6 octahedra that share corners with two equivalent Rh(3)S5 square pyramids and edges with four equivalent Rh(1)S6 octahedra. In the third Rh site, Rh(3) is bonded to one S(2), two equivalent S(1), and two equivalent S(4) atoms to form RhS5 square pyramids that share  a cornercorner with one Rh(2)S6 octahedra, corners with four equivalent Rh(1)S6 octahedra, corners with two equivalent S(1)Rh3S tetrahedra, and  an edgeedge with one Rh(3)S5 square pyramid. The corner-sharing octahedral tilt angles range from 53-64°. In the fourth Rh site, Rh(4) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(4), and two equivalent S(3) atoms. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Rh(1), one Rh(3), one Rh(4), and one S(1) atom to form distorted SRh3S tetrahedra that share  a cornercorner with one Rh(1)S6 octahedra,  a cornercorner with one Rh(3)S5 square pyramid, corners with two equivalent S(1)Rh3S tetrahedra, corners with three equivalent S(2)Rh4 tetrahedra, corners with three equivalent S(4)Rh4 tetrahedra, and corners with four equivalent S(3)Rh4 tetrahedra. The corner-sharing octahedral tilt angles are 79°. In the second S site, S(2) is bonded to one Rh(2), one Rh(3), and two equivalent Rh(1) atoms to form distorted SRh4 tetrahedra that share  a cornercorner with one S(2)Rh4 tetrahedra, corners with two equivalent S(4)Rh4 tetrahedra, corners with four equivalent S(3)Rh4 tetrahedra, corners with six equivalent S(1)Rh3S tetrahedra,  an edgeedge with one S(2)Rh4 tetrahedra, and edges with two equivalent S(3)Rh4 tetrahedra. In the third S site, S(3) is bonded to one Rh(1), one Rh(2), and two equivalent Rh(4) atoms to form SRh4 tetrahedra that share corners with two equivalent S(2)Rh4 tetrahedra, corners with two equivalent S(4)Rh4 tetrahedra, corners with four equivalent S(1)Rh3S tetrahedra, corners with four equivalent S(3)Rh4 tetrahedra,  an edgeedge with one S(2)Rh4 tetrahedra, and  an edgeedge with one S(3)Rh4 tetrahedra. In the fourth S site, S(4) is bonded to two equivalent Rh(3) and two equivalent Rh(4) atoms to form distorted SRh4 tetrahedra that share corners with two equivalent S(2)Rh4 tetrahedra, corners with four equivalent S(3)Rh4 tetrahedra, corners with six equivalent S(1)Rh3S tetrahedra, and  an edgeedge with one S(4)Rh4 tetrahedra.
Rh3S4 is Aluminum carbonitride-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to two equivalent S(1), two equivalent S(2), and two equivalent S(3) atoms to form RhS6 octahedra that share corners with four equivalent Rh(3)S5 square pyramids, corners with two equivalent S(1)Rh3S tetrahedra,  an edgeedge with one Rh(1)S6 octahedra, and edges with two equivalent Rh(2)S6 octahedra. Both Rh(1)-S(1) bond lengths are 2.33 Å. Both Rh(1)-S(2) bond lengths are 2.35 Å. Both Rh(1)-S(3) bond lengths are 2.37 Å. In the second Rh site, Rh(2) is bonded to two equivalent S(2) and four equivalent S(3) atoms to form RhS6 octahedra that share corners with two equivalent Rh(3)S5 square pyramids and edges with four equivalent Rh(1)S6 octahedra. Both Rh(2)-S(2) bond lengths are 2.37 Å. All Rh(2)-S(3) bond lengths are 2.39 Å. In the third Rh site, Rh(3) is bonded to one S(2), two equivalent S(1), and two equivalent S(4) atoms to form RhS5 square pyramids that share  a cornercorner with one Rh(2)S6 octahedra, corners with four equivalent Rh(1)S6 octahedra, corners with two equivalent S(1)Rh3S tetrahedra, and  an edgeedge with one Rh(3)S5 square pyramid. The corner-sharing octahedral tilt angles range from 53-64°. The Rh(3)-S(2) bond length is 2.32 Å. Both Rh(3)-S(1) bond lengths are 2.28 Å. There is one shorter (2.34 Å) and one longer (2.41 Å) Rh(3)-S(4) bond length. In the fourth Rh site, Rh(4) is bonded in a distorted rectangular see-saw-like geometry to one S(1), one S(4), and two equivalent S(3) atoms. The Rh(4)-S(1) bond length is 2.26 Å. The Rh(4)-S(4) bond length is 2.28 Å. There is one shorter (2.34 Å) and one longer (2.38 Å) Rh(4)-S(3) bond length. There are four inequivalent S sites. In the first S site, S(1) is bonded to one Rh(1), one Rh(3), one Rh(4), and one S(1) atom to form distorted SRh3S tetrahedra that share  a cornercorner with one Rh(1)S6 octahedra,  a cornercorner with one Rh(3)S5 square pyramid, corners with two equivalent S(1)Rh3S tetrahedra, corners with three equivalent S(2)Rh4 tetrahedra, corners with three equivalent S(4)Rh4 tetrahedra, and corners with four equivalent S(3)Rh4 tetrahedra. The corner-sharing octahedral tilt angles are 79°. The S(1)-S(1) bond length is 2.26 Å. In the second S site, S(2) is bonded to one Rh(2), one Rh(3), and two equivalent Rh(1) atoms to form distorted SRh4 tetrahedra that share  a cornercorner with one S(2)Rh4 tetrahedra, corners with two equivalent S(4)Rh4 tetrahedra, corners with four equivalent S(3)Rh4 tetrahedra, corners with six equivalent S(1)Rh3S tetrahedra,  an edgeedge with one S(2)Rh4 tetrahedra, and edges with two equivalent S(3)Rh4 tetrahedra. In the third S site, S(3) is bonded to one Rh(1), one Rh(2), and two equivalent Rh(4) atoms to form SRh4 tetrahedra that share corners with two equivalent S(2)Rh4 tetrahedra, corners with two equivalent S(4)Rh4 tetrahedra, corners with four equivalent S(1)Rh3S tetrahedra, corners with four equivalent S(3)Rh4 tetrahedra,  an edgeedge with one S(2)Rh4 tetrahedra, and  an edgeedge with one S(3)Rh4 tetrahedra. In the fourth S site, S(4) is bonded to two equivalent Rh(3) and two equivalent Rh(4) atoms to form distorted SRh4 tetrahedra that share corners with two equivalent S(2)Rh4 tetrahedra, corners with four equivalent S(3)Rh4 tetrahedra, corners with six equivalent S(1)Rh3S tetrahedra, and  an edgeedge with one S(4)Rh4 tetrahedra.