Cs3Ti2Cl9 crystallizes in the monoclinic Cm space group. There are six inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one Cl(10), one Cl(7), two equivalent Cl(1), two equivalent Cl(12), two equivalent Cl(5), and four equivalent Cl(3) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(3)Cl12 cuboctahedra, corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Ti(1)Cl6 octahedra,  a faceface with one Cs(6)Cl12 cuboctahedra, faces with three equivalent Cs(4)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra,  a faceface with one Ti(2)Cl6 octahedra, and faces with three equivalent Ti(3)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the second Cs site, Cs(2) is bonded to one Cl(11), one Cl(6), two equivalent Cl(2), two equivalent Cl(4), two equivalent Cl(9), and four equivalent Cl(8) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(5)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, corners with three equivalent Ti(2)Cl6 octahedra,  a faceface with one Cs(4)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra, faces with three equivalent Cs(6)Cl12 cuboctahedra,  a faceface with one Ti(1)Cl6 octahedra, and faces with three equivalent Ti(4)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the third Cs site, Cs(3) is bonded to one Cl(10), one Cl(4), two equivalent Cl(12), two equivalent Cl(6), two equivalent Cl(8), and four equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cs(6)Cl12 cuboctahedra, corners with six equivalent Cs(3)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(4)Cl12 cuboctahedra, faces with three equivalent Ti(2)Cl6 octahedra, and faces with three equivalent Ti(4)Cl6 octahedra. In the fourth Cs site, Cs(4) is bonded to one Cl(5), one Cl(6), two equivalent Cl(10), two equivalent Cl(2), two equivalent Cl(3), and four equivalent Cl(12) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(5)Cl12 cuboctahedra, corners with six equivalent Cs(4)Cl12 cuboctahedra, corners with three equivalent Ti(4)Cl6 octahedra,  a faceface with one Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra,  a faceface with one Ti(3)Cl6 octahedra, and faces with three equivalent Ti(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. In the fifth Cs site, Cs(5) is bonded to one Cl(11), one Cl(5), two equivalent Cl(3), two equivalent Cl(7), two equivalent Cl(9), and four equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra, corners with three equivalent Cs(4)Cl12 cuboctahedra, corners with six equivalent Cs(5)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(6)Cl12 cuboctahedra, faces with three equivalent Ti(1)Cl6 octahedra, and faces with three equivalent Ti(3)Cl6 octahedra. In the sixth Cs site, Cs(6) is bonded to one Cl(4), one Cl(7), two equivalent Cl(1), two equivalent Cl(11), two equivalent Cl(8), and four equivalent Cl(9) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(3)Cl12 cuboctahedra, corners with six equivalent Cs(6)Cl12 cuboctahedra, corners with three equivalent Ti(3)Cl6 octahedra,  a faceface with one Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra,  a faceface with one Ti(4)Cl6 octahedra, and faces with three equivalent Ti(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one Cl(11), one Cl(7), two equivalent Cl(1), and two equivalent Cl(9) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra,  a faceface with one Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra, faces with three equivalent Cs(6)Cl12 cuboctahedra, and  a faceface with one Ti(3)Cl6 octahedra. In the second Ti site, Ti(2) is bonded to one Cl(10), one Cl(6), two equivalent Cl(12), and two equivalent Cl(2) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra,  