NaCd3(RhO2)8 crystallizes in the monoclinic Pm space group. Na(1) is bonded in a 8-coordinate geometry to one O(5), one O(6), two equivalent O(11), two equivalent O(15), and two equivalent O(3) atoms. There are eight inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to one O(14), one O(9), two equivalent O(16), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the second Rh site, Rh(2) is bonded to one O(10), one O(13), two equivalent O(15), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the third Rh site, Rh(3) is bonded to one O(11), one O(16), two equivalent O(14), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. In the fourth Rh site, Rh(4) is bonded to one O(12), one O(15), two equivalent O(13), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. In the fifth Rh site, Rh(5) is bonded to one O(1), one O(5), two equivalent O(12), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. In the sixth Rh site, Rh(6) is bonded to one O(2), one O(6), two equivalent O(11), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. In the seventh Rh site, Rh(7) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(10) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the eighth Rh site, Rh(8) is bonded to one O(4), one O(8), two equivalent O(2), and two equivalent O(9) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a 8-coordinate geometry to one O(5), one O(6), two equivalent O(12), two equivalent O(16), and two equivalent O(4) atoms. In the second Cd site, Cd(2) is bonded in a 8-coordinate geometry to one O(7), one O(8), two equivalent O(1), two equivalent O(13), and two equivalent O(9) atoms. In the third Cd site, Cd(3) is bonded in a 8-coordinate geometry to one O(7), one O(8), two equivalent O(10), two equivalent O(14), and two equivalent O(2) atoms. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Rh(5), two equivalent Rh(7), and two equivalent Cd(2) atoms to form distorted OCd2Rh3 trigonal bipyramids that share corners with two equivalent O(13)Cd2Rh3 square pyramids,  a cornercorner with one O(5)NaCdRh3 trigonal bipyramid,  an edgeedge with one O(13)Cd2Rh3 square pyramid, edges with two equivalent O(1)Cd2Rh3 trigonal bipyramids, and edges with two equivalent O(3)Na2Rh3 trigonal bipyramids. In the second O site, O(2) is bonded to one Rh(6), two equivalent Rh(8), and two equivalent Cd(3) atoms to form distorted OCd2Rh3 trigonal bipyramids that share corners with two equivalent O(14)Cd2Rh3 square pyramids,  a cornercorner with one O(6)NaCdRh3 trigonal bipyramid,  an edgeedge with one O(14)Cd2Rh3 square pyramid, edges with two equivalent O(2)Cd2Rh3 trigonal bipyramids, and edges with two equivalent O(4)Cd2Rh3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(1), one Rh(7), and two equivalent Rh(5) atoms to form distorted ONa2Rh3 trigonal bipyramids that share corners with two equivalent O(15)Na2Rh3 square pyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(15)Na2Rh3 square pyramid, edges with two equivalent O(1)Cd2Rh3 trigonal bipyramids, edges with two equivalent O(3)Na2Rh3 trigonal bipyramids, and edges with two equivalent O(5)NaCdRh3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Rh(8), two equivalent Rh(6), and two equivalent Cd(1) atoms to form distorted OCd2Rh3 trigonal bipyramids that share corners with two equivalent O(16)Cd2Rh3 square pyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(16)Cd2Rh3 square pyramid, edges with two equivalent O(2)Cd2Rh3 trigonal bipyramids, edges with two equivalent O(4)Cd2Rh3 trigonal bipyramids, and edges with two equivalent O(6)NaCdRh3 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Na(1), one Rh(5), two equivalent Rh(3), and one Cd(1) atom to form distorted ONaCdRh3 trigonal bipyramids that share corners with two equivalent O(14)Cd2Rh3 square pyramids, corners with two equivalent O(15)Na2Rh3 square pyramids,  a cornercorner with one O(1)Cd2Rh3 trigonal bipyramid, corners with two equivalent O(4)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(14)Cd2Rh3 square pyramid, edges with two equivalent O(16)Cd2Rh3 square pyramids, and edges with two equivalent O(3)Na2Rh3 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Na(1), one Rh(6), two equivalent Rh(4), and one Cd(1) atom to form distorted ONaCdRh3 trigonal bipyramids that share corners with two equivalent O(13)Cd2Rh3 square pyramids, corners with two equivalent O(16)Cd2Rh3 square pyramids,  a cornercorner with one O(2)Cd2Rh3 trigonal bipyramid, corners with two equivalent O(3)Na2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(13)Cd2Rh3 square pyramid, edges with two equivalent O(15)Na2Rh3 square pyramids, and edges with two equivalent O(4)Cd2Rh3 trigonal bipyramids. