Na3P3N3O7 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. In the third Na site, Na(3) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms to form distorted NaO6 octahedra that share corners with two equivalent P(1)N2O2 tetrahedra, corners with two equivalent P(2)N2O2 tetrahedra, and corners with two equivalent P(3)N2O2 tetrahedra. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms. There are three inequivalent P sites. In the first P site, P(1) is bonded to one N(2), one N(3), one O(7), and one O(8) atom to form PN2O2 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(2)N2O2 tetrahedra, and  a cornercorner with one P(3)N2O2 tetrahedra. The corner-sharing octahedral tilt angles are 61°. In the second P site, P(2) is bonded to one N(1), one N(2), one O(4), and one O(6) atom to form PN2O2 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(1)N2O2 tetrahedra, and  a cornercorner with one P(3)N2O2 tetrahedra. The corner-sharing octahedral tilt angles are 60°. In the third P site, P(3) is bonded to one N(1), one N(3), one O(2), and one O(3) atom to form PN2O2 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(1)N2O2 tetrahedra, and  a cornercorner with one P(2)N2O2 tetrahedra. The corner-sharing octahedral tilt angles are 63°. There are three inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the second N site, N(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the third N site, N(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Na(2) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Na(4), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(4), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent Na(2) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(2), one Na(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(4) and one P(1) atom.
Na3P3N3O7 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom. The Na(1)-O(1) bond length is 2.91 Å. The Na(1)-O(2) bond length is 2.30 Å. The Na(1)-O(3) bond length is 2.25 Å. The Na(1)-O(4) bond length is 2.38 Å. The Na(1)-O(5) bond length is 2.60 Å. The Na(1)-O(7) bond length is 2.33 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(6), and one O(7) atom. The Na(2)-O(1) bond length is 2.81 Å. The Na(2)-O(3) bond length is 2.44 Å. The Na(2)-O(4) bond length is 2.42 Å. The Na(2)-O(5) bond length is 2.96 Å. The Na(2)-O(6) bond length is 2.37 Å. The Na(2)-O(7) bond length is 2.37 Å. In the third Na site, Na(3) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms to form distorted NaO6 octahedra that share corners with two equivalent P(1)N2O2 tetrahedra, corners with two equivalent P(2)N2O2 tetrahedra, and corners with two equivalent P(3)N2O2 tetrahedra. Both Na(3)-O(2) bond lengths are 2.62 Å. Both Na(3)-O(6) bond lengths are 2.49 Å. Both Na(3)-O(7) bond lengths are 2.51 Å. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms. Both Na(4)-O(2) bond lengths are 2.58 Å. Both Na(4)-O(4) bond lengths are 2.77 Å. Both Na(4)-O(8) bond lengths are 2.34 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one N(2), one N(3), one O(7), and one O(8) atom to form PN2O2 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(2)N2O2 tetrahedra, and  a cornercorner with one P(3)N2O2 tetrahedra. The corner-sharing octahedral tilt angles are 61°. The P(1)-N(2) bond length is 1.66 Å. The P(1)-N(3) bond length is 1.67 Å. The P(1)-O(7) bond length is 1.54 Å. The P(1)-O(8) bond length is 1.51 Å. In the second P site, P(2) is bonded to one N(1), one N(2), one O(4), and one O(6) atom to form PN2O2 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(1)N2O2 tetrahedra, and  a cornercorner with one P(3)N2O2 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The P(2)-N(1) bond length is 1.66 Å. The P(2)-N(2) bond length is 1.66 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.52 Å. In the third P site, P(3) is bonded to one N(1), one N(3), one O(2), and one O(3) atom to form PN2O2 tetrahedra that share  a cornercorner with one Na(3)O6 octahedra,  a cornercorner with one P(1)N2O2 tetrahedra, and  a cornercorner with one P(2)N2O2 tetrahedra. The corner-sharing octahedral tilt angles are 63°. The P(3)-N(1) bond length is 1.67 Å. The P(3)-N(3) bond length is 1.66 Å. The P(3)-O(2) bond length is 1.54 Å. The P(3)-O(3) bond length is 1.51 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the second N site, N(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the third N site, N(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(1) and two equivalent Na(2) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Na(4), and one P(3) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(3) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Na(4), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Na(1) and two equivalent Na(2) atoms. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Na(2), one Na(3), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(4) and one P(1) atom.