K3TiCl6 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form distorted KCl5 square pyramids that share corners with three equivalent Ti(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 25-38°. In the second K site, K(2) is bonded in a 5-coordinate geometry to one Cl(2), two equivalent Cl(3), and two equivalent Cl(5) atoms. In the third K site, K(3) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(3), two equivalent Cl(2), and two equivalent Cl(6) atoms. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a square co-planar geometry to two equivalent Cl(1) and two equivalent Cl(6) atoms. In the second Ti site, Ti(2) is bonded to two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms to form TiCl6 octahedra that share corners with six equivalent K(1)Cl5 square pyramids. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to one K(1), one K(3), and one Ti(1) atom. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one K(2), and two equivalent K(3) atoms. In the third Cl site, Cl(3) is bonded to one K(1), one K(3), two equivalent K(2), and one Ti(2) atom to form distorted ClK4Ti trigonal bipyramids that share corners with three equivalent Cl(5)K3Ti tetrahedra, corners with three equivalent Cl(3)K4Ti trigonal bipyramids, and edges with two equivalent Cl(5)K3Ti tetrahedra. In the fourth Cl site, Cl(4) is bonded in a distorted bent 150 degrees geometry to one K(1) and one Ti(2) atom. In the fifth Cl site, Cl(5) is bonded to one K(1), two equivalent K(2), and one Ti(2) atom to form distorted ClK3Ti tetrahedra that share  a cornercorner with one Cl(5)K3Ti tetrahedra, corners with three equivalent Cl(3)K4Ti trigonal bipyramids,  an edgeedge with one Cl(5)K3Ti tetrahedra, and edges with two equivalent Cl(3)K4Ti trigonal bipyramids. In the sixth Cl site, Cl(6) is bonded in a distorted T-shaped geometry to two equivalent K(3) and one Ti(1) atom.
K3TiCl6 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and crystallizes in the monoclinic P2_1/c space group. There are three inequivalent K sites. In the first K site, K(1) is bonded to one Cl(1), one Cl(2), one Cl(3), one Cl(4), and one Cl(5) atom to form distorted KCl5 square pyramids that share corners with three equivalent Ti(2)Cl6 octahedra. The corner-sharing octahedral tilt angles range from 25-38°. The K(1)-Cl(1) bond length is 3.11 Å. The K(1)-Cl(2) bond length is 2.92 Å. The K(1)-Cl(3) bond length is 3.57 Å. The K(1)-Cl(4) bond length is 3.12 Å. The K(1)-Cl(5) bond length is 3.12 Å. In the second K site, K(2) is bonded in a 5-coordinate geometry to one Cl(2), two equivalent Cl(3), and two equivalent Cl(5) atoms. The K(2)-Cl(2) bond length is 3.11 Å. There is one shorter (3.31 Å) and one longer (3.34 Å) K(2)-Cl(3) bond length. There is one shorter (3.12 Å) and one longer (3.20 Å) K(2)-Cl(5) bond length. In the third K site, K(3) is bonded in a 6-coordinate geometry to one Cl(1), one Cl(3), two equivalent Cl(2), and two equivalent Cl(6) atoms. The K(3)-Cl(1) bond length is 3.46 Å. The K(3)-Cl(3) bond length is 3.14 Å. There is one shorter (3.22 Å) and one longer (3.52 Å) K(3)-Cl(2) bond length. Both K(3)-Cl(6) bond lengths are 3.34 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded in a square co-planar geometry to two equivalent Cl(1) and two equivalent Cl(6) atoms. Both Ti(1)-Cl(1) bond lengths are 2.36 Å. Both Ti(1)-Cl(6) bond lengths are 2.31 Å. In the second Ti site, Ti(2) is bonded to two equivalent Cl(3), two equivalent Cl(4), and two equivalent Cl(5) atoms to form TiCl6 octahedra that share corners with six equivalent K(1)Cl5 square pyramids. Both Ti(2)-Cl(3) bond lengths are 2.50 Å. Both Ti(2)-Cl(4) bond lengths are 2.41 Å. Both Ti(2)-Cl(5) bond lengths are 2.36 Å. There are six inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to one K(1), one K(3), and one Ti(1) atom. In the second Cl site, Cl(2) is bonded in a distorted rectangular see-saw-like geometry to one K(1), one K(2), and two equivalent K(3) atoms. In the third Cl site, Cl(3) is bonded to one K(1), one K(3), two equivalent K(2), and one Ti(2) atom to form distorted ClK4Ti trigonal bipyramids that share corners with three equivalent Cl(5)K3Ti tetrahedra, corners with three equivalent Cl(3)K4Ti trigonal bipyramids, and edges with two equivalent Cl(5)K3Ti tetrahedra. In the fourth Cl site, Cl(4) is bonded in a distorted bent 150 degrees geometry to one K(1) and one Ti(2) atom. In the fifth Cl site, Cl(5) is bonded to one K(1), two equivalent K(2), and one Ti(2) atom to form distorted ClK3Ti tetrahedra that share  a cornercorner with one Cl(5)K3Ti tetrahedra, corners with three equivalent Cl(3)K4Ti trigonal bipyramids,  an edgeedge with one Cl(5)K3Ti tetrahedra, and edges with two equivalent Cl(3)K4Ti trigonal bipyramids. In the sixth Cl site, Cl(6) is bonded in a distorted T-shaped geometry to two equivalent K(3) and one Ti(1) atom.