Na3MoF6 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 distorted 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 Mo(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 Mo(1)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Mo(1) is bonded to six equivalent F(1) atoms to form MoF6 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 Mo(1) atom.
Na3MoF6 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 distorted 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 Mo(1)F6 octahedra. All Na(1)-F(1) bond lengths are 3.01 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 Mo(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 2.19 Å. Mo(1) is bonded to six equivalent F(1) atoms to form MoF6 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 Mo(1)-F(1) bond lengths are 2.06 Å. F(1) is bonded in a linear geometry to one Na(2), four equivalent Na(1), and one Mo(1) atom.