Na8Fe6P6(O8F3)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(5), one F(2), one F(4), and one F(5) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(4), one F(1), and two equivalent F(3) atoms. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one F(1), one F(4), and one F(5) atom. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(2), two equivalent O(6), one F(1), and one F(3) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(3)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 5°. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(5), one F(2), and one F(4) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedra are not tilted. In the third Fe site, Fe(3) is bonded to two equivalent O(3), two equivalent O(4), one F(1), and one F(5) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 5°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra, and corners with two equivalent Fe(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O4F2 octahedra and corners with two equivalent Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-45°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Fe(2), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(3), one Fe(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Fe(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(3), one Fe(1), and one P(1) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted square pyramidal geometry to one Na(2), two equivalent Na(3), one Fe(1), and one Fe(3) atom. In the second F site, F(2) is bonded in a square co-planar geometry to two equivalent Na(1) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(3), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(3), and one Fe(3) atom.
Na8Fe6P6(O8F3)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to two equivalent O(1), two equivalent O(5), one F(2), one F(4), and one F(5) atom. Both Na(1)-O(1) bond lengths are 2.42 Å. Both Na(1)-O(5) bond lengths are 2.44 Å. The Na(1)-F(2) bond length is 2.36 Å. The Na(1)-F(4) bond length is 2.51 Å. The Na(1)-F(5) bond length is 2.54 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to two equivalent O(2), two equivalent O(4), one F(1), and two equivalent F(3) atoms. Both Na(2)-O(2) bond lengths are 2.59 Å. Both Na(2)-O(4) bond lengths are 2.58 Å. The Na(2)-F(1) bond length is 2.64 Å. Both Na(2)-F(3) bond lengths are 2.41 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(2), one O(3), one O(4), one O(6), one F(1), one F(4), and one F(5) atom. The Na(3)-O(2) bond length is 2.65 Å. The Na(3)-O(3) bond length is 2.39 Å. The Na(3)-O(4) bond length is 2.69 Å. The Na(3)-O(6) bond length is 2.39 Å. The Na(3)-F(1) bond length is 2.57 Å. The Na(3)-F(4) bond length is 2.49 Å. The Na(3)-F(5) bond length is 2.52 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(2), two equivalent O(6), one F(1), and one F(3) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(3)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 5°. Both Fe(1)-O(2) bond lengths are 2.07 Å. Both Fe(1)-O(6) bond lengths are 2.01 Å. The Fe(1)-F(1) bond length is 2.03 Å. The Fe(1)-F(3) bond length is 1.90 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(1), two equivalent O(5), one F(2), and one F(4) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedra are not tilted. Both Fe(2)-O(1) bond lengths are 2.01 Å. Both Fe(2)-O(5) bond lengths are 2.01 Å. The Fe(2)-F(2) bond length is 2.04 Å. The Fe(2)-F(4) bond length is 1.96 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(3), two equivalent O(4), one F(1), and one F(5) atom to form FeO4F2 octahedra that share  a cornercorner with one Fe(1)O4F2 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 5°. Both Fe(3)-O(3) bond lengths are 2.00 Å. Both Fe(3)-O(4) bond lengths are 2.04 Å. The Fe(3)-F(1) bond length is 2.04 Å. The Fe(3)-F(5) bond length is 1.95 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra, and corners with two equivalent Fe(3)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-46°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.54 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Fe(1)O4F2 octahedra and corners with two equivalent Fe(2)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 43-45°. Both P(2)-O(2) bond lengths are 1.55 Å. Both P(2)-O(5) bond lengths are 1.55 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Fe(2), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(3), one Fe(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Fe(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Fe(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(3), one Fe(1), and one P(1) atom. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted square pyramidal geometry to one Na(2), two equivalent Na(3), one Fe(1), and one Fe(3) atom. In the second F site, F(2) is bonded in a square co-planar geometry to two equivalent Na(1) and two equivalent Fe(2) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to two equivalent Na(2) and one Fe(1) atom. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(3), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(1), two equivalent Na(3), and one Fe(3) atom.