Na2MnPO5F2 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(2), one O(4), two equivalent O(1), and four equivalent F(1) atoms. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with two equivalent Na(2)O4F2 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 69°. Mn(1) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent F(1) atoms. P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Na(2)O4F2 octahedra and  a cornercorner with one O(4)Na3O trigonal pyramid. The corner-sharing octahedral tilt angles are 58°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Na(2), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one P(1) and one O(4) atom. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Na(2), and one O(3) atom to form distorted ONa3O trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with four equivalent F(1)Na3Mn tetrahedra, corners with two equivalent O(4)Na3O trigonal pyramids, and edges with two equivalent F(1)Na3Mn tetrahedra. F(1) is bonded to one Na(2), two equivalent Na(1), and one Mn(1) atom to form distorted FNa3Mn tetrahedra that share corners with six equivalent F(1)Na3Mn tetrahedra, corners with two equivalent O(4)Na3O trigonal pyramids,  an edgeedge with one F(1)Na3Mn tetrahedra, and  an edgeedge with one O(4)Na3O trigonal pyramid.
Na2MnPO5F2 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(2), one O(4), two equivalent O(1), and four equivalent F(1) atoms. The Na(1)-O(2) bond length is 2.86 Å. The Na(1)-O(4) bond length is 2.56 Å. Both Na(1)-O(1) bond lengths are 3.00 Å. There are two shorter (2.42 Å) and two longer (2.70 Å) Na(1)-F(1) bond lengths. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form NaO4F2 octahedra that share corners with two equivalent Na(2)O4F2 octahedra and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 69°. Both Na(2)-O(1) bond lengths are 2.28 Å. Both Na(2)-O(4) bond lengths are 2.44 Å. Both Na(2)-F(1) bond lengths are 2.22 Å. Mn(1) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent F(1) atoms. Both Mn(1)-O(2) bond lengths are 2.33 Å. Both Mn(1)-F(1) bond lengths are 1.99 Å. P(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form PO4 tetrahedra that share corners with two equivalent Na(2)O4F2 octahedra and  a cornercorner with one O(4)Na3O trigonal pyramid. The corner-sharing octahedral tilt angles are 58°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.79 Å. Both P(1)-O(1) bond lengths are 1.50 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Na(1), one Na(2), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one P(1) and one O(4) atom. The O(3)-O(4) bond length is 1.34 Å. In the fourth O site, O(4) is bonded to one Na(1), two equivalent Na(2), and one O(3) atom to form distorted ONa3O trigonal pyramids that share  a cornercorner with one P(1)O4 tetrahedra, corners with four equivalent F(1)Na3Mn tetrahedra, corners with two equivalent O(4)Na3O trigonal pyramids, and edges with two equivalent F(1)Na3Mn tetrahedra. F(1) is bonded to one Na(2), two equivalent Na(1), and one Mn(1) atom to form distorted FNa3Mn tetrahedra that share corners with six equivalent F(1)Na3Mn tetrahedra, corners with two equivalent O(4)Na3O trigonal pyramids,  an edgeedge with one F(1)Na3Mn tetrahedra, and  an edgeedge with one O(4)Na3O trigonal pyramid.