Na2Mn(PO3)5 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(7), one O(8), and two equivalent O(4) atoms. Mn(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(7), one O(8), and two equivalent O(2) atoms to form corner-sharing PO4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. In the third P site, P(3) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. There are nine inequivalent O sites. In the first O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one P(1) atom. In the second O site, O(9) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the fourth O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the fifth O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), one Mn(1), and one P(3) atom. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(3) atom. In the seventh O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Mn(1), and one P(2) atom. In the eighth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the ninth O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(1) atom.
Na2Mn(PO3)5 crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded in a 6-coordinate geometry to one O(3), one O(5), one O(7), one O(8), and two equivalent O(4) atoms. The Na(1)-O(3) bond length is 2.96 Å. The Na(1)-O(5) bond length is 2.58 Å. The Na(1)-O(7) bond length is 2.41 Å. The Na(1)-O(8) bond length is 2.42 Å. There is one shorter (2.42 Å) and one longer (2.44 Å) Na(1)-O(4) bond length. Mn(1) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with four equivalent P(2)O4 tetrahedra. Both Mn(1)-O(3) bond lengths are 1.95 Å. Both Mn(1)-O(5) bond lengths are 2.25 Å. Both Mn(1)-O(6) bond lengths are 1.96 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(7), one O(8), and two equivalent O(2) atoms to form corner-sharing PO4 tetrahedra. The P(1)-O(7) bond length is 1.49 Å. The P(1)-O(8) bond length is 1.49 Å. Both P(1)-O(2) bond lengths are 1.65 Å. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-53°. The P(2)-O(1) bond length is 1.59 Å. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(6) bond length is 1.52 Å. The P(2)-O(9) bond length is 1.59 Å. In the third P site, P(3) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 44°. The P(3)-O(1) bond length is 1.62 Å. The P(3)-O(2) bond length is 1.59 Å. The P(3)-O(3) bond length is 1.53 Å. The P(3)-O(4) bond length is 1.49 Å. There are nine inequivalent O sites. In the first O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Na(1) and one P(1) atom. In the second O site, O(9) is bonded in a bent 150 degrees geometry to two equivalent P(2) atoms. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the fourth O site, O(2) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the fifth O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), one Mn(1), and one P(3) atom. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(3) atom. In the seventh O site, O(5) is bonded in a distorted trigonal planar geometry to one Na(1), one Mn(1), and one P(2) atom. In the eighth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(2) atom. In the ninth O site, O(7) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one P(1) atom.