Na3NO2 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. In the second Na site, Na(2) is bonded to two equivalent N(1), one O(1), and two equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing NaN2O3 trigonal bipyramids. N(1) is bonded in a 6-coordinate geometry to four equivalent Na(2) and two equivalent O(1) atoms. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and two equivalent N(1) atoms. In the second O site, O(2) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form corner-sharing ONa6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.
Na3NO2 crystallizes in the tetragonal P4_2/mnm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(2) atoms. Both Na(1)-O(1) bond lengths are 2.62 Å. Both Na(1)-O(2) bond lengths are 2.33 Å. In the second Na site, Na(2) is bonded to two equivalent N(1), one O(1), and two equivalent O(2) atoms to form a mixture of distorted edge and corner-sharing NaN2O3 trigonal bipyramids. There is one shorter (2.53 Å) and one longer (2.71 Å) Na(2)-N(1) bond length. The Na(2)-O(1) bond length is 2.68 Å. Both Na(2)-O(2) bond lengths are 2.30 Å. N(1) is bonded in a 6-coordinate geometry to four equivalent Na(2) and two equivalent O(1) atoms. Both N(1)-O(1) bond lengths are 1.50 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and two equivalent N(1) atoms. In the second O site, O(2) is bonded to two equivalent Na(1) and four equivalent Na(2) atoms to form corner-sharing ONa6 octahedra. The corner-sharing octahedral tilt angles range from 0-6°.