CsTiI3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded to four equivalent I(1) and eight equivalent I(2) atoms to form CsI12 cuboctahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, corners with six equivalent Ti(1)I6 octahedra, faces with eight equivalent Cs(1)I12 cuboctahedra, and faces with six equivalent Ti(1)I6 octahedra. The corner-sharing octahedral tilt angles are 18°. Ti(1) is bonded to two equivalent I(1) and four equivalent I(2) atoms to form TiI6 octahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, faces with six equivalent Cs(1)I12 cuboctahedra, and faces with two equivalent Ti(1)I6 octahedra. There are two inequivalent I sites. In the first I site, I(1) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted edge, corner, and face-sharing ICs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°. In the second I site, I(2) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted edge, corner, and face-sharing ICs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°.
CsTiI3 crystallizes in the orthorhombic Cmcm space group. Cs(1) is bonded to four equivalent I(1) and eight equivalent I(2) atoms to form CsI12 cuboctahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, corners with six equivalent Ti(1)I6 octahedra, faces with eight equivalent Cs(1)I12 cuboctahedra, and faces with six equivalent Ti(1)I6 octahedra. The corner-sharing octahedral tilt angles are 18°. There are two shorter (4.13 Å) and two longer (4.27 Å) Cs(1)-I(1) bond lengths. There are a spread of Cs(1)-I(2) bond distances ranging from 4.13-4.27 Å. Ti(1) is bonded to two equivalent I(1) and four equivalent I(2) atoms to form TiI6 octahedra that share corners with six equivalent Cs(1)I12 cuboctahedra, faces with six equivalent Cs(1)I12 cuboctahedra, and faces with two equivalent Ti(1)I6 octahedra. Both Ti(1)-I(1) bond lengths are 2.92 Å. All Ti(1)-I(2) bond lengths are 2.91 Å. There are two inequivalent I sites. In the first I site, I(1) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted edge, corner, and face-sharing ICs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°. In the second I site, I(2) is bonded to four equivalent Cs(1) and two equivalent Ti(1) atoms to form a mixture of distorted edge, corner, and face-sharing ICs4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 0-70°.