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Rh(7), two equivalent Rh(1), one Cd(2), and one Cd(3) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Rh(8), two equivalent Rh(2), one Cd(2), and one Cd(3) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Rh(1), two equivalent Rh(8), and two equivalent Cd(2) atoms. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Rh(2), two equivalent Rh(7), and two equivalent Cd(3) atoms. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Rh(3), and two equivalent Rh(6) atoms. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Rh(4), two equivalent Rh(5), and two equivalent Cd(1) atoms. In the thirteenth O site, O(13) is bonded to one Rh(2), two equivalent Rh(4), and two equivalent Cd(2) atoms to form OCd2Rh3 square pyramids that share corners with two equivalent O(1)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids, edges with two equivalent O(13)Cd2Rh3 square pyramids, edges with two equivalent O(15)Na2Rh3 square pyramids,  an edgeedge with one O(1)Cd2Rh3 trigonal bipyramid, and  an edgeedge with one O(6)NaCdRh3 trigonal bipyramid. In the fourteenth O site, O(14) is bonded to one Rh(1), two equivalent Rh(3), and two equivalent Cd(3) atoms to form OCd2Rh3 square pyramids that share corners with two equivalent O(2)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, edges with two equivalent O(14)Cd2Rh3 square pyramids, edges with two equivalent O(16)Cd2Rh3 square pyramids,  an edgeedge with one O(2)Cd2Rh3 trigonal bipyramid, and  an edgeedge with one O(5)NaCdRh3 trigonal bipyramid. In the fifteenth O site, O(15) is bonded to two equivalent Na(1), one Rh(4), and two equivalent Rh(2) atoms to form ONa2Rh3 square pyramids that share corners with two equivalent O(3)Na2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, edges with two equivalent O(13)Cd2Rh3 square pyramids, edges with two equivalent O(15)Na2Rh3 square pyramids,  an edgeedge with one O(3)Na2Rh3 trigonal bipyramid, and edges with two equivalent O(6)NaCdRh3 trigonal bipyramids. In the sixteenth O site, O(16) is bonded to one Rh(3), two equivalent Rh(1), and two equivalent Cd(1) atoms to form distorted OCd2Rh3 square pyramids that share corners with two equivalent O(4)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids, edges with two equivalent O(14)Cd2Rh3 square pyramids, edges with two equivalent O(16)Cd2Rh3 square pyramids,  an edgeedge with one O(4)Cd2Rh3 trigonal bipyramid, and edges with two equivalent O(5)NaCdRh3 trigonal bipyramids.
NaCd3(RhO2)8 crystallizes in the monoclinic Pm space group. Na(1) is bonded in a 8-coordinate geometry to one O(5), one O(6), two equivalent O(11), two equivalent O(15), and two equivalent O(3) atoms. The Na(1)-O(5) bond length is 2.56 Å. The Na(1)-O(6) bond length is 2.72 Å. Both Na(1)-O(11) bond lengths are 2.56 Å. Both Na(1)-O(15) bond lengths are 2.40 Å. Both Na(1)-O(3) bond lengths are 2.49 Å. There are eight inequivalent Rh sites. In the first Rh site, Rh(1) is bonded to one O(14), one O(9), two equivalent O(16), and two equivalent O(7) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Rh(1)-O(14) bond length is 2.07 Å. The Rh(1)-O(9) bond length is 2.09 Å. Both Rh(1)-O(16) bond lengths are 2.11 Å. Both Rh(1)-O(7) bond lengths are 2.05 Å. In the second Rh site, Rh(2) is bonded to one O(10), one O(13), two equivalent O(15), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Rh(2)-O(10) bond length is 2.09 Å. The Rh(2)-O(13) bond length is 2.05 Å. Both Rh(2)-O(15) bond lengths are 2.07 Å. Both Rh(2)-O(8) bond lengths are 2.05 Å. In the third Rh site, Rh(3) is bonded to one O(11), one O(16), two equivalent O(14), and two equivalent O(5) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. The