LiO5I crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share corners with two equivalent I(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and edges with two equivalent I(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-62°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to two equivalent I(1) atoms. In the second O site, O(2) is bonded in a water-like geometry to one Li(1) and one I(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one I(1) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Li(1) and one I(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one I(1) atom. I(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form IO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  an edgeedge with one I(1)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°.
LiO5I crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(2), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form distorted LiO6 octahedra that share corners with two equivalent I(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and edges with two equivalent I(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-62°. The Li(1)-O(2) bond length is 2.16 Å. The Li(1)-O(4) bond length is 2.27 Å. There is one shorter (2.10 Å) and one longer (2.20 Å) Li(1)-O(3) bond length. There is one shorter (2.11 Å) and one longer (2.39 Å) Li(1)-O(5) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a water-like geometry to two equivalent I(1) atoms. There is one shorter (2.00 Å) and one longer (2.01 Å) O(1)-I(1) bond length. In the second O site, O(2) is bonded in a water-like geometry to one Li(1) and one I(1) atom. The O(2)-I(1) bond length is 1.87 Å. In the third O site, O(3) is bonded in a trigonal planar geometry to two equivalent Li(1) and one I(1) atom. The O(3)-I(1) bond length is 1.85 Å. In the fourth O site, O(4) is bonded in a water-like geometry to one Li(1) and one I(1) atom. The O(4)-I(1) bond length is 1.87 Å. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one I(1) atom. The O(5)-I(1) bond length is 1.86 Å. I(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form IO6 octahedra that share corners with two equivalent Li(1)O6 octahedra,  an edgeedge with one I(1)O6 octahedra, and edges with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°.