Na2O6I is Hydrophilite-derived structured and crystallizes in the orthorhombic Pnnm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent I(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra, and  an edgeedge with one I(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-68°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one I(1) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one I(1) atom. I(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form IO6 octahedra that share corners with eight equivalent Na(1)O6 octahedra and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-45°.
Na2O6I is Hydrophilite-derived structured and crystallizes in the orthorhombic Pnnm space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted NaO6 octahedra that share corners with four equivalent Na(1)O6 octahedra, corners with four equivalent I(1)O6 octahedra,  an edgeedge with one Na(1)O6 octahedra, and  an edgeedge with one I(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-68°. Both Na(1)-O(2) bond lengths are 2.47 Å. There are two shorter (2.40 Å) and two longer (2.53 Å) Na(1)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one I(1) atom. The O(1)-I(1) bond length is 1.87 Å. In the second O site, O(2) is bonded in a distorted T-shaped geometry to two equivalent Na(1) and one I(1) atom. The O(2)-I(1) bond length is 1.87 Å. I(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form IO6 octahedra that share corners with eight equivalent Na(1)O6 octahedra and edges with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-45°.