LiTl4Al4O12 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pm space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one Tl(1), one Tl(2), one O(5), one O(8), and two equivalent O(3) atoms. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 5-coordinate geometry to one Li(1), one O(5), one O(8), and two equivalent O(2) atoms. In the second Tl site, Tl(2) is bonded in a 9-coordinate geometry to one Li(1), one O(5), one O(8), two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. In the third Tl site, Tl(3) is bonded in a 8-coordinate geometry to one O(1), one O(4), two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. In the fourth Tl site, Tl(4) is bonded in a 8-coordinate geometry to one O(1), one O(4), two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form distorted corner-sharing AlO6 octahedra. The corner-sharing octahedral tilt angles range from 16-38°. In the second Al site, Al(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing AlO6 octahedra. The corner-sharing octahedral tilt angles range from 20-33°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Tl(3), one Tl(4), and two equivalent Al(1) atoms to form distorted corner-sharing OAl2Tl2 tetrahedra. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Tl(1), one Tl(2), one Tl(4), one Al(1), and one Al(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Tl(2), one Tl(3), one Al(1), and one Al(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Tl(3), one Tl(4), and two equivalent Al(2) atoms. In the fifth O site, O(5) is bonded to one Li(1), one Tl(1), one Tl(2), and two equivalent Al(2) atoms to form a mixture of distorted corner and edge-sharing OLiAl2Tl2 square pyramids. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Tl(2), one Tl(3), one Tl(4), one Al(1), and one Al(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Tl(3), one Tl(4), one Al(1), and one Al(2) atom. In the eighth O site, O(8) is bonded to one Li(1), one Tl(1), one Tl(2), and two equivalent Al(1) atoms to form distorted OLiAl2Tl2 trigonal bipyramids that share  a cornercorner with one O(5)LiAl2Tl2 square pyramid, corners with two equivalent O(1)Al2Tl2 tetrahedra, and  an edgeedge with one O(5)LiAl2Tl2 square pyramid.
LiTl4Al4O12 is Orthorhombic Perovskite-derived structured and crystallizes in the monoclinic Pm space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one Tl(1), one Tl(2), one O(5), one O(8), and two equivalent O(3) atoms. The Li(1)-Tl(1) bond length is 2.43 Å. The Li(1)-Tl(2) bond length is 2.42 Å. The Li(1)-O(5) bond length is 2.02 Å. The Li(1)-O(8) bond length is 2.04 Å. Both Li(1)-O(3) bond lengths are 1.83 Å. There are four inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 5-coordinate geometry to one Li(1), one O(5), one O(8), and two equivalent O(2) atoms. The Tl(1)-O(5) bond length is 2.10 Å. The Tl(1)-O(8) bond length is 2.42 Å. Both Tl(1)-O(2) bond lengths are 2.18 Å. In the second Tl site, Tl(2) is bonded in a 9-coordinate geometry to one Li(1), one O(5), one O(8), two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. The Tl(2)-O(5) bond length is 2.52 Å. The Tl(2)-O(8) bond length is 2.39 Å. Both Tl(2)-O(2) bond lengths are 2.61 Å. Both Tl(2)-O(3) bond lengths are 2.53 Å. Both Tl(2)-O(6) bond lengths are 2.65 Å. In the third Tl site, Tl(3) is bonded in a 8-coordinate geometry to one O(1), one O(4), two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. The Tl(3)-O(1) bond length is 2.28 Å. The Tl(3)-O(4) bond length is 2.61 Å. Both Tl(3)-O(3) bond lengths are 2.57 Å. Both Tl(3)-O(6) bond lengths are 2.40 Å. Both Tl(3)-O(7) bond lengths are 2.48 Å. In the fourth Tl site, Tl(4) is bonded in a 8-coordinate geometry to one O(1), one O(4), two equivalent O(2), two equivalent O(6), and two equivalent O(7) atoms. The Tl(4)-O(1) bond length is 2.32 Å. The Tl(4)-O(4) bond length is 2.28 Å. Both Tl(4)-O(2) bond lengths are 2.58 Å. Both Tl(4)-O(6) bond lengths are 2.68 Å. Both Tl(4)-O(7) bond lengths are 2.28 Å. There are two inequivalent Al sites. In the first Al site, Al(1) is bonded to one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom to form distorted corner-sharing AlO6 octahedra. The corner-sharing octahedral tilt angles range from 16-38°. The Al(1)-O(1) bond length is 1.93 Å. The Al(1)-O(2) bond length is 2.28 Å. The Al(1)-O(3) bond length is 1.86 Å. The Al(1)-O(6) bond length is 1.94 Å. The Al(1)-O(7) bond length is 1.93 Å. The Al(1)-O(8) bond length is 2.01 Å. In the second Al site, Al(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form corner-sharing AlO6 octahedra. The corner-sharing octahedral tilt angles range from 20-33°. The Al(2)-O(2) bond length is 2.00 Å. The Al(2)-O(3) bond length is 1.89 Å. The Al(2)-O(4) bond length is 1.85 Å. The Al(2)-O(5) bond length is 2.05 Å. The Al(2)-O(6) bond length is 1.95 Å. The Al(2)-O(7) bond length is 2.06 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Tl(3), one Tl(4), and two equivalent Al(1) atoms to form distorted corner-sharing OAl2Tl2 tetrahedra. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Tl(1), one Tl(2), one Tl(4), one Al(1), and one Al(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Tl(2), one Tl(3), one Al(1), and one Al(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Tl(3), one Tl(4), and two equivalent Al(2) atoms. In the fifth O site, O(5) is bonded to one Li(1), one Tl(1), one Tl(2), and two equivalent Al(2) atoms to form a mixture of distorted corner and edge-sharing OLiAl2Tl2 square pyramids. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Tl(2), one Tl(3), one Tl(4), one Al(1), and one Al(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Tl(3), one Tl(4), one Al(1), and one Al(2) atom. In the eighth O site, O(8) is bonded to one Li(1), one Tl(1), one Tl(2), and two equivalent Al(1) atoms to form distorted OLiAl2Tl2 trigonal bipyramids that share  a cornercorner with one O(5)LiAl2Tl2 square pyramid, corners with two equivalent O(1)Al2Tl2 tetrahedra, and  an edgeedge with one O(5)LiAl2Tl2 square pyramid.