Na2FeSO4F3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form NaO4F2 octahedra that share corners with two equivalent Fe(1)O2F4 octahedra, corners with four equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 58°. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one F(1), and four equivalent F(2) atoms. Fe(1) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Na(1)O4F2 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-58°. S(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SO4 tetrahedra that share corners with two equivalent Fe(1)O2F4 octahedra and corners with four equivalent Na(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one S(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(2) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing FNa3Fe tetrahedra.
Na2FeSO4F3 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form NaO4F2 octahedra that share corners with two equivalent Fe(1)O2F4 octahedra, corners with four equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 58°. Both Na(1)-O(1) bond lengths are 2.48 Å. Both Na(1)-O(2) bond lengths are 2.52 Å. Both Na(1)-F(2) bond lengths are 2.33 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one F(1), and four equivalent F(2) atoms. The Na(2)-O(1) bond length is 2.85 Å. The Na(2)-F(1) bond length is 2.31 Å. There are two shorter (2.31 Å) and two longer (2.66 Å) Na(2)-F(2) bond lengths. Fe(1) is bonded to two equivalent O(3), two equivalent F(1), and two equivalent F(2) atoms to form FeO2F4 octahedra that share corners with two equivalent Na(1)O4F2 octahedra, corners with two equivalent Fe(1)O2F4 octahedra, and corners with two equivalent S(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 40-58°. Both Fe(1)-O(3) bond lengths are 2.01 Å. Both Fe(1)-F(1) bond lengths are 1.99 Å. Both Fe(1)-F(2) bond lengths are 1.93 Å. S(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SO4 tetrahedra that share corners with two equivalent Fe(1)O2F4 octahedra and corners with four equivalent Na(1)O4F2 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(2) bond length is 1.46 Å. Both S(1)-O(3) bond lengths are 1.52 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(1), and one S(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Fe(1) and one S(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to one Na(2) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded to one Na(1), two equivalent Na(2), and one Fe(1) atom to form a mixture of distorted corner and edge-sharing FNa3Fe tetrahedra.