Li2TiV2O6 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), two equivalent O(5), and three equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(6), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. Ti(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, edges with two equivalent Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(2), and three equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-16°. In the second V site, V(2) is bonded to one O(4), two equivalent O(1), and three equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-17°. There are six inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), one Ti(1), and two equivalent V(2) atoms to form OLi3TiV2 octahedra that share  a cornercorner with one O(2)Li3TiV2 octahedra, corners with four equivalent O(6)Li2V3 square pyramids, edges with four equivalent O(1)Li3TiV2 octahedra, edges with four equivalent O(6)Li2V3 square pyramids, and edges with two equivalent O(4)LiTi2V trigonal pyramids. The corner-sharing octahedral tilt angles are 1°. In the second O site, O(2) is bonded to three equivalent Li(1), one Ti(1), and two equivalent V(1) atoms to form OLi3TiV2 octahedra that share  a cornercorner with one O(1)Li3TiV2 octahedra, corners with four equivalent O(5)Li2V3 square pyramids,  a cornercorner with one O(4)LiTi2V trigonal pyramid, edges with four equivalent O(2)Li3TiV2 octahedra, edges with four equivalent O(5)Li2V3 square pyramids, and edges with two equivalent O(4)LiTi2V trigonal pyramids. The corner-sharing octahedral tilt angles are 1°. In the third O site, O(3) is bonded in a see-saw-like geometry to one Li(2), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Ti(1), and one V(2) atom to form OLiTi2V trigonal pyramids that share  a cornercorner with one O(2)Li3TiV2 octahedra, corners with two equivalent O(5)Li2V3 square pyramids, corners with three equivalent O(6)Li2V3 square pyramids, corners with two equivalent O(4)LiTi2V trigonal pyramids, edges with two equivalent O(1)Li3TiV2 octahedra, and edges with two equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles are 8°. In the fifth O site, O(5) is bonded to two equivalent Li(1) and three equivalent V(1) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(2)Li3TiV2 octahedra, corners with two equivalent O(4)LiTi2V trigonal pyramids, edges with four equivalent O(2)Li3TiV2 octahedra, and edges with four equivalent O(5)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 4-7°. In the sixth O site, O(6) is bonded to two equivalent Li(2) and three equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(1)Li3TiV2 octahedra, corners with three equivalent O(4)LiTi2V trigonal pyramids, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(6)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 5-6°.
Li2TiV2O6 crystallizes in the monoclinic P2_1/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), two equivalent O(5), and three equivalent O(2) atoms to form LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-17°. The Li(1)-O(4) bond length is 2.08 Å. Both Li(1)-O(5) bond lengths are 2.13 Å. There are two shorter (2.29 Å) and one longer (2.41 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded to one O(3), two equivalent O(6), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-16°. The Li(2)-O(3) bond length is 2.07 Å. Both Li(2)-O(6) bond lengths are 2.11 Å. There are two shorter (2.27 Å) and one longer (2.32 Å) Li(2)-O(1) bond length. Ti(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra, edges with two equivalent Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-5°. The Ti(1)-O(1) bond length is 1.97 Å. The Ti(1)-O(2) bond length is 2.02 Å. Both Ti(1)-O(3) bond lengths are 1.96 Å. Both Ti(1)-O(4) bond lengths are 1.99 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), two equivalent O(2), and three equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-16°. The V(1)-O(3) bond length is 2.11 Å. Both V(1)-O(2) bond lengths are 2.07 Å. There are two shorter (2.02 Å) and one longer (2.08 Å) V(1)-O(5) bond length. In the second V site, V(2) is bonded to one O(4), two equivalent O(1), and three equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-17°. The V(2)-O(4) bond length is 2.06 Å. Both V(2)-O(1) bond lengths are 2.10 Å. There are two shorter (2.03 Å) and one longer (2.05 Å) V(2)-O(6) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), one Ti(1), and two equivalent V(2) atoms to form OLi3TiV2 octahedra that share  a cornercorner with one O(2)Li3TiV2 octahedra, corners with four equivalent O(6)Li2V3 square pyramids, edges with four equivalent O(1)Li3TiV2 octahedra, edges with four equivalent O(6)Li2V3 square pyramids, and edges with two equivalent O(4)LiTi2V trigonal pyramids. The corner-sharing octahedral tilt angles are 1°. In the second O site, O(2) is bonded to three equivalent Li(1), one Ti(1), and two equivalent V(1) atoms to form OLi3TiV2 octahedra that share  a cornercorner with one O(1)Li3TiV2 octahedra, corners with four equivalent O(5)Li2V3 square pyramids,  a cornercorner with one O(4)LiTi2V trigonal pyramid, edges with four equivalent O(2)Li3TiV2 octahedra, edges with four equivalent O(5)Li2V3 square pyramids, and edges with two equivalent O(4)LiTi2V trigonal pyramids. The corner-sharing octahedral tilt angles are 1°. In the third O site, O(3) is bonded in a see-saw-like geometry to one Li(2), two equivalent Ti(1), and one V(1) atom. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Ti(1), and one V(2) atom to form OLiTi2V trigonal pyramids that share  a cornercorner with one O(2)Li3TiV2 octahedra, corners with two equivalent O(5)Li2V3 square pyramids, corners with three equivalent O(6)Li2V3 square pyramids, corners with two equivalent O(4)LiTi2V trigonal pyramids, edges with two equivalent O(1)Li3TiV2 octahedra, and edges with two equivalent O(2)Li3TiV2 octahedra. The corner-sharing octahedral tilt angles are 8°. In the fifth O site, O(5) is bonded to two equivalent Li(1) and three equivalent V(1) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(2)Li3TiV2 octahedra, corners with two equivalent O(4)LiTi2V trigonal pyramids, edges with four equivalent O(2)Li3TiV2 octahedra, and edges with four equivalent O(5)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 4-7°. In the sixth O site, O(6) is bonded to two equivalent Li(2) and three equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(1)Li3TiV2 octahedra, corners with three equivalent O(4)LiTi2V trigonal pyramids, edges with four equivalent O(1)Li3TiV2 octahedra, and edges with four equivalent O(6)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 5-6°.