Na3MnF6 is Ilmenite-like structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one F(1), one F(2), and two equivalent F(3) atoms. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-41°. Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-41°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one Mn(1) atom.
Na3MnF6 is Ilmenite-like structured and crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 4-coordinate geometry to one F(1), one F(2), and two equivalent F(3) atoms. The Na(1)-F(1) bond length is 2.36 Å. The Na(1)-F(2) bond length is 2.35 Å. There is one shorter (2.27 Å) and one longer (2.31 Å) Na(1)-F(3) bond length. In the second Na site, Na(2) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form NaF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-41°. Both Na(2)-F(1) bond lengths are 2.35 Å. Both Na(2)-F(2) bond lengths are 2.31 Å. Both Na(2)-F(3) bond lengths are 2.29 Å. Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form MnF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 36-41°. Both Mn(1)-F(1) bond lengths are 1.92 Å. Both Mn(1)-F(2) bond lengths are 1.90 Å. Both Mn(1)-F(3) bond lengths are 2.11 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one Mn(1) atom. In the third F site, F(3) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one Mn(1) atom.