NaFeP2(O3F)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one O(1), one O(4), two equivalent O(6), and one F(1) atom to form distorted NaO4F trigonal bipyramids that share corners with two equivalent P(2)O3F tetrahedra, corners with three equivalent P(1)O3F tetrahedra, edges with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Na(1)O4F trigonal bipyramid. Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share corners with three equivalent P(1)O3F tetrahedra, corners with three equivalent P(2)O3F tetrahedra, and edges with two equivalent Na(1)O4F trigonal bipyramids. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one F(1) atom to form PO3F tetrahedra that share corners with three equivalent Fe(1)O6 octahedra and corners with three equivalent Na(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-47°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(4), and one F(2) atom to form PO3F tetrahedra that share corners with three equivalent Fe(1)O6 octahedra and corners with two equivalent Na(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 33-49°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the second O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Fe(1), and one P(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(1), and one P(2) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(1), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Na(1) and one P(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one P(2) atom.
NaFeP2(O3F)2 crystallizes in the monoclinic P2_1/c space group. Na(1) is bonded to one O(1), one O(4), two equivalent O(6), and one F(1) atom to form distorted NaO4F trigonal bipyramids that share corners with two equivalent P(2)O3F tetrahedra, corners with three equivalent P(1)O3F tetrahedra, edges with two equivalent Fe(1)O6 octahedra, and  an edgeedge with one Na(1)O4F trigonal bipyramid. The Na(1)-O(1) bond length is 2.35 Å. The Na(1)-O(4) bond length is 2.30 Å. There is one shorter (2.49 Å) and one longer (2.53 Å) Na(1)-O(6) bond length. The Na(1)-F(1) bond length is 2.29 Å. Fe(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form FeO6 octahedra that share corners with three equivalent P(1)O3F tetrahedra, corners with three equivalent P(2)O3F tetrahedra, and edges with two equivalent Na(1)O4F trigonal bipyramids. The Fe(1)-O(1) bond length is 2.04 Å. The Fe(1)-O(2) bond length is 2.01 Å. The Fe(1)-O(3) bond length is 1.99 Å. The Fe(1)-O(4) bond length is 2.06 Å. The Fe(1)-O(5) bond length is 1.98 Å. The Fe(1)-O(6) bond length is 2.12 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(5), one O(6), and one F(1) atom to form PO3F tetrahedra that share corners with three equivalent Fe(1)O6 octahedra and corners with three equivalent Na(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-47°. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.51 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-F(1) bond length is 1.60 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(4), and one F(2) atom to form PO3F tetrahedra that share corners with three equivalent Fe(1)O6 octahedra and corners with two equivalent Na(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles range from 33-49°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.52 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-F(2) bond length is 1.59 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the second O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Fe(1), and one P(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(1), and one P(2) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the sixth O site, O(4) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(1), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a bent 150 degrees geometry to one Na(1) and one P(1) atom. In the second F site, F(2) is bonded in a single-bond geometry to one P(2) atom.