LiLa5Ti8O24 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pm space group. Li(1) is bonded in a square co-planar geometry to one O(12), one O(9), and two equivalent O(8) atoms. There are five inequivalent La sites. In the first La site, La(1) is bonded in a 12-coordinate geometry to one O(13), one O(16), one O(3), one O(5), two equivalent O(1), two equivalent O(14), two equivalent O(4), and two equivalent O(7) atoms. In the second La site, La(2) is bonded to one O(13), one O(16), one O(3), one O(5), two equivalent O(10), two equivalent O(11), two equivalent O(6), and two equivalent O(8) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(4)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Ti(4)O6 octahedra. In the third La site, La(3) is bonded in a 12-coordinate geometry to one O(13), one O(16), one O(3), one O(5), two equivalent O(10), two equivalent O(14), two equivalent O(4), and two equivalent O(8) atoms. In the fourth La site, La(4) is bonded to one O(12), one O(15), one O(2), one O(9), two equivalent O(1), two equivalent O(11), two equivalent O(6), and two equivalent O(7) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(2)O12 cuboctahedra, faces with two equivalent La(5)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Ti(4)O6 octahedra. In the fifth La site, La(5) is bonded to one O(12), one O(15), one O(2), one O(9), two equivalent O(1), two equivalent O(14), two equivalent O(4), and two equivalent O(7) atoms to form distorted LaO12 cuboctahedra that share faces with two equivalent La(4)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Ti(4)O6 octahedra. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  a faceface with one La(2)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 6-17°. In the second Ti site, Ti(2) is bonded to one O(10), one O(11), one O(14), one O(15), one O(3), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  a faceface with one La(2)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 9-22°. In the third Ti site, Ti(3) is bonded to one O(10), one O(16), one O(2), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra,  a faceface with one La(2)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 9-23°. In the fourth Ti site, Ti(4) is bonded to one O(1), one O(11), one O(12), one O(13), one O(14), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  a faceface with one La(2)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 6-20°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one La(1), one La(4), one La(5), one Ti(1), and one Ti(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one La(4), one La(5), and two equivalent Ti(3) atoms. In the third O site, O(3) is bonded in a 5-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one La(1), one La(3), one La(5), one Ti(1), and one Ti(3) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(1) atoms. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one La(2), one La(4), one Ti(1), and one Ti(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one La(1), one La(4), one La(5), one Ti(2), and one Ti(3) atom. In the eighth O site, O(8) is bonded to one Li(1), one La(2), one La(3), one Ti(1), and one Ti(4) atom to form a mixture of distorted edge and corner-sharing OLiLa2Ti2 trigonal bipyramids. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one La(4), one La(5), and two equivalent Ti(1) atoms. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one La(2), one La(3), one Ti(2), and one Ti(3) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one La(2), one La(4), one Ti(2), and one Ti(4) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(1), one La(4), one La(5), and two equivalent Ti(4) atoms. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(4) atoms. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one La(1), one La(3), one La(5), one Ti(2), and one Ti(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one La(4), one La(5), and two equivalent Ti(2) atoms. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(3) atoms.
LiLa5Ti8O24 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pm space group. Li(1) is bonded in a square co-planar geometry to one O(12), one O(9), and two equivalent O(8) atoms. The Li(1)-O(12) bond length is 1.95 Å. The Li(1)-O(9) bond length is 1.99 Å. Both Li(1)-O(8) bond lengths are 2.04 Å. There are five inequivalent La sites. In the first La site, La(1) is bonded in a 12-coordinate geometry to one O(13), one O(16), one O(3), one O(5), two equivalent O(1), two equivalent O(14), two equivalent O(4), and two equivalent O(7) atoms. The La(1)-O(13) bond length is 3.28 Å. The La(1)-O(16) bond length is 2.40 Å. The La(1)-O(3) bond length is 2.86 Å. The La(1)-O(5) bond length is 2.63 Å. Both La(1)-O(1) bond lengths are 3.11 Å. Both La(1)-O(14) bond lengths are 2.55 Å. Both La(1)-O(4) bond lengths are 2.70 Å. Both La(1)-O(7) bond lengths are 2.55 Å. In the second La site, La(2) is bonded to one O(13), one O(16), one O(3), one O(5), two equivalent O(10), two equivalent O(11), two equivalent O(6), and two equivalent O(8) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(4)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Ti(4)O6 octahedra. The La(2)-O(13) bond length is 2.47 Å. The La(2)-O(16) bond length is 3.01 Å. The La(2)-O(3) bond length is 2.54 Å. The La(2)-O(5) bond length is 3.06 Å. Both La(2)-O(10) bond lengths are 2.75 Å. Both La(2)-O(11) bond lengths are 2.85 Å. Both La(2)-O(6) bond lengths are 2.59 Å. Both