CsTi2(OF)3 crystallizes in the orthorhombic F222 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 4-coordinate geometry to two equivalent F(2) and two equivalent F(3) atoms. In the second Cs site, Cs(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form distorted CsO4F2 octahedra that share corners with twelve equivalent Ti(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 66-70°. Ti(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form TiO3F3 octahedra that share corners with three equivalent Cs(2)O4F2 octahedra and corners with six equivalent Ti(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 25-70°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cs(2) and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Cs(2) and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Ti(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Cs(2) and two equivalent Ti(1) atoms. In the second F site, F(1) is bonded in a 2-coordinate geometry to one Cs(2) and two equivalent Ti(1) atoms. In the third F site, F(2) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Ti(1) atoms. In the fourth F site, F(3) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Ti(1) atoms.
CsTi2(OF)3 crystallizes in the orthorhombic F222 space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 4-coordinate geometry to two equivalent F(2) and two equivalent F(3) atoms. Both Cs(1)-F(2) bond lengths are 3.16 Å. Both Cs(1)-F(3) bond lengths are 3.04 Å. In the second Cs site, Cs(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(1) atoms to form distorted CsO4F2 octahedra that share corners with twelve equivalent Ti(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 66-70°. Both Cs(2)-O(1) bond lengths are 3.47 Å. Both Cs(2)-O(2) bond lengths are 3.21 Å. Both Cs(2)-F(1) bond lengths are 3.06 Å. Ti(1) is bonded to one O(1), one O(2), one O(3), one F(1), one F(2), and one F(3) atom to form TiO3F3 octahedra that share corners with three equivalent Cs(2)O4F2 octahedra and corners with six equivalent Ti(1)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 25-70°. The Ti(1)-O(1) bond length is 1.89 Å. The Ti(1)-O(2) bond length is 1.84 Å. The Ti(1)-O(3) bond length is 1.89 Å. The Ti(1)-F(1) bond length is 2.02 Å. The Ti(1)-F(2) bond length is 2.10 Å. The Ti(1)-F(3) bond length is 2.01 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Cs(2) and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Cs(2) and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Ti(1) atoms. There are four inequivalent F sites. In the first F site, F(1) is bonded in a 2-coordinate geometry to one Cs(2) and two equivalent Ti(1) atoms. The F(1)-Cs(2) bond length is 3.06 Å. In the second F site, F(1) is bonded in a 2-coordinate geometry to one Cs(2) and two equivalent Ti(1) atoms. Both F(1)-Ti(1) bond lengths are 2.02 Å. In the third F site, F(2) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Ti(1) atoms. In the fourth F site, F(3) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Ti(1) atoms.