Na2CuAsF6 crystallizes in the cubic Fm-3m space group. 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 Cu(1)F6 octahedra, and faces with four equivalent As(1)F6 octahedra. Cu(1) is bonded to six equivalent F(1) atoms to form CuF6 octahedra that share corners with six equivalent As(1)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. As(1) is bonded to six equivalent F(1) atoms to form AsF6 octahedra that share corners with six equivalent Cu(1)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 four equivalent Na(1), one Cu(1), and one As(1) atom.
Na2CuAsF6 crystallizes in the cubic Fm-3m space group. 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 Cu(1)F6 octahedra, and faces with four equivalent As(1)F6 octahedra. All Na(1)-F(1) bond lengths are 2.98 Å. Cu(1) is bonded to six equivalent F(1) atoms to form CuF6 octahedra that share corners with six equivalent As(1)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All Cu(1)-F(1) bond lengths are 2.15 Å. As(1) is bonded to six equivalent F(1) atoms to form AsF6 octahedra that share corners with six equivalent Cu(1)F6 octahedra and faces with eight equivalent Na(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. All As(1)-F(1) bond lengths are 2.07 Å. F(1) is bonded in a linear geometry to four equivalent Na(1), one Cu(1), and one As(1) atom.