Na3NO2 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and crystallizes in the orthorhombic Ima2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one N(1), one O(2), and two equivalent O(1) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms. N(1) is bonded in a distorted single-bond geometry to two equivalent Na(1), two equivalent Na(2), and one O(2) atom. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form corner-sharing ONa6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one N(1) atom.
Na3NO2 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and crystallizes in the orthorhombic Ima2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one N(1), one O(2), and two equivalent O(1) atoms. The Na(1)-N(1) bond length is 2.80 Å. The Na(1)-O(2) bond length is 2.68 Å. There is one shorter (2.26 Å) and one longer (2.29 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms. There is one shorter (2.79 Å) and one longer (2.83 Å) Na(2)-N(1) bond length. Both Na(2)-O(1) bond lengths are 2.25 Å. Both Na(2)-O(2) bond lengths are 2.61 Å. N(1) is bonded in a distorted single-bond geometry to two equivalent Na(1), two equivalent Na(2), and one O(2) atom. The N(1)-O(2) bond length is 1.28 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(2) and four equivalent Na(1) atoms to form corner-sharing ONa6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), two equivalent Na(2), and one N(1) atom.