CsScCl3 crystallizes in the hexagonal P6_3/mmc space group. Cs(1) is bonded to twelve equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Sc(1)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Sc(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 18°. Sc(1) is bonded to six equivalent Cl(1) atoms to form ScCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Sc(1)Cl6 octahedra. Cl(1) is bonded to four equivalent Cs(1) and two equivalent Sc(1) atoms to form a mixture of distorted face, edge, and corner-sharing ClCs4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 0-73°.
CsScCl3 crystallizes in the hexagonal P6_3/mmc space group. Cs(1) is bonded to twelve equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with six equivalent Sc(1)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Sc(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are six shorter (3.72 Å) and six longer (3.76 Å) Cs(1)-Cl(1) bond lengths. Sc(1) is bonded to six equivalent Cl(1) atoms to form ScCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Sc(1)Cl6 octahedra. All Sc(1)-Cl(1) bond lengths are 2.60 Å. Cl(1) is bonded to four equivalent Cs(1) and two equivalent Sc(1) atoms to form a mixture of distorted face, edge, and corner-sharing ClCs4Sc2 octahedra. The corner-sharing octahedral tilt angles range from 0-73°.