NaO2 crystallizes in the trigonal R-3m space group. Na(1) is bonded to eight equivalent O(1) atoms to form NaO8 hexagonal bipyramids that share corners with eight equivalent O(1)Na4O trigonal bipyramids and edges with twelve equivalent Na(1)O8 hexagonal bipyramids. O(1) is bonded to four equivalent Na(1) and one O(1) atom to form ONa4O trigonal bipyramids that share corners with four equivalent Na(1)O8 hexagonal bipyramids, corners with sixteen equivalent O(1)Na4O trigonal bipyramids, and edges with six equivalent O(1)Na4O trigonal bipyramids.
NaO2 crystallizes in the trigonal R-3m space group. Na(1) is bonded to eight equivalent O(1) atoms to form NaO8 hexagonal bipyramids that share corners with eight equivalent O(1)Na4O trigonal bipyramids and edges with twelve equivalent Na(1)O8 hexagonal bipyramids. There are six shorter (2.59 Å) and two longer (2.60 Å) Na(1)-O(1) bond lengths. O(1) is bonded to four equivalent Na(1) and one O(1) atom to form ONa4O trigonal bipyramids that share corners with four equivalent Na(1)O8 hexagonal bipyramids, corners with sixteen equivalent O(1)Na4O trigonal bipyramids, and edges with six equivalent O(1)Na4O trigonal bipyramids. The O(1)-O(1) bond length is 1.36 Å.