CsTiF4 crystallizes in the tetragonal P4/nmm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to four equivalent F(1) and eight equivalent F(2) atoms. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to four equivalent F(1) and eight equivalent F(2) atoms. Ti(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form corner-sharing TiF6 octahedra. The corner-sharing octahedral tilt angles are 23°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cs(2), and two equivalent Ti(1) atoms. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Ti(1) atom.
CsTiF4 crystallizes in the tetragonal P4/nmm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 12-coordinate geometry to four equivalent F(1) and eight equivalent F(2) atoms. All Cs(1)-F(1) bond lengths are 3.43 Å. All Cs(1)-F(2) bond lengths are 3.17 Å. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to four equivalent F(1) and eight equivalent F(2) atoms. All Cs(2)-F(1) bond lengths are 3.15 Å. There are four shorter (2.99 Å) and four longer (3.39 Å) Cs(2)-F(2) bond lengths. Ti(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form corner-sharing TiF6 octahedra. The corner-sharing octahedral tilt angles are 23°. Both Ti(1)-F(2) bond lengths are 1.89 Å. All Ti(1)-F(1) bond lengths are 2.04 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to one Cs(1), one Cs(2), and two equivalent Ti(1) atoms. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent Cs(1), two equivalent Cs(2), and one Ti(1) atom.