Rh(3)-O(11) bond length is 2.07 Å. The Rh(3)-O(16) bond length is 2.06 Å. Both Rh(3)-O(14) bond lengths are 2.13 Å. Both Rh(3)-O(5) bond lengths are 2.03 Å. In the fourth Rh site, Rh(4) is bonded to one O(12), one O(15), two equivalent O(13), and two equivalent O(6) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. The Rh(4)-O(12) bond length is 2.13 Å. The Rh(4)-O(15) bond length is 2.05 Å. Both Rh(4)-O(13) bond lengths are 2.13 Å. Both Rh(4)-O(6) bond lengths are 2.04 Å. In the fifth Rh site, Rh(5) is bonded to one O(1), one O(5), two equivalent O(12), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. The Rh(5)-O(1) bond length is 2.07 Å. The Rh(5)-O(5) bond length is 2.07 Å. Both Rh(5)-O(12) bond lengths are 2.12 Å. Both Rh(5)-O(3) bond lengths are 2.06 Å. In the sixth Rh site, Rh(6) is bonded to one O(2), one O(6), two equivalent O(11), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 51-59°. The Rh(6)-O(2) bond length is 2.07 Å. The Rh(6)-O(6) bond length is 2.09 Å. Both Rh(6)-O(11) bond lengths are 2.06 Å. Both Rh(6)-O(4) bond lengths are 2.11 Å. In the seventh Rh site, Rh(7) is bonded to one O(3), one O(7), two equivalent O(1), and two equivalent O(10) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Rh(7)-O(3) bond length is 2.05 Å. The Rh(7)-O(7) bond length is 2.13 Å. Both Rh(7)-O(1) bond lengths are 2.09 Å. Both Rh(7)-O(10) bond lengths are 2.10 Å. In the eighth Rh site, Rh(8) is bonded to one O(4), one O(8), two equivalent O(2), and two equivalent O(9) atoms to form a mixture of corner and edge-sharing RhO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Rh(8)-O(4) bond length is 2.08 Å. The Rh(8)-O(8) bond length is 2.11 Å. Both Rh(8)-O(2) bond lengths are 2.09 Å. Both Rh(8)-O(9) bond lengths are 2.11 Å. There are three inequivalent Cd sites. In the first Cd site, Cd(1) is bonded in a 8-coordinate geometry to one O(5), one O(6), two equivalent O(12), two equivalent O(16), and two equivalent O(4) atoms. The Cd(1)-O(5) bond length is 2.56 Å. The Cd(1)-O(6) bond length is 2.39 Å. Both Cd(1)-O(12) bond lengths are 2.49 Å. Both Cd(1)-O(16) bond lengths are 2.41 Å. Both Cd(1)-O(4) bond lengths are 2.47 Å. In the second Cd site, Cd(2) is bonded in a 8-coordinate geometry to one O(7), one O(8), two equivalent O(1), two equivalent O(13), and two equivalent O(9) atoms. The Cd(2)-O(7) bond length is 2.42 Å. The Cd(2)-O(8) bond length is 2.69 Å. Both Cd(2)-O(1) bond lengths are 2.49 Å. Both Cd(2)-O(13) bond lengths are 2.39 Å. Both Cd(2)-O(9) bond lengths are 2.51 Å. In the third Cd site, Cd(3) is bonded in a 8-coordinate geometry to one O(7), one O(8), two equivalent O(10), two equivalent O(14), and two equivalent O(2) atoms. The Cd(3)-O(7) bond length is 2.69 Å. The Cd(3)-O(8) bond length is 2.41 Å. Both Cd(3)-O(10) bond lengths are 2.51 Å. Both Cd(3)-O(14) bond lengths are 2.41 Å. Both Cd(3)-O(2) bond lengths are 2.48 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded to one Rh(5), two equivalent Rh(7), and two equivalent Cd(2) atoms to form distorted OCd2Rh3 trigonal bipyramids that share corners with two equivalent O(13)Cd2Rh3 square pyramids,  a cornercorner with one O(5)NaCdRh3 trigonal bipyramid,  an edgeedge with one O(13)Cd2Rh3 square pyramid, edges with two equivalent O(1)Cd2Rh3 trigonal bipyramids, and edges with two equivalent O(3)Na2Rh3 trigonal bipyramids. In the second O site, O(2) is bonded to one Rh(6), two equivalent Rh(8), and two equivalent Cd(3) atoms to form distorted OCd2Rh3 trigonal bipyramids that share corners with two equivalent O(14)Cd2Rh3 square pyramids,  a cornercorner with one O(6)NaCdRh3 trigonal bipyramid,  an edgeedge with one O(14)Cd2Rh3 square pyramid, edges with two equivalent O(2)Cd2Rh3 trigonal bipyramids, and edges with two equivalent O(4)Cd2Rh3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(1), one Rh(7), and two equivalent Rh(5) atoms to form distorted ONa2Rh3 trigonal bipyramids that share corners with two equivalent O(15)Na2Rh3 square pyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(15)Na2Rh3 square pyramid, edges with two equivalent O(1)Cd2Rh3 trigonal bipyramids, edges with two equivalent O(3)Na2Rh3 trigonal bipyramids, and edges with two