La3IrI3 is Ilmenite-like structured and crystallizes in the monoclinic C2 space group. There are six inequivalent La sites. In the first La site, La(1) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(5) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the second La site, La(2) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(6) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the third La site, La(3) is bonded to two equivalent Ir(1), one I(1), one I(2), one I(5), and one I(6) atom to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. In the fourth La site, La(4) is bonded to two equivalent Ir(2), one I(1), one I(2), one I(5), and one I(6) atom to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the fifth La site, La(5) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(2) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. In the sixth La site, La(6) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(1) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to one La(1), one La(2), one La(5), one La(6), and two equivalent La(3) atoms to form edge-sharing IrLa6 octahedra. In the second Ir site, Ir(2) is bonded to one La(1), one La(2), one La(5), one La(6), and two equivalent La(4) atoms to form edge-sharing IrLa6 octahedra. There are six inequivalent I sites. In the first I site, I(1) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(6) atoms. In the second I site, I(2) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(5) atoms. In the third I site, I(3) is bonded in a distorted rectangular see-saw-like geometry to one La(1), one La(2), one La(5), and one La(6) atom. In the fourth I site, I(4) is bonded in a distorted rectangular see-saw-like geometry to one La(1), one La(2), one La(5), and one La(6) atom. In the fifth I site, I(5) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(1) atoms. In the sixth I site, I(6) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(2) atoms.
La3IrI3 is Ilmenite-like structured and crystallizes in the monoclinic C2 space group. There are six inequivalent La sites. In the first La site, La(1) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(5) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. The La(1)-Ir(1) bond length is 2.91 Å. The La(1)-Ir(2) bond length is 2.90 Å. The La(1)-I(3) bond length is 3.33 Å. The La(1)-I(4) bond length is 3.49 Å. There is one shorter (3.34 Å) and one longer (3.49 Å) La(1)-I(5) bond length. In the second La site, La(2) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(6) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. The La(2)-Ir(1) bond length is 2.89 Å. The La(2)-Ir(2) bond length is 2.90 Å. The La(2)-I(3) bond length is 3.50 Å. The La(2)-I(4) bond length is 3.34 Å. There is one shorter (3.34 Å) and one longer (3.50 Å) La(2)-I(6) bond length. In the third La site, La(3) is bonded to two equivalent Ir(1), one I(1), one I(2), one I(5), and one I(6) atom to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. There is one shorter (2.90 Å) and one longer (2.91 Å) La(3)-Ir(1) bond length. The La(3)-I(1) bond length is 3.48 Å. The La(3)-I(2) bond length is 3.33 Å. The La(3)-I(5) bond length is 3.48 Å. The La(3)-I(6) bond length is 3.34 Å. In the fourth La site, La(4) is bonded to two equivalent Ir(2), one I(1), one I(2), one I(5), and one I(6) atom to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. There is one shorter (2.90 Å) and one longer (2.91 Å) La(4)-Ir(2) bond length. The La(4)-I(1) bond length is 3.33 Å. The La(4)-I(2) bond length is 3.48 Å. The La(4)-I(5) bond length is 3.33 Å. The La(4)-I(6) bond length is 3.48 Å. In the fifth La site, La(5) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(2) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. The La(5)-Ir(1) bond length is 2.90 Å. The La(5)-Ir(2) bond length is 2.90 Å. The La(5)-I(3) bond length is 3.49 Å. The La(5)-I(4) bond length is 3.34 Å. There is one shorter (3.34 Å) and one longer (3.48 Å) La(5)-I(2) bond length. In the sixth La site, La(6) is bonded to one Ir(1), one Ir(2), one I(3), one I(4), and two equivalent I(1) atoms to form a mixture of distorted corner and edge-sharing LaIr2I4 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. The La(6)-Ir(1) bond length is 2.91 Å. The La(6)-Ir(2) bond length is 2.89 Å. The La(6)-I(3) bond length is 3.34 Å. The La(6)-I(4) bond length is 3.49 Å. There is one shorter (3.34 Å) and one longer (3.49 Å) La(6)-I(1) bond length. There are two inequivalent Ir sites. In the first Ir site, Ir(1) is bonded to one La(1), one La(2), one La(5), one La(6), and two equivalent La(3) atoms to form edge-sharing IrLa6 octahedra. In the second Ir site, Ir(2) is bonded to one La(1), one La(2), one La(5), one La(6), and two equivalent La(4) atoms to form edge-sharing IrLa6 octahedra. There are six inequivalent I sites. In the first I site, I(1) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(6) atoms. In the second I site, I(2) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(5) atoms. In the third I site, I(3) is bonded in a distorted rectangular see-saw-like geometry to one La(1), one La(2), one La(5), and one La(6) atom. In the fourth I site, I(4) is bonded in a distorted rectangular see-saw-like geometry to one La(1), one La(2), one La(5), and one La(6) atom. In the fifth I site, I(5) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(1) atoms. In the sixth I site, I(6) is bonded in a distorted rectangular see-saw-like geometry to one La(3), one La(4), and two equivalent La(2) atoms.