La(2)-O(8) bond lengths are 2.75 Å. In the third La site, La(3) is bonded in a 12-coordinate geometry to one O(13), one O(16), one O(3), one O(5), two equivalent O(10), two equivalent O(14), two equivalent O(4), and two equivalent O(8) atoms. The La(3)-O(13) bond length is 2.82 Å. The La(3)-O(16) bond length is 2.57 Å. The La(3)-O(3) bond length is 2.69 Å. The La(3)-O(5) bond length is 2.72 Å. Both La(3)-O(10) bond lengths are 2.57 Å. Both La(3)-O(14) bond lengths are 2.57 Å. Both La(3)-O(4) bond lengths are 3.09 Å. Both La(3)-O(8) bond lengths are 2.68 Å. In the fourth La site, La(4) is bonded to one O(12), one O(15), one O(2), one O(9), two equivalent O(1), two equivalent O(11), two equivalent O(6), and two equivalent O(7) atoms to form distorted LaO12 cuboctahedra that share corners with four equivalent La(2)O12 cuboctahedra, faces with two equivalent La(5)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Ti(4)O6 octahedra. The La(4)-O(12) bond length is 2.89 Å. The La(4)-O(15) bond length is 2.84 Å. The La(4)-O(2) bond length is 2.51 Å. The La(4)-O(9) bond length is 2.62 Å. Both La(4)-O(1) bond lengths are 2.54 Å. Both La(4)-O(11) bond lengths are 2.64 Å. Both La(4)-O(6) bond lengths are 3.02 Å. Both La(4)-O(7) bond lengths are 2.85 Å. In the fifth La site, La(5) is bonded to one O(12), one O(15), one O(2), one O(9), two equivalent O(1), two equivalent O(14), two equivalent O(4), and two equivalent O(7) atoms to form distorted LaO12 cuboctahedra that share faces with two equivalent La(4)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Ti(4)O6 octahedra. The La(5)-O(12) bond length is 2.76 Å. The La(5)-O(15) bond length is 2.48 Å. The La(5)-O(2) bond length is 2.66 Å. The La(5)-O(9) bond length is 2.90 Å. Both La(5)-O(1) bond lengths are 2.73 Å. Both La(5)-O(14) bond lengths are 2.98 Å. Both La(5)-O(4) bond lengths are 2.47 Å. Both La(5)-O(7) bond lengths are 2.72 Å. There are four inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  a faceface with one La(2)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 6-17°. The Ti(1)-O(1) bond length is 2.03 Å. The Ti(1)-O(4) bond length is 1.93 Å. The Ti(1)-O(5) bond length is 1.96 Å. The Ti(1)-O(6) bond length is 2.01 Å. The Ti(1)-O(8) bond length is 1.91 Å. The Ti(1)-O(9) bond length is 1.97 Å. In the second Ti site, Ti(2) is bonded to one O(10), one O(11), one O(14), one O(15), one O(3), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  a faceface with one La(2)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 9-22°. The Ti(2)-O(10) bond length is 2.02 Å. The Ti(2)-O(11) bond length is 1.85 Å. The Ti(2)-O(14) bond length is 2.13 Å. The Ti(2)-O(15) bond length is 1.94 Å. The Ti(2)-O(3) bond length is 2.00 Å. The Ti(2)-O(7) bond length is 1.93 Å. In the third Ti site, Ti(3) is bonded to one O(10), one O(16), one O(2), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra,  a faceface with one La(2)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 9-23°. The Ti(3)-O(10) bond length is 1.87 Å. The Ti(3)-O(16) bond length is 2.02 Å. The Ti(3)-O(2) bond length is 1.95 Å. The Ti(3)-O(4) bond length is 2.10 Å. The Ti(3)-O(6) bond length is 1.86 Å. The Ti(3)-O(7) bond length is 2.10 Å. In the fourth Ti site, Ti(4) is bonded to one O(1), one O(11), one O(12), one O(13), one O(14), and one O(8) atom to form TiO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Ti(4)O6 octahedra,  a faceface with one La(2)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 6-20°. The Ti(4)-O(1) bond length is 1.91 Å. The Ti(4)-O(11) bond length is 2.01 Å. The Ti(4)-O(12) bond length is 1.97 Å. The Ti(4)-O(13) bond length is 1.97 Å. The Ti(4)-O(14) bond length is 1.92 Å. The Ti(4)-O(8) bond length is 2.05 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one La(1), one La(4), one La(5), one Ti(1), and one Ti(4) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one La(4), one La(5), and two equivalent Ti(3) atoms. In the third O site, O(3) is bonded in a 5-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(2) atoms. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one La(1), one La(3), one La(5), one Ti(1), and one Ti(3) atom. In the fifth O site, O(5) is bonded in a 2-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(1) atoms. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one La(2), one La(4), one Ti(1), and one Ti(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one La(1), one La(4), one La(5), one Ti(2), and one Ti(3) atom. In the eighth O site, O(8) is bonded to one Li(1), one La(2), one La(3), one Ti(1), and one Ti(4) atom to form a mixture of distorted edge and corner-sharing OLiLa2Ti2 trigonal bipyramids. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one La(4), one La(5), and two equivalent Ti(1) atoms. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one La(2), one La(3), one Ti(2), and one Ti(3) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one La(2), one La(4), one Ti(2), and one Ti(4) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(1), one La(4), one La(5), and two equivalent Ti(4) atoms. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(4) atoms. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one La(1), one La(3), one La(5), one Ti(2), and one Ti(4) atom. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one La(4), one La(5), and two equivalent Ti(2) atoms. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one La(1), one La(2), one La(3), and two equivalent Ti(3) atoms.