Cs3MnCl5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cl(1) and eight equivalent Cl(2) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Cl(1) and six equivalent Cl(2) atoms. Mn(1) is bonded in a tetrahedral geometry to four equivalent Cl(2) atoms. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Cs(1) and four equivalent Cs(2) atoms to form corner-sharing ClCs6 octahedra. The corner-sharing octahedral tilt angles range from 0-39°. In the second Cl site, Cl(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), three equivalent Cs(2), and one Mn(1) atom.
Cs3MnCl5 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 10-coordinate geometry to two equivalent Cl(1) and eight equivalent Cl(2) atoms. Both Cs(1)-Cl(1) bond lengths are 3.69 Å. All Cs(1)-Cl(2) bond lengths are 3.83 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Cl(1) and six equivalent Cl(2) atoms. Both Cs(2)-Cl(1) bond lengths are 3.47 Å. There are two shorter (3.43 Å) and four longer (3.65 Å) Cs(2)-Cl(2) bond lengths. Mn(1) is bonded in a tetrahedral geometry to four equivalent Cl(2) atoms. All Mn(1)-Cl(2) bond lengths are 2.34 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Cs(1) and four equivalent Cs(2) atoms to form corner-sharing ClCs6 octahedra. The corner-sharing octahedral tilt angles range from 0-39°. In the second Cl site, Cl(2) is bonded in a 6-coordinate geometry to two equivalent Cs(1), three equivalent Cs(2), and one Mn(1) atom.