CsMnF4 crystallizes in the tetragonal P4/n 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. Mn(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles are 17°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(1), one Cs(2), and two equivalent Mn(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 Mn(1) atom.
CsMnF4 crystallizes in the tetragonal P4/n 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 3.22 Å. There are four shorter (3.02 Å) and four longer (3.28 Å) Cs(1)-F(2) bond lengths. 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 3.47 Å. There are four shorter (3.09 Å) and four longer (3.17 Å) Cs(2)-F(2) bond lengths. Mn(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles are 17°. Both Mn(1)-F(2) bond lengths are 1.83 Å. There are two shorter (1.88 Å) and two longer (2.13 Å) Mn(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted linear geometry to one Cs(1), one Cs(2), and two equivalent Mn(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 Mn(1) atom.