Na5Fe3F14 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one F(1), one F(3), one F(4), one F(6), and two equivalent F(5) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), and two equivalent F(7) atoms. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(3), two equivalent F(5), and two equivalent F(7) atoms. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(5), two equivalent F(6), and two equivalent F(7) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 42°. In the second Fe site, Fe(2) is bonded to two equivalent F(2), two equivalent F(4), and two equivalent F(6) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 32-42°. In the third Fe site, Fe(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 32°. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one Fe(3) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Na(2), one Fe(2), and one Fe(3) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), one Na(3), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(1), and one Fe(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded to one Na(3), two equivalent Na(2), and one Fe(1) atom to form distorted corner-sharing FNa3Fe tetrahedra.
Na5Fe3F14 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one F(1), one F(3), one F(4), one F(6), and two equivalent F(5) atoms. The Na(1)-F(1) bond length is 2.35 Å. The Na(1)-F(3) bond length is 2.38 Å. The Na(1)-F(4) bond length is 2.41 Å. The Na(1)-F(6) bond length is 2.48 Å. There is one shorter (2.28 Å) and one longer (2.37 Å) Na(1)-F(5) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one F(1), one F(2), one F(3), one F(4), and two equivalent F(7) atoms. The Na(2)-F(1) bond length is 2.40 Å. The Na(2)-F(2) bond length is 2.81 Å. The Na(2)-F(3) bond length is 2.31 Å. The Na(2)-F(4) bond length is 2.37 Å. There is one shorter (2.35 Å) and one longer (2.39 Å) Na(2)-F(7) bond length. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(3), two equivalent F(5), and two equivalent F(7) atoms. Both Na(3)-F(1) bond lengths are 2.47 Å. Both Na(3)-F(3) bond lengths are 2.93 Å. Both Na(3)-F(5) bond lengths are 2.84 Å. Both Na(3)-F(7) bond lengths are 2.58 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent F(5), two equivalent F(6), and two equivalent F(7) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 42°. Both Fe(1)-F(5) bond lengths are 1.94 Å. Both Fe(1)-F(6) bond lengths are 2.01 Å. Both Fe(1)-F(7) bond lengths are 1.96 Å. In the second Fe site, Fe(2) is bonded to two equivalent F(2), two equivalent F(4), and two equivalent F(6) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles range from 32-42°. Both Fe(2)-F(2) bond lengths are 1.94 Å. Both Fe(2)-F(4) bond lengths are 1.92 Å. Both Fe(2)-F(6) bond lengths are 1.97 Å. In the third Fe site, Fe(3) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing FeF6 octahedra. The corner-sharing octahedral tilt angles are 32°. Both Fe(3)-F(1) bond lengths are 1.95 Å. Both Fe(3)-F(2) bond lengths are 1.98 Å. Both Fe(3)-F(3) bond lengths are 1.94 Å. There are seven inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one Fe(3) atom. In the second F site, F(2) is bonded in a distorted bent 150 degrees geometry to one Na(2), one Fe(2), and one Fe(3) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), one Na(3), and one Fe(3) atom. In the fourth F site, F(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(1), one Na(2), and one Fe(2) atom. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(1), and one Fe(1) atom. In the sixth F site, F(6) is bonded in a distorted trigonal planar geometry to one Na(1), one Fe(1), and one Fe(2) atom. In the seventh F site, F(7) is bonded to one Na(3), two equivalent Na(2), and one Fe(1) atom to form distorted corner-sharing FNa3Fe tetrahedra.