Re(RhO3)2 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Re(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ReO6 octahedra that share corners with eight equivalent Rh(1)O6 octahedra and edges with two equivalent Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. Rh(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form RhO6 octahedra that share corners with four equivalent Re(1)O6 octahedra, corners with four equivalent Rh(1)O6 octahedra,  an edgeedge with one Re(1)O6 octahedra, and  an edgeedge with one Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. There are two inequivalent O sites. In the first O site, O(2) is bonded in a trigonal planar geometry to one Re(1) and two equivalent Rh(1) atoms. In the second O site, O(1) is bonded in a distorted trigonal planar geometry to one Re(1) and two equivalent Rh(1) atoms.
Re(RhO3)2 is Hydrophilite-derived structured and crystallizes in the tetragonal P4_2/mnm space group. Re(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form ReO6 octahedra that share corners with eight equivalent Rh(1)O6 octahedra and edges with two equivalent Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. Both Re(1)-O(1) bond lengths are 1.93 Å. All Re(1)-O(2) bond lengths are 1.92 Å. Rh(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form RhO6 octahedra that share corners with four equivalent Re(1)O6 octahedra, corners with four equivalent Rh(1)O6 octahedra,  an edgeedge with one Re(1)O6 octahedra, and  an edgeedge with one Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. Both Rh(1)-O(1) bond lengths are 2.02 Å. There are two shorter (1.99 Å) and two longer (2.03 Å) Rh(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(2) is bonded in a trigonal planar geometry to one Re(1) and two equivalent Rh(1) atoms. In the second O site, O(1) is bonded in a distorted trigonal planar geometry to one Re(1) and two equivalent Rh(1) atoms.