Rh2Ge3Se3 is Spinel-like structured and crystallizes in the trigonal R-3 space group. There are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to three equivalent Ge(1) and three equivalent Se(2) atoms to form RhGe3Se3 octahedra that share corners with six equivalent Rh(2)Ge3Se3 octahedra, corners with six equivalent Ge(2)Rh2Se2 tetrahedra, and corners with six equivalent Se(1)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 55-62°. In the second Rh site, Rh(2) is bonded to one Ge(1), two equivalent Ge(2), one Se(2), and two equivalent Se(1) atoms to form RhGe3Se3 octahedra that share corners with two equivalent Rh(1)Ge3Se3 octahedra, corners with four equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with four equivalent Ge(1)Rh2Se2 tetrahedra, and corners with four equivalent Se(2)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 55-62°. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Rh(1), one Rh(2), and two equivalent Se(1) atoms to form distorted GeRh2Se2 tetrahedra that share corners with four equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(1)Rh2Se2 tetrahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with four equivalent Se(2)Ge2Rh2 tetrahedra, and  an edgeedge with one Ge(1)Rh2Se2 tetrahedra. The corner-sharing octahedral tilt angles range from 69-70°. In the second Ge site, Ge(2) is bonded to two equivalent Rh(2) and two equivalent Se(2) atoms to form distorted GeRh2Se2 tetrahedra that share corners with two equivalent Rh(1)Ge3Se3 octahedra, corners with two equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(1)Rh2Se2 tetrahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(2)Ge2Rh2 tetrahedra, corners with four equivalent Se(1)Ge2Rh2 tetrahedra, and  an edgeedge with one Ge(2)Rh2Se2 tetrahedra. The corner-sharing octahedral tilt angles range from 68-71°. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Rh(2) and two equivalent Ge(1) atoms to form SeGe2Rh2 tetrahedra that share corners with two equivalent Rh(1)Ge3Se3 octahedra, corners with two equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(1)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with two equivalent Se(2)Ge2Rh2 tetrahedra, corners with four equivalent Ge(2)Rh2Se2 tetrahedra, and  an edgeedge with one Se(1)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 68-72°. In the second Se site, Se(2) is bonded to one Rh(1), one Rh(2), and two equivalent Ge(2) atoms to form SeGe2Rh2 tetrahedra that share corners with four equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with two equivalent Se(2)Ge2Rh2 tetrahedra, corners with four equivalent Ge(1)Rh2Se2 tetrahedra, and  an edgeedge with one Se(2)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 68-72°.
Rh2Ge3Se3 is Spinel-like structured and crystallizes in the trigonal R-3 space group. There are two inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to three equivalent Ge(1) and three equivalent Se(2) atoms to form RhGe3Se3 octahedra that share corners with six equivalent Rh(2)Ge3Se3 octahedra, corners with six equivalent Ge(2)Rh2Se2 tetrahedra, and corners with six equivalent Se(1)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 55-62°. All Rh(1)-Ge(1) bond lengths are 2.42 Å. All Rh(1)-Se(2) bond lengths are 2.50 Å. In the second Rh site, Rh(2) is bonded to one Ge(1), two equivalent Ge(2), one Se(2), and two equivalent Se(1) atoms to form RhGe3Se3 octahedra that share corners with two equivalent Rh(1)Ge3Se3 octahedra, corners with four equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with four equivalent Ge(1)Rh2Se2 tetrahedra, and corners with four equivalent Se(2)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 55-62°. The Rh(2)-Ge(1) bond length is 2.39 Å. There is one shorter (2.40 Å) and one longer (2.41 Å) Rh(2)-Ge(2) bond length. The Rh(2)-Se(2) bond length is 2.54 Å. There is one shorter (2.51 Å) and one longer (2.53 Å) Rh(2)-Se(1) bond length. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one Rh(1), one Rh(2), and two equivalent Se(1) atoms to form distorted GeRh2Se2 tetrahedra that share corners with four equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(1)Rh2Se2 tetrahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with four equivalent Se(2)Ge2Rh2 tetrahedra, and  an edgeedge with one Ge(1)Rh2Se2 tetrahedra. The corner-sharing octahedral tilt angles range from 69-70°. There is one shorter (2.52 Å) and one longer (2.68 Å) Ge(1)-Se(1) bond length. In the second Ge site, Ge(2) is bonded to two equivalent Rh(2) and two equivalent Se(2) atoms to form distorted GeRh2Se2 tetrahedra that share corners with two equivalent Rh(1)Ge3Se3 octahedra, corners with two equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(1)Rh2Se2 tetrahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(2)Ge2Rh2 tetrahedra, corners with four equivalent Se(1)Ge2Rh2 tetrahedra, and  an edgeedge with one Ge(2)Rh2Se2 tetrahedra. The corner-sharing octahedral tilt angles range from 68-71°. There is one shorter (2.52 Å) and one longer (2.68 Å) Ge(2)-Se(2) bond length. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded to two equivalent Rh(2) and two equivalent Ge(1) atoms to form SeGe2Rh2 tetrahedra that share corners with two equivalent Rh(1)Ge3Se3 octahedra, corners with two equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(1)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with two equivalent Se(2)Ge2Rh2 tetrahedra, corners with four equivalent Ge(2)Rh2Se2 tetrahedra, and  an edgeedge with one Se(1)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 68-72°. In the second Se site, Se(2) is bonded to one Rh(1), one Rh(2), and two equivalent Ge(2) atoms to form SeGe2Rh2 tetrahedra that share corners with four equivalent Rh(2)Ge3Se3 octahedra, corners with two equivalent Ge(2)Rh2Se2 tetrahedra, corners with two equivalent Se(1)Ge2Rh2 tetrahedra, corners with two equivalent Se(2)Ge2Rh2 tetrahedra, corners with four equivalent Ge(1)Rh2Se2 tetrahedra, and  an edgeedge with one Se(2)Ge2Rh2 tetrahedra. The corner-sharing octahedral tilt angles range from 68-72°.