CsTiCl3 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 Ti(1)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Ti(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 17°. Ti(1) is bonded to six equivalent Cl(1) atoms to form TiCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Ti(1)Cl6 octahedra. Cl(1) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°.
CsTiCl3 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 Ti(1)Cl6 octahedra, faces with eight equivalent Cs(1)Cl12 cuboctahedra, and faces with six equivalent Ti(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 17°. All Cs(1)-Cl(1) bond lengths are 3.70 Å. Ti(1) is bonded to six equivalent Cl(1) atoms to form TiCl6 octahedra that share corners with six equivalent Cs(1)Cl12 cuboctahedra, faces with six equivalent Cs(1)Cl12 cuboctahedra, and faces with two equivalent Ti(1)Cl6 octahedra. All Ti(1)-Cl(1) bond lengths are 2.53 Å. Cl(1) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted corner, edge, and face-sharing ClCs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-74°.