CsTi(NbCl3)6 crystallizes in the trigonal P-31c space group. Cs(1) is bonded in a 12-coordinate geometry to six equivalent Cl(1) and six equivalent Cl(3) atoms. Ti(1) is bonded to six equivalent Cl(3) atoms to form TiCl6 octahedra that share corners with six equivalent Nb(1)Cl5 square pyramids. Nb(1) is bonded to one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted NbCl5 square pyramids that share  a cornercorner with one Ti(1)Cl6 octahedra and corners with four equivalent Nb(1)Cl5 square pyramids. The corner-sharing octahedral tilt angles are 43°. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Nb(1) atoms. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to two equivalent Nb(1) atoms. In the third Cl site, Cl(3) is bonded in a 2-coordinate geometry to one Cs(1), one Ti(1), and one Nb(1) atom.
CsTi(NbCl3)6 crystallizes in the trigonal P-31c space group. Cs(1) is bonded in a 12-coordinate geometry to six equivalent Cl(1) and six equivalent Cl(3) atoms. All Cs(1)-Cl(1) bond lengths are 3.77 Å. All Cs(1)-Cl(3) bond lengths are 3.86 Å. Ti(1) is bonded to six equivalent Cl(3) atoms to form TiCl6 octahedra that share corners with six equivalent Nb(1)Cl5 square pyramids. All Ti(1)-Cl(3) bond lengths are 2.48 Å. Nb(1) is bonded to one Cl(3), two equivalent Cl(1), and two equivalent Cl(2) atoms to form distorted NbCl5 square pyramids that share  a cornercorner with one Ti(1)Cl6 octahedra and corners with four equivalent Nb(1)Cl5 square pyramids. The corner-sharing octahedral tilt angles are 43°. The Nb(1)-Cl(3) bond length is 2.73 Å. There is one shorter (2.46 Å) and one longer (2.47 Å) Nb(1)-Cl(1) bond length. Both Nb(1)-Cl(2) bond lengths are 2.46 Å. There are three inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 2-coordinate geometry to one Cs(1) and two equivalent Nb(1) atoms. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to two equivalent Nb(1) atoms. In the third Cl site, Cl(3) is bonded in a 2-coordinate geometry to one Cs(1), one Ti(1), and one Nb(1) atom.