a faceface with one Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra, faces with three equivalent Cs(4)Cl12 cuboctahedra, and  a faceface with one Ti(4)Cl6 octahedra. In the third Ti site, Ti(3) is bonded to one Cl(5), one Cl(7), two equivalent Cl(1), and two equivalent Cl(3) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(6)Cl12 cuboctahedra,  a faceface with one Cs(4)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra, and  a faceface with one Ti(1)Cl6 octahedra. In the fourth Ti site, Ti(4) is bonded to one Cl(4), one Cl(6), two equivalent Cl(2), and two equivalent Cl(8) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(4)Cl12 cuboctahedra,  a faceface with one Cs(6)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra, and  a faceface with one Ti(2)Cl6 octahedra. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(6), two equivalent Cs(5), one Ti(1), and one Ti(3) atom. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), two equivalent Cs(3), one Ti(2), and one Ti(4) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Cs(4), one Cs(5), two equivalent Cs(1), and one Ti(3) atom. In the fourth Cl site, Cl(4) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(6), two equivalent Cs(2), and one Ti(4) atom. In the fifth Cl site, Cl(5) is bonded in a distorted single-bond geometry to one Cs(4), one Cs(5), two equivalent Cs(1), and one Ti(3) atom. In the sixth Cl site, Cl(6) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), two equivalent Cs(3), one Ti(2), and one Ti(4) atom. In the seventh Cl site, Cl(7) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(6), two equivalent Cs(5), one Ti(1), and one Ti(3) atom. In the eighth Cl site, Cl(8) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(6), two equivalent Cs(2), and one Ti(4) atom. In the ninth Cl site, Cl(9) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(5), two equivalent Cs(6), and one Ti(1) atom. In the tenth Cl site, Cl(10) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), two equivalent Cs(4), and one Ti(2) atom. In the eleventh Cl site, Cl(11) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(5), two equivalent Cs(6), and one Ti(1) atom. In the twelfth Cl site, Cl(12) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), two equivalent Cs(4), and one Ti(2) atom.
Cs3Ti2Cl9 crystallizes in the monoclinic Cm space group. There are six inequivalent Cs sites. In the first Cs site, Cs(1) is bonded to one Cl(10), one Cl(7), two equivalent Cl(1), two equivalent Cl(12), two equivalent Cl(5), and four equivalent Cl(3) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(3)Cl12 cuboctahedra, corners with six equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Ti(1)Cl6 octahedra,  a faceface with one Cs(6)Cl12 cuboctahedra, faces with three equivalent Cs(4)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra,  a faceface with one Ti(2)Cl6 octahedra, and faces with three equivalent Ti(3)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. The Cs(1)-Cl(10) bond length is 3.62 Å. The Cs(1)-Cl(7) bond length is 3.87 Å. Both Cs(1)-Cl(1) bond lengths are 3.87 Å. Both Cs(1)-Cl(12) bond lengths are 3.63 Å. Both Cs(1)-Cl(5) bond lengths are 3.70 Å. All Cs(1)-Cl(3) bond lengths are 3.70 Å. In the second Cs site, Cs(2) is bonded to one Cl(11), one Cl(6), two equivalent Cl(2), two equivalent Cl(4), two equivalent Cl(9), and four equivalent Cl(8) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(5)Cl12 cuboctahedra, corners with six equivalent Cs(2)Cl12 cuboctahedra, corners with three equivalent Ti(2)Cl6 octahedra,  a faceface with one Cs(4)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra, faces