Ti7Cl16 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent Cl(2) and four equivalent Cl(5) atoms to form edge-sharing TiCl6 octahedra. In the second Ti site, Ti(2) is bonded to one Cl(3), one Cl(4), two equivalent Cl(5), and two equivalent Cl(6) atoms to form distorted edge-sharing TiCl6 octahedra. In the third Ti site, Ti(3) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form distorted edge-sharing TiCl6 octahedra. There are six inequivalent Cl sites. In the first Cl site, Cl(6) is bonded in a distorted L-shaped geometry to one Ti(2) and one Ti(3) atom. In the second Cl site, Cl(1) is bonded in a 2-coordinate geometry to two equivalent Ti(3) atoms. In the third Cl site, Cl(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1) and two equivalent Ti(3) atoms. In the fourth Cl site, Cl(3) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2) and two equivalent Ti(3) atoms. In the fifth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Ti(2) and two equivalent Ti(3) atoms. In the sixth Cl site, Cl(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one Ti(3) atom.
Ti7Cl16 crystallizes in the orthorhombic Pnnm space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent Cl(2) and four equivalent Cl(5) atoms to form edge-sharing TiCl6 octahedra. Both Ti(1)-Cl(2) bond lengths are 2.49 Å. All Ti(1)-Cl(5) bond lengths are 2.56 Å. In the second Ti site, Ti(2) is bonded to one Cl(3), one Cl(4), two equivalent Cl(5), and two equivalent Cl(6) atoms to form distorted edge-sharing TiCl6 octahedra. The Ti(2)-Cl(3) bond length is 2.63 Å. The Ti(2)-Cl(4) bond length is 2.41 Å. Both Ti(2)-Cl(5) bond lengths are 2.55 Å. Both Ti(2)-Cl(6) bond lengths are 2.37 Å. In the third Ti site, Ti(3) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), one Cl(5), and one Cl(6) atom to form distorted edge-sharing TiCl6 octahedra. The Ti(3)-Cl(1) bond length is 2.35 Å. The Ti(3)-Cl(2) bond length is 2.66 Å. The Ti(3)-Cl(3) bond length is 2.61 Å. The Ti(3)-Cl(4) bond length is 2.41 Å. The Ti(3)-Cl(5) bond length is 2.59 Å. The Ti(3)-Cl(6) bond length is 2.36 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(6) is bonded in a distorted L-shaped geometry to one Ti(2) and one Ti(3) atom. In the second Cl site, Cl(1) is bonded in a 2-coordinate geometry to two equivalent Ti(3) atoms. In the third Cl site, Cl(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1) and two equivalent Ti(3) atoms. In the fourth Cl site, Cl(3) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2) and two equivalent Ti(3) atoms. In the fifth Cl site, Cl(4) is bonded in a 3-coordinate geometry to one Ti(2) and two equivalent Ti(3) atoms. In the sixth Cl site, Cl(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one Ti(3) atom.