Li2TiV3O8 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. Ti(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form TiO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-12°. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the fifth V site, V(5) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one V(1), one V(2), and one V(4) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(2)Li2V3 square pyramid, corners with four equivalent O(1)Li2V3 square pyramids, and edges with four equivalent O(3)Li2TiV2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(1), one V(3), and one V(5) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid, corners with four equivalent O(2)Li2V3 square pyramids, and edges with four equivalent O(4)Li2TiV2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(4), one Ti(1), one V(2), and one V(4) atom to form OLi2TiV2 square pyramids that share  a cornercorner with one O(4)Li2TiV2 square pyramid, corners with four equivalent O(3)Li2TiV2 square pyramids, and edges with four equivalent O(1)Li2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(1), one V(3), and one V(5) atom to form OLi2TiV2 square pyramids that share  a cornercorner with one O(3)Li2TiV2 square pyramid, corners with four equivalent O(4)Li2TiV2 square pyramids, and edges with four equivalent O(2)Li2V3 square pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(1), one V(1), and one V(3) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one V(1), and one V(5) atom.
Li2TiV3O8 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with four equivalent V(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. Both Li(1)-O(2) bond lengths are 2.20 Å. Both Li(1)-O(4) bond lengths are 2.18 Å. Both Li(1)-O(7) bond lengths are 2.25 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with two equivalent V(5)O6 octahedra, corners with four equivalent V(4)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both Li(2)-O(1) bond lengths are 2.20 Å. Both Li(2)-O(3) bond lengths are 2.17 Å. Both Li(2)-O(8) bond lengths are 2.23 Å. In the third Li site, Li(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-13°. Both Li(3)-O(2) bond lengths are 2.19 Å. Both Li(3)-O(4) bond lengths are 2.21 Å. Both Li(3)-O(5) bond lengths are 2.22 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-12°. Both Li(4)-O(1) bond lengths are 2.19 Å. Both Li(4)-O(3) bond lengths are 2.21 Å. Both Li(4)-O(6) bond lengths are 2.21 Å. Ti(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form TiO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The Ti(1)-O(3) bond length is 1.97 Å. The Ti(1)-O(4) bond length is 1.98 Å. The Ti(1)-O(5) bond length is 2.02 Å. The Ti(1)-O(6) bond length is 1.97 Å. The Ti(1)-O(7) bond length is 1.97 Å. The Ti(1)-O(8) bond length is 1.95 Å. There are five inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, and edges with two equivalent Ti(1)O6 octahedra. The V(1)-O(1) bond length is 1.98 Å. The V(1)-O(2) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.91 Å. The V(1)-O(6) bond length is 1.94 Å. The V(1)-O(7) bond length is 1.99 Å. The V(1)-O(8) bond length is 1.98 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both V(2)-O(1) bond lengths are 2.04 Å. Both V(2)-O(3) bond lengths are 2.06 Å. Both V(2)-O(5) bond lengths are 2.10 Å. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-12°. Both V(3)-O(2) bond lengths are 2.04 Å. Both V(3)-O(4) bond lengths are 2.05 Å. Both V(3)-O(6) bond lengths are 2.11 Å. In the fourth V site, V(4) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both V(4)-O(1) bond lengths are 2.06 Å. Both V(4)-O(3) bond lengths are 2.06 Å. Both V(4)-O(7) bond lengths are 2.06 Å. In the fifth V site, V(5) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-11°. Both V(5)-O(2) bond lengths are 2.06 Å. Both V(5)-O(4) bond lengths are 2.05 Å. Both V(5)-O(8) bond lengths are 2.08 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(4), one V(1), one V(2), and one V(4) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(2)Li2V3 square pyramid, corners with four equivalent O(1)Li2V3 square pyramids, and edges with four equivalent O(3)Li2TiV2 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(3), one V(1), one V(3), and one V(5) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(1)Li2V3 square pyramid, corners with four equivalent O(2)Li2V3 square pyramids, and edges with four equivalent O(4)Li2TiV2 square pyramids. In the third O site, O(3) is bonded to one Li(2), one Li(4), one Ti(1), one V(2), and one V(4) atom to form OLi2TiV2 square pyramids that share  a cornercorner with one O(4)Li2TiV2 square pyramid, corners with four equivalent O(3)Li2TiV2 square pyramids, and edges with four equivalent O(1)Li2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one Ti(1), one V(3), and one V(5) atom to form OLi2TiV2 square pyramids that share  a cornercorner with one O(3)Li2TiV2 square pyramid, corners with four equivalent O(4)Li2TiV2 square pyramids, and edges with four equivalent O(2)Li2V3 square pyramids. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(3), one Ti(1), one V(1), and one V(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(4), one Ti(1), one V(1), and one V(3) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), one V(1), and one V(4) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Ti(1), one V(1), and one V(5) atom.