with three equivalent Cs(6)Cl12 cuboctahedra,  a faceface with one Ti(1)Cl6 octahedra, and faces with three equivalent Ti(4)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. The Cs(2)-Cl(11) bond length is 3.63 Å. The Cs(2)-Cl(6) bond length is 3.87 Å. Both Cs(2)-Cl(2) bond lengths are 3.88 Å. Both Cs(2)-Cl(4) bond lengths are 3.70 Å. Both Cs(2)-Cl(9) bond lengths are 3.63 Å. All Cs(2)-Cl(8) bond lengths are 3.70 Å. In the third Cs site, Cs(3) is bonded to one Cl(10), one Cl(4), two equivalent Cl(12), two equivalent Cl(6), two equivalent Cl(8), and four equivalent Cl(2) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra, corners with three equivalent Cs(6)Cl12 cuboctahedra, corners with six equivalent Cs(3)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(4)Cl12 cuboctahedra, faces with three equivalent Ti(2)Cl6 octahedra, and faces with three equivalent Ti(4)Cl6 octahedra. The Cs(3)-Cl(10) bond length is 3.61 Å. The Cs(3)-Cl(4) bond length is 3.61 Å. Both Cs(3)-Cl(12) bond lengths are 3.61 Å. Both Cs(3)-Cl(6) bond lengths are 3.69 Å. Both Cs(3)-Cl(8) bond lengths are 3.61 Å. There are two shorter (3.68 Å) and two longer (3.70 Å) Cs(3)-Cl(2) bond lengths. In the fourth Cs site, Cs(4) is bonded to one Cl(5), one Cl(6), two equivalent Cl(10), two equivalent Cl(2), two equivalent Cl(3), and four equivalent Cl(12) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(5)Cl12 cuboctahedra, corners with six equivalent Cs(4)Cl12 cuboctahedra, corners with three equivalent Ti(4)Cl6 octahedra,  a faceface with one Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra,  a faceface with one Ti(3)Cl6 octahedra, and faces with three equivalent Ti(2)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. The Cs(4)-Cl(5) bond length is 3.63 Å. The Cs(4)-Cl(6) bond length is 3.87 Å. Both Cs(4)-Cl(10) bond lengths are 3.70 Å. Both Cs(4)-Cl(2) bond lengths are 3.87 Å. Both Cs(4)-Cl(3) bond lengths are 3.63 Å. All Cs(4)-Cl(12) bond lengths are 3.70 Å. In the fifth Cs site, Cs(5) is bonded to one Cl(11), one Cl(5), two equivalent Cl(3), two equivalent Cl(7), two equivalent Cl(9), and four equivalent Cl(1) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra, corners with three equivalent Cs(4)Cl12 cuboctahedra, corners with six equivalent Cs(5)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(6)Cl12 cuboctahedra, faces with three equivalent Ti(1)Cl6 octahedra, and faces with three equivalent Ti(3)Cl6 octahedra. The Cs(5)-Cl(11) bond length is 3.61 Å. The Cs(5)-Cl(5) bond length is 3.61 Å. Both Cs(5)-Cl(3) bond lengths are 3.61 Å. Both Cs(5)-Cl(7) bond lengths are 3.69 Å. Both Cs(5)-Cl(9) bond lengths are 3.61 Å. All Cs(5)-Cl(1) bond lengths are 3.69 Å. In the sixth Cs site, Cs(6) is bonded to one Cl(4), one Cl(7), two equivalent Cl(1), two equivalent Cl(11), two equivalent Cl(8), and four equivalent Cl(9) atoms to form CsCl12 cuboctahedra that share corners with three equivalent Cs(3)Cl12 cuboctahedra, corners with six equivalent Cs(6)Cl12 cuboctahedra, corners with three equivalent Ti(3)Cl6 octahedra,  a faceface with one Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra,  a faceface with one Ti(4)Cl6 octahedra, and faces with three equivalent Ti(1)Cl6 octahedra. The corner-sharing octahedral tilt angles are 15°. The Cs(6)-Cl(4) bond length is 3.63 Å. The Cs(6)-Cl(7) bond length is 3.88 Å. Both Cs(6)-Cl(1) bond lengths are 3.88 Å. Both Cs(6)-Cl(11) bond lengths are 3.70 Å. Both Cs(6)-Cl(8) bond lengths are 3.64 Å. All Cs(6)-Cl(9) bond lengths are 3.70 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one Cl(11), one Cl(7), two equivalent Cl(1), and two equivalent