CsMnI3 crystallizes in the hexagonal P6_3/mmc space group. Cs(1) is bonded to twelve equivalent I(1) atoms to form CsI12 cuboctahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, corners with six equivalent Mn(1)I6 octahedra, faces with eight equivalent Cs(1)I12 cuboctahedra, and faces with six equivalent Mn(1)I6 octahedra. The corner-sharing octahedral tilt angles are 18°. Mn(1) is bonded to six equivalent I(1) atoms to form MnI6 octahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, faces with six equivalent Cs(1)I12 cuboctahedra, and faces with two equivalent Mn(1)I6 octahedra. I(1) is bonded to four equivalent Cs(1) and two equivalent Mn(1) atoms to form a mixture of distorted face, corner, and edge-sharing ICs4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°.
CsMnI3 crystallizes in the hexagonal P6_3/mmc space group. Cs(1) is bonded to twelve equivalent I(1) atoms to form CsI12 cuboctahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, corners with six equivalent Mn(1)I6 octahedra, faces with eight equivalent Cs(1)I12 cuboctahedra, and faces with six equivalent Mn(1)I6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are six shorter (4.14 Å) and six longer (4.27 Å) Cs(1)-I(1) bond lengths. Mn(1) is bonded to six equivalent I(1) atoms to form MnI6 octahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, faces with six equivalent Cs(1)I12 cuboctahedra, and faces with two equivalent Mn(1)I6 octahedra. All Mn(1)-I(1) bond lengths are 2.92 Å. I(1) is bonded to four equivalent Cs(1) and two equivalent Mn(1) atoms to form a mixture of distorted face, corner, and edge-sharing ICs4Mn2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°.