Na3CoF6 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 8-coordinate geometry to two equivalent F(2), three equivalent F(1), and three 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 Co(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-40°. Co(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CoF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-40°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(2), three equivalent Na(1), and one Co(1) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one Co(1) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(1), and one Co(1) atom.
Na3CoF6 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 8-coordinate geometry to two equivalent F(2), three equivalent F(1), and three equivalent F(3) atoms. There is one shorter (2.26 Å) and one longer (2.30 Å) Na(1)-F(2) bond length. There are a spread of Na(1)-F(1) bond distances ranging from 2.28-2.84 Å. There are a spread of Na(1)-F(3) bond distances ranging from 2.28-2.70 Å. 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 Co(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-40°. Both Na(2)-F(1) bond lengths are 2.25 Å. Both Na(2)-F(2) bond lengths are 2.24 Å. Both Na(2)-F(3) bond lengths are 2.19 Å. Co(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form CoF6 octahedra that share corners with six equivalent Na(2)F6 octahedra. The corner-sharing octahedral tilt angles range from 33-40°. Both Co(1)-F(1) bond lengths are 1.86 Å. Both Co(1)-F(2) bond lengths are 1.86 Å. Both Co(1)-F(3) bond lengths are 1.85 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to one Na(2), three equivalent Na(1), and one Co(1) atom. In the second F site, F(2) is bonded in a distorted see-saw-like geometry to one Na(2), two equivalent Na(1), and one Co(1) atom. In the third F site, F(3) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(1), and one Co(1) atom.