Cl(9) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(1)Cl12 cuboctahedra,  a faceface with one Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra, faces with three equivalent Cs(6)Cl12 cuboctahedra, and  a faceface with one Ti(3)Cl6 octahedra. The Ti(1)-Cl(11) bond length is 2.35 Å. The Ti(1)-Cl(7) bond length is 2.53 Å. Both Ti(1)-Cl(1) bond lengths are 2.53 Å. Both Ti(1)-Cl(9) bond lengths are 2.35 Å. In the second Ti site, Ti(2) is bonded to one Cl(10), one Cl(6), two equivalent Cl(12), and two equivalent Cl(2) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(2)Cl12 cuboctahedra,  a faceface with one Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra, faces with three equivalent Cs(4)Cl12 cuboctahedra, and  a faceface with one Ti(4)Cl6 octahedra. The Ti(2)-Cl(10) bond length is 2.36 Å. The Ti(2)-Cl(6) bond length is 2.53 Å. Both Ti(2)-Cl(12) bond lengths are 2.35 Å. Both Ti(2)-Cl(2) bond lengths are 2.53 Å. In the third Ti site, Ti(3) is bonded to one Cl(5), one Cl(7), two equivalent Cl(1), and two equivalent Cl(3) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(6)Cl12 cuboctahedra,  a faceface with one Cs(4)Cl12 cuboctahedra, faces with three equivalent Cs(1)Cl12 cuboctahedra, faces with three equivalent Cs(5)Cl12 cuboctahedra, and  a faceface with one Ti(1)Cl6 octahedra. The Ti(3)-Cl(5) bond length is 2.35 Å. The Ti(3)-Cl(7) bond length is 2.53 Å. Both Ti(3)-Cl(1) bond lengths are 2.53 Å. Both Ti(3)-Cl(3) bond lengths are 2.35 Å. In the fourth Ti site, Ti(4) is bonded to one Cl(4), one Cl(6), two equivalent Cl(2), and two equivalent Cl(8) atoms to form TiCl6 octahedra that share corners with three equivalent Cs(4)Cl12 cuboctahedra,  a faceface with one Cs(6)Cl12 cuboctahedra, faces with three equivalent Cs(2)Cl12 cuboctahedra, faces with three equivalent Cs(3)Cl12 cuboctahedra, and  a faceface with one Ti(2)Cl6 octahedra. The Ti(4)-Cl(4) bond length is 2.36 Å. The Ti(4)-Cl(6) bond length is 2.53 Å. Both Ti(4)-Cl(2) bond lengths are 2.53 Å. Both Ti(4)-Cl(8) bond lengths are 2.35 Å. There are twelve inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(6), two equivalent Cs(5), one Ti(1), and one Ti(3) atom. In the second Cl site, Cl(2) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), two equivalent Cs(3), one Ti(2), and one Ti(4) atom. In the third Cl site, Cl(3) is bonded in a distorted single-bond geometry to one Cs(4), one Cs(5), two equivalent Cs(1), and one Ti(3) atom. In the fourth Cl site, Cl(4) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(6), two equivalent Cs(2), and one Ti(4) atom. In the fifth Cl site, Cl(5) is bonded in a distorted single-bond geometry to one Cs(4), one Cs(5), two equivalent Cs(1), and one Ti(3) atom. In the sixth Cl site, Cl(6) is bonded in a 2-coordinate geometry to one Cs(2), one Cs(4), two equivalent Cs(3), one Ti(2), and one Ti(4) atom. In the seventh Cl site, Cl(7) is bonded in a 2-coordinate geometry to one Cs(1), one Cs(6), two equivalent Cs(5), one Ti(1), and one Ti(3) atom. In the eighth Cl site, Cl(8) is bonded in a distorted single-bond geometry to one Cs(3), one Cs(6), two equivalent Cs(2), and one Ti(4) atom. In the ninth Cl site, Cl(9) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(5), two equivalent Cs(6), and one Ti(1) atom. In the tenth Cl site, Cl(10) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), two equivalent Cs(4), and one Ti(2) atom. In the eleventh Cl site, Cl(11) is bonded in a distorted single-bond geometry to one Cs(2), one Cs(5), two equivalent Cs(6), and one Ti(1) atom. In the twelfth Cl site, Cl(12) is bonded in a distorted single-bond geometry to one Cs(1), one Cs(3), two equivalent Cs(4), and one Ti(2) atom.