La3TiO4Cl5 crystallizes in the orthorhombic Pnma space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a distorted bent 120 degrees geometry to two equivalent O(2), one Cl(1), one Cl(3), two equivalent Cl(5), and three equivalent Cl(4) atoms. In the second La site, La(2) is bonded in a 2-coordinate geometry to two equivalent O(1), one Cl(1), one Cl(5), two equivalent Cl(3), and three equivalent Cl(2) atoms. In the third La site, La(3) is bonded in a 2-coordinate geometry to two equivalent O(3), one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(1), and two equivalent Cl(3) atoms. Ti(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(4) atoms to form corner-sharing TiO5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent La(2) and one Ti(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent La(1) and one Ti(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to two equivalent La(3) and one Ti(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to two equivalent Ti(1) atoms. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(2)La4 tetrahedra,  a cornercorner with one Cl(5)La4 tetrahedra, corners with two equivalent Cl(1)La4 tetrahedra, corners with five equivalent Cl(4)La4 tetrahedra, corners with five equivalent Cl(3)La5 trigonal bipyramids, edges with two equivalent Cl(2)La4 tetrahedra, edges with two equivalent Cl(5)La4 tetrahedra, and  an edgeedge with one Cl(3)La5 trigonal bipyramid. In the second Cl site, Cl(2) is bonded to one La(3) and three equivalent La(2) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(1)La4 tetrahedra,  a cornercorner with one Cl(4)La4 tetrahedra, corners with two equivalent Cl(2)La4 tetrahedra, corners with four equivalent Cl(5)La4 tetrahedra, corners with two equivalent Cl(3)La5 trigonal bipyramids, edges with two equivalent Cl(1)La4 tetrahedra, edges with two equivalent Cl(2)La4 tetrahedra, and edges with three equivalent Cl(3)La5 trigonal bipyramids. In the third Cl site, Cl(3) is bonded to one La(1), two equivalent La(2), and two equivalent La(3) atoms to form distorted ClLa5 trigonal bipyramids that share  a cornercorner with one Cl(4)La4 tetrahedra, corners with two equivalent Cl(2)La4 tetrahedra, corners with two equivalent Cl(5)La4 tetrahedra, corners with five equivalent Cl(1)La4 tetrahedra,  an edgeedge with one Cl(1)La4 tetrahedra, edges with two equivalent Cl(4)La4 tetrahedra, edges with two equivalent Cl(5)La4 tetrahedra, edges with three equivalent Cl(2)La4 tetrahedra, and edges with two equivalent Cl(3)La5 trigonal bipyramids. In the fourth Cl site, Cl(4) is bonded to one La(3) and three equivalent La(1) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(2)La4 tetrahedra, corners with two equivalent Cl(4)La4 tetrahedra, corners with five equivalent Cl(1)La4 tetrahedra, corners with five equivalent Cl(5)La4 tetrahedra,  a cornercorner with one Cl(3)La5 trigonal bipyramid,  an edgeedge with one Cl(5)La4 tetrahedra, edges with two equivalent Cl(4)La4 tetrahedra, and edges with two equivalent Cl(3)La5 trigonal bipyramids. In the fifth Cl site, Cl(5) is bonded to one La(2), one La(3), and two equivalent La(1) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(1)La4 tetrahedra, corners with two equivalent Cl(5)La4 tetrahedra, corners with four equivalent Cl(2)La4 tetrahedra, corners with five equivalent Cl(4)La4 tetrahedra, corners with two equivalent Cl(3)La5 trigonal bipyramids,  an edgeedge with one Cl(4)La4 tetrahedra, edges with two equivalent Cl(1)La4 tetrahedra, and edges with two equivalent Cl(3)La5 trigonal bipyramids.
