Li4Ti3V3(SbO8)2 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-73°. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Sb(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. In the second Ti site, Ti(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Sb(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one O(8) and two equivalent O(1) atoms. In the second Sb site, Sb(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted SbO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-55°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), one V(2), and one Sb(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(4) and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one V(1) atom to form distorted corner-sharing OLiTi2V tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Ti(2), and two equivalent V(2) atoms to form OLiTiV2 tetrahedra that share corners with two equivalent O(12)LiV2Sb tetrahedra, corners with four equivalent O(9)LiTiVSb tetrahedra, and  an edgeedge with one O(8)LiV2Sb trigonal pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one Ti(1), and one V(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one Sb(2) atom. In the eighth O site, O(8) is bonded to one Li(3), two equivalent V(2), and one Sb(1) atom to form OLiV2Sb trigonal pyramids that share  a cornercorner with one O(4)LiTi2V tetrahedra, corners with two equivalent O(9)LiTiVSb tetrahedra, corners with two equivalent O(12)LiV2Sb tetrahedra, and  an edgeedge with one O(5)LiTiV2 tetrahedra. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one V(2), and one Sb(2) atom to form distorted OLiTiVSb tetrahedra that share  a cornercorner with one O(9)LiTiVSb tetrahedra,  a cornercorner with one O(12)LiV2Sb tetrahedra, corners with two equivalent O(5)LiTiV2 tetrahedra,  a cornercorner with one O(8)LiV2Sb trigonal pyramid,  an edgeedge with one O(9)LiTiVSb tetrahedra, and  an edgeedge with one O(12)LiV2Sb tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(2), and two equivalent V(2) atoms. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), one V(1), and one Sb(2) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Sb(2) atom to form distorted OLiV2Sb tetrahedra that share corners with two equivalent O(5)LiTiV2 tetrahedra, corners with two equivalent O(9)LiTiVSb tetrahedra, corners with two equivalent O(8)LiV2Sb trigonal pyramids, and edges with two equivalent O(9)LiTiVSb tetrahedra.
Li4Ti3V3(SbO8)2 is beta indium sulfide-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with three equivalent Sb(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 53-73°. The Li(1)-O(12) bond length is 2.01 Å. The Li(1)-O(3) bond length is 2.15 Å. Both Li(1)-O(9) bond lengths are 1.99 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. The Li(2)-O(5) bond length is 1.89 Å. The Li(2)-O(7) bond length is 2.00 Å. Both Li(2)-O(11) bond lengths are 1.97 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. The Li(3)-O(4) bond length is 1.96 Å. The Li(3)-O(8) bond length is 2.02 Å. Both Li(3)-O(1) bond lengths are 2.01 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Ti(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-55°. The Li(4)-O(10) bond length is 2.30 Å. The Li(4)-O(2) bond length is 1.97 Å. Both Li(4)-O(6) bond lengths are 1.99 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form TiO6 octahedra that share corners with two equivalent Sb(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. The Ti(1)-O(11) bond length is 2.08 Å. The Ti(1)-O(2) bond length is 1.93 Å. The Ti(1)-O(3) bond length is 2.01 Å. The Ti(1)-O(4) bond length is 2.00 Å. The Ti(1)-O(6) bond length is 1.92 Å. The Ti(1)-O(7) bond length is 2.06 Å. In the second Ti site, Ti(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form TiO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The Ti(2)-O(10) bond length is 2.03 Å. The Ti(2)-O(5) bond length is 1.97 Å. Both Ti(2)-O(1) bond lengths are 2.11 Å. Both Ti(2)-O(9) bond lengths are 1.93 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Sb(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and edges with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The V(1)-O(3) bond length is 2.05 Å. The V(1)-O(4) bond length is 2.09 Å. Both V(1)-O(11) bond lengths are 2.02 Å. Both V(1)-O(6) bond lengths are 1.94 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The V(2)-O(1) bond length is 2.05 Å. The V(2)-O(10) bond length is 2.01 Å. The V(2)-O(12) bond length is 1.93 Å. The V(2)-O(5) bond length is 2.05 Å. The V(2)-O(8) bond length is 2.07 Å. The V(2)-O(9) bond length is 1.99 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded in a 3-coordinate geometry to one O(8) and two equivalent O(1) atoms. The Sb(1)-O(8) bond length is 2.08 Å. Both Sb(1)-O(1) bond lengths are 2.06 Å. In the second Sb site, Sb(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted SbO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-55°. The Sb(2)-O(12) bond length is 2.47 Å. The Sb(2)-O(7) bond length is 2.12 Å. Both Sb(2)-O(11) bond lengths are 2.13 Å. Both Sb(2)-O(9) bond lengths are 2.43 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(2), one V(2), and one Sb(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(4) and two equivalent Ti(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Ti(1), and one V(1) atom to form distorted corner-sharing OLiTi2V tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Ti(2), and two equivalent V(2) atoms to form OLiTiV2 tetrahedra that share corners with two equivalent O(12)LiV2Sb tetrahedra, corners with four equivalent O(9)LiTiVSb tetrahedra, and  an edgeedge with one O(8)LiV2Sb trigonal pyramid. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one Ti(1), and one V(1) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), two equivalent Ti(1), and one Sb(2) atom. In the eighth O site, O(8) is bonded to one Li(3), two equivalent V(2), and one Sb(1) atom to form OLiV2Sb trigonal pyramids that share  a cornercorner with one O(4)LiTi2V tetrahedra, corners with two equivalent O(9)LiTiVSb tetrahedra, corners with two equivalent O(12)LiV2Sb tetrahedra, and  an edgeedge with one O(5)LiTiV2 tetrahedra. In the ninth O site, O(9) is bonded to one Li(1), one Ti(2), one V(2), and one Sb(2) atom to form distorted OLiTiVSb tetrahedra that share  a cornercorner with one O(9)LiTiVSb tetrahedra,  a cornercorner with one O(12)LiV2Sb tetrahedra, corners with two equivalent O(5)LiTiV2 tetrahedra,  a cornercorner with one O(8)LiV2Sb trigonal pyramid,  an edgeedge with one O(9)LiTiVSb tetrahedra, and  an edgeedge with one O(12)LiV2Sb tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(2), and two equivalent V(2) atoms. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ti(1), one V(1), and one Sb(2) atom. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Sb(2) atom to form distorted OLiV2Sb tetrahedra that share corners with two equivalent O(5)LiTiV2 tetrahedra, corners with two equivalent O(9)LiTiVSb tetrahedra, corners with two equivalent O(8)LiV2Sb trigonal pyramids, and edges with two equivalent O(9)LiTiVSb tetrahedra.