Li2IrO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fddd space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Ir(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with four equivalent Ir(1)O6 octahedra, and edges with five equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ir(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with five equivalent Li(1)O6 octahedra, and edges with five equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. 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 Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with five equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°.
Li2IrO3 is Caswellsilverite-like structured and crystallizes in the orthorhombic Fddd space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Ir(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with four equivalent Ir(1)O6 octahedra, and edges with five equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. Both Li(1)-O(1) bond lengths are 2.13 Å. There are two shorter (2.09 Å) and two longer (2.14 Å) Li(1)-O(2) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Ir(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with five equivalent Li(1)O6 octahedra, and edges with five equivalent Ir(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. Both Li(2)-O(1) bond lengths are 2.06 Å. There are two shorter (2.09 Å) and two longer (2.13 Å) Li(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 Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Ir(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with five equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. Both Ir(1)-O(1) bond lengths are 2.04 Å. There are two shorter (2.02 Å) and two longer (2.05 Å) Ir(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. In the second O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(2), and two equivalent Ir(1) atoms to form a mixture of corner and edge-sharing OLi4Ir2 octahedra. The corner-sharing octahedral tilt angles range from 1-5°.