NaRh(SO4)2 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(1) and four equivalent O(2) atoms. Rh(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form RhO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. S(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with three equivalent Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Rh(1), and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Rh(1) and one S(1) atom.
NaRh(SO4)2 crystallizes in the monoclinic C2/m space group. Na(1) is bonded in a distorted hexagonal planar geometry to two equivalent O(1) and four equivalent O(2) atoms. Both Na(1)-O(1) bond lengths are 2.43 Å. All Na(1)-O(2) bond lengths are 2.51 Å. Rh(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form RhO6 octahedra that share corners with six equivalent S(1)O4 tetrahedra. Both Rh(1)-O(3) bond lengths are 2.05 Å. All Rh(1)-O(2) bond lengths are 2.07 Å. S(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form SO4 tetrahedra that share corners with three equivalent Rh(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-51°. The S(1)-O(1) bond length is 1.45 Å. The S(1)-O(3) bond length is 1.49 Å. Both S(1)-O(2) bond lengths are 1.52 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Rh(1), and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Rh(1) and one S(1) atom.