Na4Mn2P2O7F6 crystallizes in the monoclinic P2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(3) atoms to form distorted NaO2F4 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(4)F6 octahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 71°. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent F(2) atoms. In the fourth Na site, Na(4) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted NaF6 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Na(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 22-43°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(4), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with four equivalent Na(4)F6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and edges with two equivalent Na(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 22-43°. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Na(4)F6 octahedra, corners with two equivalent Na(1)O2F4 octahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-71°. P(1) 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 Na(1)O2F4 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-70°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(3), one Mn(1), and one P(1) atom. There are three inequivalent F sites. In the first F site, F(2) is bonded to one Na(2), one Na(3), one Na(4), and one Mn(2) atom to form distorted corner-sharing FNa3Mn tetrahedra. In the second F site, F(3) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Na(4), and one Mn(1) atom. In the third F site, F(1) is bonded in a distorted T-shaped geometry to one Na(1), one Na(4), and one Mn(1) atom.
Na4Mn2P2O7F6 crystallizes in the monoclinic P2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(3) atoms to form distorted NaO2F4 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Na(4)F6 octahedra, and edges with two equivalent Mn(1)O2F4 octahedra. The corner-sharing octahedral tilt angles are 71°. Both Na(1)-O(3) bond lengths are 2.42 Å. Both Na(1)-F(1) bond lengths are 2.38 Å. Both Na(1)-F(3) bond lengths are 2.48 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms. Both Na(2)-O(1) bond lengths are 2.54 Å. Both Na(2)-F(2) bond lengths are 2.36 Å. Both Na(2)-F(3) bond lengths are 2.35 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(4), and two equivalent F(2) atoms. Both Na(3)-O(3) bond lengths are 2.81 Å. Both Na(3)-O(4) bond lengths are 2.32 Å. Both Na(3)-F(2) bond lengths are 2.52 Å. In the fourth Na site, Na(4) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form distorted NaF6 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent Mn(1)O2F4 octahedra, and edges with two equivalent Na(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 22-43°. Both Na(4)-F(1) bond lengths are 2.34 Å. Both Na(4)-F(2) bond lengths are 2.46 Å. Both Na(4)-F(3) bond lengths are 2.33 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(4), two equivalent F(1), and two equivalent F(3) atoms to form MnO2F4 octahedra that share corners with four equivalent Na(4)F6 octahedra, corners with two equivalent P(1)O4 tetrahedra, and edges with two equivalent Na(1)O2F4 octahedra. The corner-sharing octahedral tilt angles range from 22-43°. Both Mn(1)-O(4) bond lengths are 2.18 Å. Both Mn(1)-F(1) bond lengths are 1.88 Å. Both Mn(1)-F(3) bond lengths are 1.92 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Na(4)F6 octahedra, corners with two equivalent Na(1)O2F4 octahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-71°. Both Mn(2)-O(1) bond lengths are 1.98 Å. Both Mn(2)-O(3) bond lengths are 2.24 Å. Both Mn(2)-F(2) bond lengths are 1.90 Å. P(1) 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 Na(1)O2F4 octahedra,  a cornercorner with one Mn(1)O2F4 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-70°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.64 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.51 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(3), one Mn(1), and one P(1) atom. There are three inequivalent F sites. In the first F site, F(2) is bonded to one Na(2), one Na(3), one Na(4), and one Mn(2) atom to form distorted corner-sharing FNa3Mn tetrahedra. In the second F site, F(3) is bonded in a distorted see-saw-like geometry to one Na(1), one Na(2), one Na(4), and one Mn(1) atom. In the third F site, F(1) is bonded in a distorted T-shaped geometry to one Na(1), one Na(4), and one Mn(1) atom.