equivalent O(5)NaCdRh3 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Rh(8), two equivalent Rh(6), and two equivalent Cd(1) atoms to form distorted OCd2Rh3 trigonal bipyramids that share corners with two equivalent O(16)Cd2Rh3 square pyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(16)Cd2Rh3 square pyramid, edges with two equivalent O(2)Cd2Rh3 trigonal bipyramids, edges with two equivalent O(4)Cd2Rh3 trigonal bipyramids, and edges with two equivalent O(6)NaCdRh3 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Na(1), one Rh(5), two equivalent Rh(3), and one Cd(1) atom to form distorted ONaCdRh3 trigonal bipyramids that share corners with two equivalent O(14)Cd2Rh3 square pyramids, corners with two equivalent O(15)Na2Rh3 square pyramids,  a cornercorner with one O(1)Cd2Rh3 trigonal bipyramid, corners with two equivalent O(4)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(14)Cd2Rh3 square pyramid, edges with two equivalent O(16)Cd2Rh3 square pyramids, and edges with two equivalent O(3)Na2Rh3 trigonal bipyramids. In the sixth O site, O(6) is bonded to one Na(1), one Rh(6), two equivalent Rh(4), and one Cd(1) atom to form distorted ONaCdRh3 trigonal bipyramids that share corners with two equivalent O(13)Cd2Rh3 square pyramids, corners with two equivalent O(16)Cd2Rh3 square pyramids,  a cornercorner with one O(2)Cd2Rh3 trigonal bipyramid, corners with two equivalent O(3)Na2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids,  an edgeedge with one O(13)Cd2Rh3 square pyramid, edges with two equivalent O(15)Na2Rh3 square pyramids, and edges with two equivalent O(4)Cd2Rh3 trigonal bipyramids. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Rh(7), two equivalent Rh(1), one Cd(2), and one Cd(3) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Rh(8), two equivalent Rh(2), one Cd(2), and one Cd(3) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Rh(1), two equivalent Rh(8), and two equivalent Cd(2) atoms. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Rh(2), two equivalent Rh(7), and two equivalent Cd(3) atoms. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Rh(3), and two equivalent Rh(6) atoms. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Rh(4), two equivalent Rh(5), and two equivalent Cd(1) atoms. In the thirteenth O site, O(13) is bonded to one Rh(2), two equivalent Rh(4), and two equivalent Cd(2) atoms to form OCd2Rh3 square pyramids that share corners with two equivalent O(1)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids, edges with two equivalent O(13)Cd2Rh3 square pyramids, edges with two equivalent O(15)Na2Rh3 square pyramids,  an edgeedge with one O(1)Cd2Rh3 trigonal bipyramid, and  an edgeedge with one O(6)NaCdRh3 trigonal bipyramid. In the fourteenth O site, O(14) is bonded to one Rh(1), two equivalent Rh(3), and two equivalent Cd(3) atoms to form OCd2Rh3 square pyramids that share corners with two equivalent O(2)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, edges with two equivalent O(14)Cd2Rh3 square pyramids, edges with two equivalent O(16)Cd2Rh3 square pyramids,  an edgeedge with one O(2)Cd2Rh3 trigonal bipyramid, and  an edgeedge with one O(5)NaCdRh3 trigonal bipyramid. In the fifteenth O site, O(15) is bonded to two equivalent Na(1), one Rh(4), and two equivalent Rh(2) atoms to form ONa2Rh3 square pyramids that share corners with two equivalent O(3)Na2Rh3 trigonal bipyramids, corners with two equivalent O(5)NaCdRh3 trigonal bipyramids, edges with two equivalent O(13)Cd2Rh3 square pyramids, edges with two equivalent O(15)Na2Rh3 square pyramids,  an edgeedge with one O(3)Na2Rh3 trigonal bipyramid, and edges with two equivalent O(6)NaCdRh3 trigonal bipyramids. In the sixteenth O site, O(16) is bonded to one Rh(3), two equivalent Rh(1), and two equivalent Cd(1) atoms to form distorted OCd2Rh3 square pyramids that share corners with two equivalent O(4)Cd2Rh3 trigonal bipyramids, corners with two equivalent O(6)NaCdRh3 trigonal bipyramids, edges with two equivalent O(14)Cd2Rh3 square pyramids, edges with two equivalent O(16)Cd2Rh3 square pyramids,  an edgeedge with one O(4)Cd2Rh3 trigonal bipyramid, and edges with two equivalent O(5)NaCdRh3 trigonal bipyramids.