LiTi3V5O16 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(11), one O(12), one O(15), and one O(3) atom to form LiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-64°. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(14), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. In the second Ti site, Ti(2) is bonded to one O(16), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the third Ti site, Ti(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second V site, V(2) is bonded to one O(14), one O(16), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. In the third V site, V(3) is bonded to one O(11), one O(12), one O(14), one O(15), one O(16), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(13), one O(15), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. In the fifth V site, V(5) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(5) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(5) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Ti(1), one Ti(2), and one V(2) atom to form distorted OLiTi2V trigonal pyramids that share  a cornercorner with one O(11)LiTiV2 tetrahedra,  a cornercorner with one O(12)LiTiV2 tetrahedra, and  a cornercorner with one O(15)LiV3 tetrahedra. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(2), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2), one V(1), and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Ti(3), one V(3), and one V(5) atom to form distorted OLiTiV2 tetrahedra that share  a cornercorner with one O(12)LiTiV2 tetrahedra,  a cornercorner with one O(15)LiV3 tetrahedra,  a cornercorner with one O(3)LiTi2V trigonal pyramid,  an edgeedge with one O(12)LiTiV2 tetrahedra, and  an edgeedge with one O(15)LiV3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(1), one Ti(3), one V(3), and one V(4) atom to form distorted OLiTiV2 tetrahedra that share  a cornercorner with one O(11)LiTiV2 tetrahedra,  a cornercorner with one O(15)LiV3 tetrahedra,  a cornercorner with one O(3)LiTi2V trigonal pyramid,  an edgeedge with one O(11)LiTiV2 tetrahedra, and  an edgeedge with one O(15)LiV3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Ti(3), one V(4), and one V(5) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ti(1), one V(2), and one V(3) atom. In the fifteenth O site, O(15) is bonded to one Li(1), one V(3), one V(4), and one V(5) atom to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(11)LiTiV2 tetrahedra,  a cornercorner with one O(12)LiTiV2 tetrahedra,  a cornercorner with one O(3)LiTi2V trigonal pyramid,  an edgeedge with one O(11)LiTiV2 tetrahedra, and  an edgeedge with one O(12)LiTiV2 tetrahedra. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ti(2), one V(2), and one V(3) atom.
LiTi3V5O16 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(11), one O(12), one O(15), and one O(3) atom to form LiO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, and corners with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-64°. The Li(1)-O(11) bond length is 1.99 Å. The Li(1)-O(12) bond length is 1.99 Å. The Li(1)-O(15) bond length is 1.97 Å. The Li(1)-O(3) bond length is 1.96 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(14), one O(2), one O(3), one O(4), one O(7), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-55°. The Ti(1)-O(14) bond length is 1.89 Å. The Ti(1)-O(2) bond length is 1.96 Å. The Ti(1)-O(3) bond length is 2.03 Å. The Ti(1)-O(4) bond length is 1.92 Å. The Ti(1)-O(7) bond length is 2.10 Å. The Ti(1)-O(9) bond length is 2.02 Å. In the second Ti site, Ti(2) is bonded to one O(16), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form TiO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The Ti(2)-O(16) bond length is 1.99 Å. The Ti(2)-O(2) bond length is 2.14 Å. The Ti(2)-O(3) bond length is 2.01 Å. The Ti(2)-O(4) bond length is 1.96 Å. The Ti(2)-O(8) bond length is 1.92 Å. The Ti(2)-O(9) bond length is 1.90 Å. In the third Ti site, Ti(3) is bonded to one O(1), one O(11), one O(12), one O(13), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. The Ti(3)-O(1) bond length is 1.91 Å. The Ti(3)-O(11) bond length is 2.13 Å. The Ti(3)-O(12) bond length is 2.03 Å. The Ti(3)-O(13) bond length is 1.92 Å. The Ti(3)-O(5) bond length is 1.96 Å. The Ti(3)-O(6) bond length is 1.98 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(10), one O(2), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent Ti(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra,  