LiIO3 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted edge-sharing LiO5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one I(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(1) and one I(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one I(1) atom. I(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom.
LiIO3 crystallizes in the orthorhombic Pna2_1 space group. Li(1) is bonded to one O(2), two equivalent O(1), and two equivalent O(3) atoms to form distorted edge-sharing LiO5 trigonal bipyramids. The Li(1)-O(2) bond length is 1.95 Å. There is one shorter (1.99 Å) and one longer (2.02 Å) Li(1)-O(1) bond length. There is one shorter (2.05 Å) and one longer (2.11 Å) Li(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one I(1) atom. The O(1)-I(1) bond length is 1.80 Å. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Li(1) and one I(1) atom. The O(2)-I(1) bond length is 1.81 Å. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one I(1) atom. The O(3)-I(1) bond length is 1.81 Å. I(1) is bonded in a distorted trigonal non-coplanar geometry to one O(1), one O(2), and one O(3) atom.