K2Rh2O5 crystallizes in the tetragonal P4/mmm space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to eight equivalent O(1) atoms to form distorted KO8 hexagonal bipyramids that share corners with eight equivalent K(2)O12 cuboctahedra, edges with four equivalent K(1)O8 hexagonal bipyramids, edges with eight equivalent Rh(1)O5 square pyramids, and faces with two equivalent K(2)O12 cuboctahedra. In the second K site, K(2) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form KO12 cuboctahedra that share corners with four equivalent K(2)O12 cuboctahedra, corners with eight equivalent K(1)O8 hexagonal bipyramids, faces with four equivalent K(2)O12 cuboctahedra, faces with two equivalent K(1)O8 hexagonal bipyramids, and faces with eight equivalent Rh(1)O5 square pyramids. Rh(1) is bonded to one O(2) and four equivalent O(1) atoms to form RhO5 square pyramids that share corners with five equivalent Rh(1)O5 square pyramids, edges with four equivalent K(1)O8 hexagonal bipyramids, and faces with four equivalent K(2)O12 cuboctahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent K(1), two equivalent K(2), and two equivalent Rh(1) atoms to form a mixture of distorted edge, face, and corner-sharing OK4Rh2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. In the second O site, O(2) is bonded to four equivalent K(2) and two equivalent Rh(1) atoms to form a mixture of edge, face, and corner-sharing OK4Rh2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°.
K2Rh2O5 crystallizes in the tetragonal P4/mmm space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to eight equivalent O(1) atoms to form distorted KO8 hexagonal bipyramids that share corners with eight equivalent K(2)O12 cuboctahedra, edges with four equivalent K(1)O8 hexagonal bipyramids, edges with eight equivalent Rh(1)O5 square pyramids, and faces with two equivalent K(2)O12 cuboctahedra. All K(1)-O(1) bond lengths are 2.75 Å. In the second K site, K(2) is bonded to four equivalent O(2) and eight equivalent O(1) atoms to form KO12 cuboctahedra that share corners with four equivalent K(2)O12 cuboctahedra, corners with eight equivalent K(1)O8 hexagonal bipyramids, faces with four equivalent K(2)O12 cuboctahedra, faces with two equivalent K(1)O8 hexagonal bipyramids, and faces with eight equivalent Rh(1)O5 square pyramids. All K(2)-O(2) bond lengths are 2.73 Å. All K(2)-O(1) bond lengths are 2.97 Å. Rh(1) is bonded to one O(2) and four equivalent O(1) atoms to form RhO5 square pyramids that share corners with five equivalent Rh(1)O5 square pyramids, edges with four equivalent K(1)O8 hexagonal bipyramids, and faces with four equivalent K(2)O12 cuboctahedra. The Rh(1)-O(2) bond length is 2.00 Å. All Rh(1)-O(1) bond lengths are 1.95 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent K(1), two equivalent K(2), and two equivalent Rh(1) atoms to form a mixture of distorted edge, face, and corner-sharing OK4Rh2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. In the second O site, O(2) is bonded to four equivalent K(2) and two equivalent Rh(1) atoms to form a mixture of edge, face, and corner-sharing OK4Rh2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°.