an edgeedge with one Ti(2)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The V(1)-O(1) bond length is 2.08 Å. The V(1)-O(10) bond length is 1.93 Å. The V(1)-O(2) bond length is 1.88 Å. The V(1)-O(6) bond length is 2.03 Å. The V(1)-O(7) bond length is 2.01 Å. The V(1)-O(8) bond length is 1.94 Å. In the second V site, V(2) is bonded to one O(14), one O(16), one O(3), one O(4), one O(7), and one O(8) atom to form VO6 octahedra that share corners with two equivalent V(3)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with two equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-53°. The V(2)-O(14) bond length is 1.99 Å. The V(2)-O(16) bond length is 1.94 Å. The V(2)-O(3) bond length is 2.02 Å. The V(2)-O(4) bond length is 1.97 Å. The V(2)-O(7) bond length is 1.85 Å. The V(2)-O(8) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(11), one O(12), one O(14), one O(15), one O(16), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ti(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. The V(3)-O(11) bond length is 2.09 Å. The V(3)-O(12) bond length is 2.11 Å. The V(3)-O(14) bond length is 2.09 Å. The V(3)-O(15) bond length is 2.01 Å. The V(3)-O(16) bond length is 2.00 Å. The V(3)-O(9) bond length is 2.01 Å. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(13), one O(15), one O(5), and one O(6) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-48°. The V(4)-O(10) bond length is 2.01 Å. The V(4)-O(12) bond length is 1.92 Å. The V(4)-O(13) bond length is 1.99 Å. The V(4)-O(15) bond length is 2.01 Å. The V(4)-O(5) bond length is 1.96 Å. The V(4)-O(6) bond length is 1.93 Å. In the fifth V site, V(5) is bonded to one O(1), one O(10), one O(11), one O(13), one O(15), and one O(5) atom to form VO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Ti(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-51°. The V(5)-O(1) bond length is 1.98 Å. The V(5)-O(10) bond length is 2.01 Å. The V(5)-O(11) bond length is 1.88 Å. The V(5)-O(13) bond length is 1.99 Å. The V(5)-O(15) bond length is 2.00 Å. The V(5)-O(5) bond length is 1.96 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(5) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one Ti(2), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Ti(1), one Ti(2), and one V(2) atom to form distorted OLiTi2V trigonal pyramids that share  a cornercorner with one O(11)LiTiV2 tetrahedra,  a cornercorner with one O(12)LiTiV2 tetrahedra, and  a cornercorner with one O(15)LiV3 tetrahedra. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Ti(1), one Ti(2), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Ti(3), one V(4), and one V(5) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ti(3), one V(1), and one V(4) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Ti(1), one V(1), and one V(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Ti(2), one V(1), and one V(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Ti(1), one Ti(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one V(1), one V(4), and one V(5) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Ti(3), one V(3), and one V(5) atom to form distorted OLiTiV2 tetrahedra that share  a cornercorner with one O(12)LiTiV2 tetrahedra,  a cornercorner with one O(15)LiV3 tetrahedra,  a cornercorner with one O(3)LiTi2V trigonal pyramid,  an edgeedge with one O(12)LiTiV2 tetrahedra, and  an edgeedge with one O(15)LiV3 tetrahedra. In the twelfth O site, O(12) is bonded to one Li(1), one Ti(3), one V(3), and one V(4) atom to form distorted OLiTiV2 tetrahedra that share  a cornercorner with one O(11)LiTiV2 tetrahedra,  a cornercorner with one O(15)LiV3 tetrahedra,  a cornercorner with one O(3)LiTi2V trigonal pyramid,  an edgeedge with one O(11)LiTiV2 tetrahedra, and  an edgeedge with one O(15)LiV3 tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Ti(3), one V(4), and one V(5) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Ti(1), one V(2), and one V(3) atom. In the fifteenth O site, O(15) is bonded to one Li(1), one V(3), one V(4), and one V(5) atom to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(11)LiTiV2 tetrahedra,  a cornercorner with one O(12)LiTiV2 tetrahedra,  a cornercorner with one O(3)LiTi2V trigonal pyramid,  an edgeedge with one O(11)LiTiV2 tetrahedra, and  an edgeedge with one O(12)LiTiV2 tetrahedra. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Ti(2), one V(2), and one V(3) atom.