LiLa5Ti8O24 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a distorted see-saw-like geometry to two equivalent O(4) and two equivalent O(9) atoms. There are five inequivalent La sites. In the first La site, La(1) is bonded to two equivalent O(2), two equivalent O(7), two equivalent O(8), two equivalent O(9), and four equivalent O(6) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(3)O12 cuboctahedra, corners with four equivalent La(5)O12 cuboctahedra, faces with two equivalent La(4)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. In the second La site, La(2) is bonded to two equivalent O(10), two equivalent O(3), two equivalent O(4), two equivalent O(5), and four equivalent O(1) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(4)O12 cuboctahedra, faces with two equivalent La(3)O12 cuboctahedra, faces with two equivalent La(5)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. In the third La site, La(3) is bonded to two equivalent O(10), two equivalent O(2), two equivalent O(3), two equivalent O(7), and four equivalent O(1) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with four equivalent La(5)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, faces with two equivalent La(4)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. In the fourth La site, La(4) is bonded to two equivalent O(10), two equivalent O(2), two equivalent O(3), two equivalent O(7), and four equivalent O(6) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(2)O12 cuboctahedra, faces with two equivalent La(1)O12 cuboctahedra, faces with two equivalent La(3)O12 cuboctahedra, faces with two equivalent La(5)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. In the fifth La site, La(5) is bonded to two equivalent O(10), two equivalent O(3), two equivalent O(4), two equivalent O(5), and four equivalent O(6) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with four equivalent La(3)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, faces with two equivalent La(4)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(10), one O(2), one O(5), one O(6), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  a faceface with one La(1)O12 cuboctahedra,  a faceface with one La(2)O12 cuboctahedra,  a faceface with one La(3)O12 cuboctahedra,  a faceface with one La(4)O12 cuboctahedra, and  a faceface with one La(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 7-28°. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  a faceface with one La(1)O12 cuboctahedra,  a faceface with one La(2)O12 cuboctahedra,  a faceface with one La(3)O12 cuboctahedra,  a faceface with one La(4)O12 cuboctahedra, and  a faceface with one La(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 7-23°. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one La(2), one La(3), one Ti(1), and one Ti(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one La(1), one La(3), one La(4), and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one La(2), one La(3), one La(4), one La(5), and two equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one La(2), one La(5), and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to one La(2), one La(5), and two equivalent Ti(1) atoms to form distorted edge-sharing OLa2Ti2 trigonal pyramids. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one La(1), one La(4), one La(5), one Ti(1), and one Ti(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one La(1), one La(3), one La(4), and two equivalent Ti(2) atoms. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one La(1) and two equivalent Ti(1) atoms. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Li(1), one La(1), and two equivalent Ti(2) atoms. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one La(2), one La(3), one La(4), one La(5), and two equivalent Ti(1) atoms.
LiLa5Ti8O24 crystallizes in the orthorhombic Pmm2 space group. Li(1) is bonded in a distorted see-saw-like geometry to two equivalent O(4) and two equivalent O(9) atoms. Both Li(1)-O(4) bond lengths are 1.94 Å. Both Li(1)-O(9) bond lengths are 2.18 Å. There are five inequivalent La sites. In the first La site, La(1) is bonded to two equivalent O(2), two equivalent O(7), two equivalent O(8), two equivalent O(9), and four equivalent O(6) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(3)O12 cuboctahedra, corners with four equivalent La(5)O12 cuboctahedra, faces with two equivalent La(4)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. Both La(1)-O(2) bond lengths are 2.52 Å. Both La(1)-O(7) bond lengths are 3.12 Å. Both La(1)-O(8) bond lengths are 2.60 Å. Both La(1)-O(9) bond lengths are 2.58 Å. All La(1)-O(6) bond