Na3CoF6 is (Cubic) Perovskite-like structured and crystallizes in the cubic Fm-3m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to twelve equivalent F(1) atoms to form NaF12 cuboctahedra that share corners with twelve equivalent Na(1)F12 cuboctahedra, faces with six equivalent Na(1)F12 cuboctahedra, faces with four equivalent Na(2)F6 octahedra, and faces with four equivalent Co(1)F6 octahedra. In the second Na site, Na(2) is bonded to six equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Co(1)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Co(1) is bonded to six equivalent F(1) atoms to form CoF6 octahedra that share corners with six equivalent Na(2)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. F(1) is bonded in a linear geometry to one Na(2), four equivalent Na(1), and one Co(1) atom.
Na3CoF6 is (Cubic) Perovskite-like structured and crystallizes in the cubic Fm-3m space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to twelve equivalent F(1) atoms to form NaF12 cuboctahedra that share corners with twelve equivalent Na(1)F12 cuboctahedra, faces with six equivalent Na(1)F12 cuboctahedra, faces with four equivalent Na(2)F6 octahedra, and faces with four equivalent Co(1)F6 octahedra. All Na(1)-F(1) bond lengths are 2.90 Å. In the second Na site, Na(2) is bonded to six equivalent F(1) atoms to form NaF6 octahedra that share corners with six equivalent Co(1)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Na(2)-F(1) bond lengths are 2.18 Å. Co(1) is bonded to six equivalent F(1) atoms to form CoF6 octahedra that share corners with six equivalent Na(2)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Co(1)-F(1) bond lengths are 1.92 Å. F(1) is bonded in a linear geometry to one Na(2), four equivalent Na(1), and one Co(1) atom.