NaIrO3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1) and six equivalent O(2) atoms. Ir(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing IrO6 octahedra. The corner-sharing octahedral tilt angles are 46°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent Ir(1) atoms to form distorted ONa2Ir2 tetrahedra that share corners with eight equivalent O(2)Na3Ir2 square pyramids, corners with four equivalent O(1)Na2Ir2 tetrahedra, and edges with six equivalent O(2)Na3Ir2 square pyramids. In the second O site, O(2) is bonded to three equivalent Na(1) and two equivalent Ir(1) atoms to form distorted ONa3Ir2 square pyramids that share corners with nine equivalent O(2)Na3Ir2 square pyramids, corners with four equivalent O(1)Na2Ir2 tetrahedra, edges with six equivalent O(2)Na3Ir2 square pyramids, and edges with three equivalent O(1)Na2Ir2 tetrahedra.
NaIrO3 crystallizes in the orthorhombic Cmcm space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1) and six equivalent O(2) atoms. Both Na(1)-O(1) bond lengths are 2.34 Å. There are four shorter (2.47 Å) and two longer (2.59 Å) Na(1)-O(2) bond lengths. Ir(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing IrO6 octahedra. The corner-sharing octahedral tilt angles are 46°. Both Ir(1)-O(1) bond lengths are 1.94 Å. All Ir(1)-O(2) bond lengths are 1.98 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent Ir(1) atoms to form distorted ONa2Ir2 tetrahedra that share corners with eight equivalent O(2)Na3Ir2 square pyramids, corners with four equivalent O(1)Na2Ir2 tetrahedra, and edges with six equivalent O(2)Na3Ir2 square pyramids. In the second O site, O(2) is bonded to three equivalent Na(1) and two equivalent Ir(1) atoms to form distorted ONa3Ir2 square pyramids that share corners with nine equivalent O(2)Na3Ir2 square pyramids, corners with four equivalent O(1)Na2Ir2 tetrahedra, edges with six equivalent O(2)Na3Ir2 square pyramids, and edges with three equivalent O(1)Na2Ir2 tetrahedra.