La3TiO4Cl5 crystallizes in the orthorhombic Pnma space group. There are three inequivalent La sites. In the first La site, La(1) is bonded in a distorted bent 120 degrees geometry to two equivalent O(2), one Cl(1), one Cl(3), two equivalent Cl(5), and three equivalent Cl(4) atoms. Both La(1)-O(2) bond lengths are 2.31 Å. The La(1)-Cl(1) bond length is 3.03 Å. The La(1)-Cl(3) bond length is 3.45 Å. Both La(1)-Cl(5) bond lengths are 3.12 Å. There are two shorter (3.10 Å) and one longer (3.16 Å) La(1)-Cl(4) bond length. In the second La site, La(2) is bonded in a 2-coordinate geometry to two equivalent O(1), one Cl(1), one Cl(5), two equivalent Cl(3), and three equivalent Cl(2) atoms. Both La(2)-O(1) bond lengths are 2.29 Å. The La(2)-Cl(1) bond length is 3.07 Å. The La(2)-Cl(5) bond length is 3.00 Å. Both La(2)-Cl(3) bond lengths are 3.29 Å. There is one shorter (3.00 Å) and two longer (3.13 Å) La(2)-Cl(2) bond lengths. In the third La site, La(3) is bonded in a 2-coordinate geometry to two equivalent O(3), one Cl(2), one Cl(4), one Cl(5), two equivalent Cl(1), and two equivalent Cl(3) atoms. Both La(3)-O(3) bond lengths are 2.28 Å. The La(3)-Cl(2) bond length is 2.99 Å. The La(3)-Cl(4) bond length is 3.11 Å. The La(3)-Cl(5) bond length is 3.23 Å. Both La(3)-Cl(1) bond lengths are 3.14 Å. Both La(3)-Cl(3) bond lengths are 3.30 Å. Ti(1) is bonded to one O(1), one O(2), one O(3), and two equivalent O(4) atoms to form corner-sharing TiO5 trigonal bipyramids. The Ti(1)-O(1) bond length is 1.85 Å. The Ti(1)-O(2) bond length is 1.85 Å. The Ti(1)-O(3) bond length is 1.85 Å. Both Ti(1)-O(4) bond lengths are 2.04 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent La(2) and one Ti(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to two equivalent La(1) and one Ti(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to two equivalent La(3) and one Ti(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to two equivalent Ti(1) atoms. There are five inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one La(1), one La(2), and two equivalent La(3) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(2)La4 tetrahedra,  a cornercorner with one Cl(5)La4 tetrahedra, corners with two equivalent Cl(1)La4 tetrahedra, corners with five equivalent Cl(4)La4 tetrahedra, corners with five equivalent Cl(3)La5 trigonal bipyramids, edges with two equivalent Cl(2)La4 tetrahedra, edges with two equivalent Cl(5)La4 tetrahedra, and  an edgeedge with one Cl(3)La5 trigonal bipyramid. In the second Cl site, Cl(2) is bonded to one La(3) and three equivalent La(2) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(1)La4 tetrahedra,  a cornercorner with one Cl(4)La4 tetrahedra, corners with two equivalent Cl(2)La4 tetrahedra, corners with four equivalent Cl(5)La4 tetrahedra, corners with two equivalent Cl(3)La5 trigonal bipyramids, edges with two equivalent Cl(1)La4 tetrahedra, edges with two equivalent Cl(2)La4 tetrahedra, and edges with three equivalent Cl(3)La5 trigonal bipyramids. In the third Cl site, Cl(3) is bonded to one La(1), two equivalent La(2), and two equivalent La(3) atoms to form distorted ClLa5 trigonal bipyramids that share  a cornercorner with one Cl(4)La4 tetrahedra, corners with two equivalent Cl(2)La4 tetrahedra, corners with two equivalent Cl(5)La4 tetrahedra, corners with five equivalent Cl(1)La4 tetrahedra,  an edgeedge with one Cl(1)La4 tetrahedra, edges with two equivalent Cl(4)La4 tetrahedra, edges with two equivalent Cl(5)La4 tetrahedra, edges with three equivalent Cl(2)La4 tetrahedra, and edges with two equivalent Cl(3)La5 trigonal bipyramids. In the fourth Cl site, Cl(4) is bonded to one La(3) and three equivalent La(1) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(2)La4 tetrahedra, corners with two equivalent Cl(4)La4 tetrahedra, corners with five equivalent Cl(1)La4 tetrahedra, corners with five equivalent Cl(5)La4 tetrahedra,  a cornercorner with one Cl(3)La5 trigonal bipyramid,  an edgeedge with one Cl(5)La4 tetrahedra, edges with two equivalent Cl(4)La4 tetrahedra, and edges with two equivalent Cl(3)La5 trigonal bipyramids. In the fifth Cl site, Cl(5) is bonded to one La(2), one La(3), and two equivalent La(1) atoms to form ClLa4 tetrahedra that share  a cornercorner with one Cl(1)La4 tetrahedra, corners with two equivalent Cl(5)La4 tetrahedra, corners with four equivalent Cl(2)La4 tetrahedra, corners with five equivalent Cl(4)La4 tetrahedra, corners with two equivalent Cl(3)La5 trigonal bipyramids,  an edgeedge with one Cl(4)La4 tetrahedra, edges with two equivalent Cl(1)La4 tetrahedra, and edges with two equivalent Cl(3)La5 trigonal bipyramids.