Na3IrCd2O6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Cd(1)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with four equivalent Cd(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-16°. In the second Na site, Na(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Cd(1)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. Ir(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form IrO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with six equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Cd(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted CdO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, edges with three equivalent Cd(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-18°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(2), one Ir(1), and two equivalent Cd(1) atoms to form a mixture of distorted corner and edge-sharing ONa3Cd2Ir octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), one Ir(1), and two equivalent Cd(1) atoms to form a mixture of corner and edge-sharing ONa3Cd2Ir octahedra. The corner-sharing octahedral tilt angles range from 0-11°.
Na3IrCd2O6 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Cd(1)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with four equivalent Cd(1)O6 octahedra, and edges with six equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-16°. Both Na(1)-O(1) bond lengths are 2.73 Å. All Na(1)-O(2) bond lengths are 2.37 Å. In the second Na site, Na(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Cd(1)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. Both Na(2)-O(1) bond lengths are 2.38 Å. There are two shorter (2.38 Å) and two longer (2.68 Å) Na(2)-O(2) bond lengths. Ir(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form IrO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with six equivalent Cd(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. Both Ir(1)-O(1) bond lengths are 2.01 Å. All Ir(1)-O(2) bond lengths are 2.02 Å. Cd(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted CdO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, edges with three equivalent Cd(1)O6 octahedra, and edges with four equivalent Na(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-18°. Both Cd(1)-O(1) bond lengths are 2.35 Å. There are two shorter (2.35 Å) and two longer (2.39 Å) Cd(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), two equivalent Na(2), one Ir(1), and two equivalent Cd(1) atoms to form a mixture of distorted corner and edge-sharing ONa3Cd2Ir octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the second O site, O(2) is bonded to one Na(1), two equivalent Na(2), one Ir(1), and two equivalent Cd(1) atoms to form a mixture of corner and edge-sharing ONa3Cd2Ir octahedra. The corner-sharing octahedral tilt angles range from 0-11°.