K3TiCl6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(3) atoms. In the second K site, K(2) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(1), and two equivalent Cl(3) atoms. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(2), two equivalent Cl(5), two equivalent Cl(6), and three equivalent Cl(4) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms. In the second Ti site, Ti(2) is bonded in an octahedral geometry to two equivalent Cl(4), two equivalent Cl(5), and two equivalent Cl(6) atoms. There are six inequivalent Cl sites. In the first Cl site, Cl(5) is bonded in a 1-coordinate geometry to one K(1), one K(2), two equivalent K(3), and one Ti(2) atom. In the second Cl site, Cl(6) is bonded in a 5-coordinate geometry to one K(1), one K(2), two equivalent K(3), and one Ti(2) atom. In the third Cl site, Cl(1) is bonded in a 5-coordinate geometry to one K(1), one K(3), two equivalent K(2), and one Ti(1) atom. In the fourth Cl site, Cl(2) is bonded in a 5-coordinate geometry to one K(2), one K(3), two equivalent K(1), and one Ti(1) atom. In the fifth Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Ti(1) atom. In the sixth Cl site, Cl(4) is bonded in a 6-coordinate geometry to one K(1), one K(2), three equivalent K(3), and one Ti(2) atom.
K3TiCl6 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent K sites. In the first K site, K(1) is bonded in a 8-coordinate geometry to one Cl(1), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(2), and two equivalent Cl(3) atoms. The K(1)-Cl(1) bond length is 3.17 Å. The K(1)-Cl(4) bond length is 3.14 Å. The K(1)-Cl(5) bond length is 3.26 Å. The K(1)-Cl(6) bond length is 3.18 Å. There is one shorter (3.26 Å) and one longer (3.46 Å) K(1)-Cl(2) bond length. There is one shorter (3.12 Å) and one longer (3.14 Å) K(1)-Cl(3) bond length. In the second K site, K(2) is bonded in a 8-coordinate geometry to one Cl(2), one Cl(4), one Cl(5), one Cl(6), two equivalent Cl(1), and two equivalent Cl(3) atoms. The K(2)-Cl(2) bond length is 3.09 Å. The K(2)-Cl(4) bond length is 3.61 Å. The K(2)-Cl(5) bond length is 3.26 Å. The K(2)-Cl(6) bond length is 3.01 Å. There is one shorter (3.34 Å) and one longer (3.45 Å) K(2)-Cl(1) bond length. There is one shorter (3.14 Å) and one longer (3.17 Å) K(2)-Cl(3) bond length. In the third K site, K(3) is bonded in a 9-coordinate geometry to one Cl(1), one Cl(2), two equivalent Cl(5), two equivalent Cl(6), and three equivalent Cl(4) atoms. The K(3)-Cl(1) bond length is 3.63 Å. The K(3)-Cl(2) bond length is 3.36 Å. There is one shorter (3.29 Å) and one longer (3.60 Å) K(3)-Cl(5) bond length. There is one shorter (3.19 Å) and one longer (3.57 Å) K(3)-Cl(6) bond length. There are a spread of K(3)-Cl(4) bond distances ranging from 3.20-3.68 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in an octahedral geometry to two equivalent Cl(1), two equivalent Cl(2), and two equivalent Cl(3) atoms. Both Ti(1)-Cl(1) bond lengths are 2.40 Å. Both Ti(1)-Cl(2) bond lengths are 2.46 Å. Both Ti(1)-Cl(3) bond lengths are 2.47 Å. In the second Ti site, Ti(2) is bonded in an octahedral geometry to two equivalent Cl(4), two equivalent Cl(5), and two equivalent Cl(6) atoms. Both Ti(2)-Cl(4) bond lengths are 2.50 Å. Both Ti(2)-Cl(5) bond lengths are 2.38 Å. Both Ti(2)-Cl(6) bond lengths are 2.44 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(5) is bonded in a 1-coordinate geometry to one K(1), one K(2), two equivalent K(3), and one Ti(2) atom. In the second Cl site, Cl(6) is bonded in a 5-coordinate geometry to one K(1), one K(2), two equivalent K(3), and one Ti(2) atom. In the third Cl site, Cl(1) is bonded in a 5-coordinate geometry to one K(1), one K(3), two equivalent K(2), and one Ti(1) atom. In the fourth Cl site, Cl(2) is bonded in a 5-coordinate geometry to one K(2), one K(3), two equivalent K(1), and one Ti(1) atom. In the fifth Cl site, Cl(3) is bonded in a 5-coordinate geometry to two equivalent K(1), two equivalent K(2), and one Ti(1) atom. In the sixth Cl site, Cl(4) is bonded in a 6-coordinate geometry to one K(1), one K(2), three equivalent K(3), and one Ti(2) atom.