Li2V6O13 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(6), and two equivalent O(7) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(5), one O(7), and three equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one V(2)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. In the second V site, V(2) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 23°. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), and three equivalent O(3) atoms. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(2) atoms. In the second O site, O(2) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(7)Li4V2 octahedra, corners with two equivalent O(2)LiV3 tetrahedra, edges with two equivalent O(7)Li4V2 octahedra, and edges with two equivalent O(2)LiV3 tetrahedra. The corner-sharing octahedral tilt angles are 30°. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(2) and three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(3) atom. In the seventh O site, O(7) is bonded to four equivalent Li(1) and two equivalent V(1) atoms to form distorted OLi4V2 octahedra that share corners with two equivalent O(2)LiV3 tetrahedra, edges with two equivalent O(7)Li4V2 octahedra, and edges with four equivalent O(2)LiV3 tetrahedra.
Li2V6O13 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(6), and two equivalent O(7) atoms. The Li(1)-O(2) bond length is 1.97 Å. Both Li(1)-O(6) bond lengths are 2.12 Å. Both Li(1)-O(7) bond lengths are 2.52 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(5), one O(7), and three equivalent O(2) atoms to form distorted VO5 trigonal bipyramids that share  a cornercorner with one V(2)O6 octahedra, corners with three equivalent V(1)O5 trigonal bipyramids, and edges with two equivalent V(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 9°. The V(1)-O(5) bond length is 1.71 Å. The V(1)-O(7) bond length is 1.96 Å. There are two shorter (1.98 Å) and one longer (2.05 Å) V(1)-O(2) bond length. In the second V site, V(2) is bonded to one O(3), one O(5), two equivalent O(1), and two equivalent O(4) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 23°. The V(2)-O(3) bond length is 2.05 Å. The V(2)-O(5) bond length is 2.04 Å. There is one shorter (1.88 Å) and one longer (1.97 Å) V(2)-O(1) bond length. Both V(2)-O(4) bond lengths are 1.89 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(4), one O(6), and three equivalent O(3) atoms. The V(3)-O(1) bond length is 1.95 Å. The V(3)-O(4) bond length is 2.05 Å. The V(3)-O(6) bond length is 1.68 Å. There are two shorter (1.94 Å) and one longer (2.51 Å) V(3)-O(3) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(3) and two equivalent V(2) atoms. In the second O site, O(2) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 tetrahedra that share  a cornercorner with one O(7)Li4V2 octahedra, corners with two equivalent O(2)LiV3 tetrahedra, edges with two equivalent O(7)Li4V2 octahedra, and edges with two equivalent O(2)LiV3 tetrahedra. The corner-sharing octahedral tilt angles are 30°. In the third O site, O(3) is bonded in a 4-coordinate geometry to one V(2) and three equivalent V(3) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(2) atoms. In the fifth O site, O(5) is bonded in a linear geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to two equivalent Li(1) and one V(3) atom. In the seventh O site, O(7) is bonded to four equivalent Li(1) and two equivalent V(1) atoms to form distorted OLi4V2 octahedra that share corners with two equivalent O(2)LiV3 tetrahedra, edges with two equivalent O(7)Li4V2 octahedra, and edges with four equivalent O(2)LiV3 tetrahedra.