lengths are 2.83 Å. In the second La site, La(2) is bonded to two equivalent O(10), two equivalent O(3), two equivalent O(4), two equivalent O(5), and four equivalent O(1) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(4)O12 cuboctahedra, faces with two equivalent La(3)O12 cuboctahedra, faces with two equivalent La(5)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. Both La(2)-O(10) bond lengths are 2.94 Å. Both La(2)-O(3) bond lengths are 2.55 Å. Both La(2)-O(4) bond lengths are 2.90 Å. Both La(2)-O(5) bond lengths are 2.54 Å. All La(2)-O(1) bond lengths are 2.64 Å. In the third La site, La(3) is bonded to two equivalent O(10), two equivalent O(2), two equivalent O(3), two equivalent O(7), and four equivalent O(1) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with four equivalent La(5)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, faces with two equivalent La(4)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. Both La(3)-O(10) bond lengths are 2.50 Å. Both La(3)-O(2) bond lengths are 2.88 Å. Both La(3)-O(3) bond lengths are 3.01 Å. Both La(3)-O(7) bond lengths are 2.59 Å. All La(3)-O(1) bond lengths are 2.66 Å. In the fourth La site, La(4) is bonded to two equivalent O(10), two equivalent O(2), two equivalent O(3), two equivalent O(7), and four equivalent O(6) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(2)O12 cuboctahedra, faces with two equivalent La(1)O12 cuboctahedra, faces with two equivalent La(3)O12 cuboctahedra, faces with two equivalent La(5)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. Both La(4)-O(10) bond lengths are 2.53 Å. Both La(4)-O(2) bond lengths are 2.76 Å. Both La(4)-O(3) bond lengths are 3.03 Å. Both La(4)-O(7) bond lengths are 2.61 Å. All La(4)-O(6) bond lengths are 2.59 Å. In the fifth La site, La(5) is bonded to two equivalent O(10), two equivalent O(3), two equivalent O(4), two equivalent O(5), and four equivalent O(6) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with four equivalent La(3)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, faces with two equivalent La(4)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(2)O6 octahedra. Both La(5)-O(10) bond lengths are 3.02 Å. Both La(5)-O(3) bond lengths are 2.51 Å. Both La(5)-O(4) bond lengths are 2.79 Å. Both La(5)-O(5) bond lengths are 2.55 Å. All La(5)-O(6) bond lengths are 2.71 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(10), one O(2), one O(5), one O(6), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra,  a faceface with one La(1)O12 cuboctahedra,  a faceface with one La(2)O12 cuboctahedra,  a faceface with one La(3)O12 cuboctahedra,  a faceface with one La(4)O12 cuboctahedra, and  a faceface with one La(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 7-28°. The Ti(1)-O(1) bond length is 1.94 Å. The Ti(1)-O(10) bond length is 2.08 Å. The Ti(1)-O(2) bond length is 1.98 Å. The Ti(1)-O(5) bond length is 1.96 Å. The Ti(1)-O(6) bond length is 2.00 Å. The Ti(1)-O(8) bond length is 1.89 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra,  a faceface with one La(1)O12 cuboctahedra,  a faceface with one La(2)O12 cuboctahedra,  a faceface with one La(3)O12 cuboctahedra,  a faceface with one La(4)O12 cuboctahedra, and  a faceface with one La(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 7-23°. The Ti(2)-O(1) bond length is 1.92 Å. The Ti(2)-O(3) bond length is 2.05 Å. The Ti(2)-O(4) bond length is 1.95 Å. The Ti(2)-O(6) bond length is 2.02 Å. The Ti(2)-O(7) bond length is 1.98 Å. The Ti(2)-O(9) bond length is 1.92 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one La(2), one La(3), one Ti(1), and one Ti(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one La(1), one La(3), one La(4), and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one La(2), one La(3), one La(4), one La(5), and two equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one La(2), one La(5), and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to one La(2), one La(5), and two equivalent Ti(1) atoms to form distorted edge-sharing OLa2Ti2 trigonal pyramids. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one La(1), one La(4), one La(5), one Ti(1), and one Ti(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one La(1), one La(3), one La(4), and two equivalent Ti(2) atoms. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one La(1) and two equivalent Ti(1) atoms. In the ninth O site, O(9) is bonded in a distorted see-saw-like geometry to one Li(1), one La(1), and two equivalent Ti(2) atoms. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one La(2), one La(3), one La(4), one La(5), and two equivalent Ti(1) atoms.