CsSbClF3 crystallizes in the tetragonal I-42m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to four equivalent Cl(1), two equivalent F(2), and four equivalent F(1) atoms. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to four equivalent Cl(1), four equivalent F(1), and four equivalent F(2) atoms. Sb(1) is bonded in a 3-coordinate geometry to two equivalent Cl(1), one F(2), and two equivalent F(1) atoms. Cl(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Sb2 octahedra. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), and one Sb(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Cs(1), two equivalent Cs(2), and one Sb(1) atom.
CsSbClF3 crystallizes in the tetragonal I-42m space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to four equivalent Cl(1), two equivalent F(2), and four equivalent F(1) atoms. All Cs(1)-Cl(1) bond lengths are 3.73 Å. Both Cs(1)-F(2) bond lengths are 3.12 Å. All Cs(1)-F(1) bond lengths are 3.19 Å. In the second Cs site, Cs(2) is bonded in a 12-coordinate geometry to four equivalent Cl(1), four equivalent F(1), and four equivalent F(2) atoms. All Cs(2)-Cl(1) bond lengths are 3.67 Å. All Cs(2)-F(1) bond lengths are 3.20 Å. All Cs(2)-F(2) bond lengths are 3.62 Å. Sb(1) is bonded in a 3-coordinate geometry to two equivalent Cl(1), one F(2), and two equivalent F(1) atoms. Both Sb(1)-Cl(1) bond lengths are 2.93 Å. The Sb(1)-F(2) bond length is 1.97 Å. Both Sb(1)-F(1) bond lengths are 2.01 Å. Cl(1) is bonded to two equivalent Cs(1), two equivalent Cs(2), and two equivalent Sb(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Sb2 octahedra. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(2), and one Sb(1) atom. In the second F site, F(2) is bonded in a distorted single-bond geometry to one Cs(1), two equivalent Cs(2), and one Sb(1) atom.