CsScI3 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 Sc(1)I6 octahedra, faces with eight equivalent Cs(1)I12 cuboctahedra, and faces with six equivalent Sc(1)I6 octahedra. The corner-sharing octahedral tilt angles are 20°. Sc(1) is bonded to six equivalent I(1) atoms to form ScI6 octahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, faces with six equivalent Cs(1)I12 cuboctahedra, and faces with two equivalent Sc(1)I6 octahedra. I(1) is bonded to four equivalent Cs(1) and two equivalent Sc(1) atoms to form a mixture of distorted edge, corner, and face-sharing ICs4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 0-72°.
CsScI3 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 Sc(1)I6 octahedra, faces with eight equivalent Cs(1)I12 cuboctahedra, and faces with six equivalent Sc(1)I6 octahedra. The corner-sharing octahedral tilt angles are 20°. There are six shorter (4.16 Å) and six longer (4.25 Å) Cs(1)-I(1) bond lengths. Sc(1) is bonded to six equivalent I(1) atoms to form ScI6 octahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, faces with six equivalent Cs(1)I12 cuboctahedra, and faces with two equivalent Sc(1)I6 octahedra. All Sc(1)-I(1) bond lengths are 2.98 Å. I(1) is bonded to four equivalent Cs(1) and two equivalent Sc(1) atoms to form a mixture of distorted edge, corner, and face-sharing ICs4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 0-72°.