NaO2I crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six equivalent O(1) atoms to form edge-sharing NaO6 octahedra. O(1) is bonded to three equivalent Na(1) and two equivalent I(1) atoms to form a mixture of distorted edge and corner-sharing ONa3I2 trigonal bipyramids. I(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms.
NaO2I crystallizes in the tetragonal I4_1/amd space group. Na(1) is bonded to six equivalent O(1) atoms to form edge-sharing NaO6 octahedra. There are four shorter (2.47 Å) and two longer (2.58 Å) Na(1)-O(1) bond lengths. O(1) is bonded to three equivalent Na(1) and two equivalent I(1) atoms to form a mixture of distorted edge and corner-sharing ONa3I2 trigonal bipyramids. Both O(1)-I(1) bond lengths are 2.21 Å. I(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms.