LiIrO2 is Caswellsilverite structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Ir(2)O6 octahedra, corners with four equivalent Ir(1)O6 octahedra, edges with two equivalent Ir(2)O6 octahedra, edges with four equivalent Ir(1)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Ir(2)O6 octahedra, corners with four equivalent Ir(1)O6 octahedra, edges with two equivalent Ir(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, edges with three equivalent Ir(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. In the second Ir site, Ir(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with six equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Ir(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Ir(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.
LiIrO2 is Caswellsilverite structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Ir(2)O6 octahedra, corners with four equivalent Ir(1)O6 octahedra, edges with two equivalent Ir(2)O6 octahedra, edges with four equivalent Ir(1)O6 octahedra, and edges with six equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. Both Li(1)-O(2) bond lengths are 2.26 Å. All Li(1)-O(1) bond lengths are 2.26 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Ir(2)O6 octahedra, corners with four equivalent Ir(1)O6 octahedra, edges with two equivalent Ir(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-8°. Both Li(2)-O(2) bond lengths are 2.34 Å. There are two shorter (2.19 Å) and two longer (2.26 Å) Li(2)-O(1) bond lengths. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, edges with three equivalent Ir(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Ir(1)-O(2) bond lengths are 2.09 Å. There are two shorter (2.10 Å) and two longer (2.11 Å) Ir(1)-O(1) bond lengths. In the second Ir site, Ir(2) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with six equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-8°. Both Ir(2)-O(2) bond lengths are 2.10 Å. All Ir(2)-O(1) bond lengths are 2.10 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one Ir(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), one Ir(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-3°.