LiIrO2 is Caswellsilverite structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with six equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. In the second Ir site, Ir(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, and edges with three equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ir(1), and two equivalent Ir(2) atoms to form a mixture of edge and corner-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Ir(1), and two equivalent Ir(2) atoms to form a mixture of edge and corner-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Ir(1), and two equivalent Ir(2) atoms to form a mixture of edge and corner-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.
LiIrO2 is Caswellsilverite structured and crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Li(1)-O(1) bond lengths are 2.22 Å. Both Li(1)-O(2) bond lengths are 2.24 Å. Both Li(1)-O(3) bond lengths are 2.34 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles are 7°. Both Li(2)-O(1) bond lengths are 2.28 Å. Both Li(2)-O(2) bond lengths are 2.27 Å. Both Li(2)-O(3) bond lengths are 2.23 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ir(1)O6 octahedra, corners with four equivalent Ir(2)O6 octahedra, edges with two equivalent Ir(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with four equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Both Li(3)-O(1) bond lengths are 2.45 Å. Both Li(3)-O(2) bond lengths are 2.23 Å. Both Li(3)-O(3) bond lengths are 2.14 Å. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with six equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-9°. Both Ir(1)-O(1) bond lengths are 2.09 Å. Both Ir(1)-O(2) bond lengths are 2.10 Å. Both Ir(1)-O(3) bond lengths are 2.09 Å. In the second Ir site, Ir(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted IrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, and edges with three equivalent Ir(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Both Ir(2)-O(1) bond lengths are 2.09 Å. There is one shorter (2.09 Å) and one longer (2.10 Å) Ir(2)-O(2) bond length. Both Ir(2)-O(3) bond lengths are 2.10 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Ir(1), and two equivalent Ir(2) atoms to form a mixture of edge and corner-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Ir(1), and two equivalent Ir(2) atoms to form a mixture of edge and corner-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Ir(1), and two equivalent Ir(2) atoms to form a mixture of edge and corner-sharing OLi3Ir3 octahedra. The corner-sharing octahedral tilt angles range from 0-10°.