Na3N2O9 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted corner-sharing NaO4 trigonal pyramids. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(7), two equivalent O(3), and two equivalent O(6) atoms. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(5), two equivalent O(8), and two equivalent O(9) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one O(4) and one O(6) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one O(3), one O(7), and one O(9) atom. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one O(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Na(2) and one O(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one N(2) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Na(1) and one N(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one O(7) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(2) and one N(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one N(2), and one O(5) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Na(3) atoms. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to two equivalent Na(3) and one N(2) atom.
Na3N2O9 crystallizes in the triclinic P1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted corner-sharing NaO4 trigonal pyramids. The Na(1)-O(4) bond length is 2.37 Å. The Na(1)-O(8) bond length is 2.22 Å. Both Na(1)-O(1) bond lengths are 2.40 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(2), one O(7), two equivalent O(3), and two equivalent O(6) atoms. The Na(2)-O(2) bond length is 2.92 Å. The Na(2)-O(7) bond length is 2.41 Å. There is one shorter (2.52 Å) and one longer (2.65 Å) Na(2)-O(3) bond length. There is one shorter (2.45 Å) and one longer (2.50 Å) Na(2)-O(6) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(5), two equivalent O(8), and two equivalent O(9) atoms. The Na(3)-O(5) bond length is 2.31 Å. There is one shorter (2.43 Å) and one longer (2.47 Å) Na(3)-O(8) bond length. There is one shorter (2.64 Å) and one longer (2.68 Å) Na(3)-O(9) bond length. There are two inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one O(4) and one O(6) atom. The N(1)-O(4) bond length is 1.26 Å. The N(1)-O(6) bond length is 1.26 Å. In the second N site, N(2) is bonded in a trigonal planar geometry to one O(3), one O(7), and one O(9) atom. The N(2)-O(3) bond length is 1.23 Å. The N(2)-O(7) bond length is 1.54 Å. The N(2)-O(9) bond length is 1.21 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one O(2) atom. The O(1)-O(2) bond length is 1.28 Å. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Na(2) and one O(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one N(2) atom. In the fourth O site, O(4) is bonded in a water-like geometry to one Na(1) and one N(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Na(3) and one O(7) atom. The O(5)-O(7) bond length is 1.35 Å. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(2) and one N(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one N(2), and one O(5) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Na(3) atoms. In the ninth O site, O(9) is bonded in a distorted single-bond geometry to two equivalent Na(3) and one N(2) atom.