NaIO3 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form corner-sharing NaO6 octahedra. The corner-sharing octahedral tilt angles range from 53-68°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Na(1) and one I(1) atom. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one I(1) atom. I(1) is bonded in a trigonal non-coplanar geometry to one O(2) and two equivalent O(1) atoms.
NaIO3 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form corner-sharing NaO6 octahedra. The corner-sharing octahedral tilt angles range from 53-68°. Both Na(1)-O(2) bond lengths are 2.41 Å. There are two shorter (2.37 Å) and two longer (2.42 Å) Na(1)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Na(1) and one I(1) atom. The O(1)-I(1) bond length is 1.82 Å. In the second O site, O(2) is bonded in a trigonal non-coplanar geometry to two equivalent Na(1) and one I(1) atom. The O(2)-I(1) bond length is 1.80 Å. I(1) is bonded in a trigonal non-coplanar geometry to one O(2) and two equivalent O(1) atoms.