Na3Ir(NO2)6 crystallizes in the trigonal R-3m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of face and corner-sharing NaO6 octahedra. In the second Na site, Na(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form a mixture of distorted face and corner-sharing NaO12 cuboctahedra. The corner-sharing octahedral tilt angles are 45°. Ir(1) is bonded in an octahedral geometry to six equivalent N(1) atoms. N(1) is bonded in a trigonal planar geometry to one Ir(1), one O(1), and one O(2) atom. There are two inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one N(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), and one N(1) atom.
Na3Ir(NO2)6 crystallizes in the trigonal R-3m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form a mixture of face and corner-sharing NaO6 octahedra. All Na(1)-O(1) bond lengths are 2.36 Å. All Na(1)-O(2) bond lengths are 2.40 Å. In the second Na site, Na(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form a mixture of distorted face and corner-sharing NaO12 cuboctahedra. The corner-sharing octahedral tilt angles are 45°. All Na(2)-O(1) bond lengths are 2.95 Å. All Na(2)-O(2) bond lengths are 2.66 Å. Ir(1) is bonded in an octahedral geometry to six equivalent N(1) atoms. All Ir(1)-N(1) bond lengths are 2.09 Å. N(1) is bonded in a trigonal planar geometry to one Ir(1), one O(1), and one O(2) atom. The N(1)-O(1) bond length is 1.25 Å. The N(1)-O(2) bond length is 1.25 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one N(1) atom. In the second O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), and one N(1) atom.