LiTi2VO6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Ti(2)O4 tetrahedra, corners with four equivalent Ti(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  an edgeedge with one Ti(2)O4 tetrahedra. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form TiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and corners with two equivalent Ti(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-72°. In the second Ti site, Ti(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form TiO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with two equivalent Ti(2)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-63°. V(1) 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 three equivalent Ti(1)O4 tetrahedra, corners with three equivalent Ti(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Ti(1), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Ti(1), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OLiTiV2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to one Li(1), one Ti(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OLiTiV2 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(2), and one V(1) atom.
LiTi2VO6 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share corners with two equivalent Ti(2)O4 tetrahedra, corners with four equivalent Ti(1)O4 tetrahedra, edges with three equivalent V(1)O6 octahedra, and  an edgeedge with one Ti(2)O4 tetrahedra. The Li(1)-O(1) bond length is 2.46 Å. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(3) bond length is 2.11 Å. The Li(1)-O(4) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.13 Å. The Li(1)-O(6) bond length is 2.54 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form TiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, and corners with two equivalent Ti(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-72°. The Ti(1)-O(2) bond length is 1.78 Å. The Ti(1)-O(3) bond length is 1.86 Å. There is one shorter (1.84 Å) and one longer (1.85 Å) Ti(1)-O(1) bond length. In the second Ti site, Ti(2) is bonded to one O(5), one O(6), and two equivalent O(4) atoms to form TiO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent V(1)O6 octahedra, corners with two equivalent Ti(2)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-63°. The Ti(2)-O(5) bond length is 1.86 Å. The Ti(2)-O(6) bond length is 1.77 Å. There is one shorter (1.84 Å) and one longer (1.86 Å) Ti(2)-O(4) bond length. V(1) 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 three equivalent Ti(1)O4 tetrahedra, corners with three equivalent Ti(2)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The V(1)-O(2) bond length is 2.00 Å. The V(1)-O(6) bond length is 1.96 Å. There is one shorter (2.09 Å) and one longer (2.16 Å) V(1)-O(3) bond length. There is one shorter (2.07 Å) and one longer (2.11 Å) V(1)-O(5) bond length. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Ti(1), and one V(1) atom. In the third O site, O(3) is bonded to one Li(1), one Ti(1), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OLiTiV2 tetrahedra. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Ti(2) atoms. In the fifth O site, O(5) is bonded to one Li(1), one Ti(2), and two equivalent V(1) atoms to form a mixture of distorted corner and edge-sharing OLiTiV2 trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(2), and one V(1) atom.