Cs2KMnF6 crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded to four equivalent F(1) and eight equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with twelve equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, faces with four equivalent K(1)F6 octahedra, and faces with four equivalent Mn(1)F6 octahedra. K(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form KF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Mn(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form MnF6 octahedra that share corners with six equivalent K(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cs(1), one K(1), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FCs4KMn octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second F site, F(2) is bonded in a 2-coordinate geometry to four equivalent Cs(1), one K(1), and one Mn(1) atom.
Cs2KMnF6 crystallizes in the tetragonal I4/mmm space group. Cs(1) is bonded to four equivalent F(1) and eight equivalent F(2) atoms to form CsF12 cuboctahedra that share corners with twelve equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, faces with four equivalent K(1)F6 octahedra, and faces with four equivalent Mn(1)F6 octahedra. All Cs(1)-F(1) bond lengths are 3.22 Å. All Cs(1)-F(2) bond lengths are 3.31 Å. K(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form KF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Both K(1)-F(1) bond lengths are 2.61 Å. All K(1)-F(2) bond lengths are 2.63 Å. Mn(1) is bonded to two equivalent F(1) and four equivalent F(2) atoms to form MnF6 octahedra that share corners with six equivalent K(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Both Mn(1)-F(1) bond lengths are 2.14 Å. All Mn(1)-F(2) bond lengths are 1.91 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Cs(1), one K(1), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FCs4KMn octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second F site, F(2) is bonded in a 2-coordinate geometry to four equivalent Cs(1), one K(1), and one Mn(1) atom.