LiTiV2O6 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) 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 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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-23°. Ti(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles are 23°. 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(1), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles are 23°. In the second V site, V(2) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-15°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(2) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(5)Li2TiV2 square pyramids, corners with three equivalent O(4)LiTi2V trigonal pyramids, edges with two equivalent O(5)Li2TiV2 square pyramids, and edges with two equivalent O(3)Li2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Ti(1), and one V(1) atom to form OLiTi2V trigonal pyramids that share corners with three equivalent O(3)Li2V3 square pyramids, corners with two equivalent O(4)LiTi2V trigonal pyramids, and edges with two equivalent O(5)Li2TiV2 square pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(1), one Ti(1), and two equivalent V(2) atoms to form OLi2TiV2 square pyramids that share corners with four equivalent O(3)Li2V3 square pyramids, edges with two equivalent O(5)Li2TiV2 square pyramids, edges with two equivalent O(3)Li2V3 square pyramids, and edges with two equivalent O(4)LiTi2V trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms.
LiTiV2O6 crystallizes in the triclinic P1 space group. Li(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) 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 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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-23°. The Li(1)-O(1) bond length is 2.18 Å. The Li(1)-O(4) bond length is 2.15 Å. There is one shorter (2.18 Å) and one longer (2.28 Å) Li(1)-O(3) bond length. There is one shorter (2.21 Å) and one longer (2.22 Å) Li(1)-O(5) bond length. Ti(1) is bonded to one O(1), one O(5), two equivalent O(2), and two equivalent O(4) atoms to form TiO6 octahedra that share  a cornercorner with one Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles are 23°. The Ti(1)-O(1) bond length is 1.94 Å. The Ti(1)-O(5) bond length is 2.02 Å. There is one shorter (1.90 Å) and one longer (1.93 Å) Ti(1)-O(2) bond length. There is one shorter (2.03 Å) and one longer (2.09 Å) Ti(1)-O(4) bond length. 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(1), and two equivalent O(6) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles are 23°. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 1.94 Å. There is one shorter (2.01 Å) and one longer (2.08 Å) V(1)-O(1) bond length. There is one shorter (1.81 Å) and one longer (2.04 Å) V(1)-O(6) bond length. In the second V site, V(2) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with four equivalent Li(1)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(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 13-15°. The V(2)-O(2) bond length is 2.10 Å. The V(2)-O(6) bond length is 2.11 Å. There is one shorter (2.02 Å) and one longer (2.04 Å) V(2)-O(3) bond length. There is one shorter (2.04 Å) and one longer (2.05 Å) V(2)-O(5) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Ti(1), and two equivalent V(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Ti(1) and one V(2) atom. In the third O site, O(3) is bonded to two equivalent Li(1), one V(1), and two equivalent V(2) atoms to form OLi2V3 square pyramids that share corners with four equivalent O(5)Li2TiV2 square pyramids, corners with three equivalent O(4)LiTi2V trigonal pyramids, edges with two equivalent O(5)Li2TiV2 square pyramids, and edges with two equivalent O(3)Li2V3 square pyramids. In the fourth O site, O(4) is bonded to one Li(1), two equivalent Ti(1), and one V(1) atom to form OLiTi2V trigonal pyramids that share corners with three equivalent O(3)Li2V3 square pyramids, corners with two equivalent O(4)LiTi2V trigonal pyramids, and edges with two equivalent O(5)Li2TiV2 square pyramids. In the fifth O site, O(5) is bonded to two equivalent Li(1), one Ti(1), and two equivalent V(2) atoms to form OLi2TiV2 square pyramids that share corners with four equivalent O(3)Li2V3 square pyramids, edges with two equivalent O(5)Li2TiV2 square pyramids, edges with two equivalent O(3)Li2V3 square pyramids, and edges with two equivalent O(4)LiTi2V trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one V(2) and two equivalent V(1) atoms.