Cs3TiF6 crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to four equivalent F(2) and eight equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with twelve equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F6 octahedra, and faces with four equivalent Ti(1)F6 octahedra. In the second Cs site, Cs(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form CsF6 octahedra that share corners with six equivalent Ti(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Ti(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form TiF6 octahedra that share corners with six equivalent Cs(2)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 in a 2-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Ti(1) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Ti(1) atom.
Cs3TiF6 crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to four equivalent F(2) and eight equivalent F(1) atoms to form distorted CsF12 cuboctahedra that share corners with twelve equivalent Cs(1)F12 cuboctahedra, faces with six equivalent Cs(1)F12 cuboctahedra, faces with four equivalent Cs(2)F6 octahedra, and faces with four equivalent Ti(1)F6 octahedra. All Cs(1)-F(2) bond lengths are 3.38 Å. All Cs(1)-F(1) bond lengths are 3.40 Å. In the second Cs site, Cs(2) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form CsF6 octahedra that share corners with six equivalent Ti(1)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Both Cs(2)-F(2) bond lengths are 2.79 Å. All Cs(2)-F(1) bond lengths are 2.79 Å. Ti(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form TiF6 octahedra that share corners with six equivalent Cs(2)F6 octahedra and faces with eight equivalent Cs(1)F12 cuboctahedra. The corner-sharing octahedra are not tilted. Both Ti(1)-F(2) bond lengths are 2.00 Å. All Ti(1)-F(1) bond lengths are 1.96 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Ti(1) atom. In the second F site, F(2) is bonded in a 2-coordinate geometry to one Cs(2), four equivalent Cs(1), and one Ti(1) atom.