Li3V6O13 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded to one O(5), two equivalent O(1), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing LiO5 square pyramids. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), and three equivalent O(5) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(1), and two equivalent O(4) atoms. In the third V site, V(3) is bonded to one O(2), one O(6), one O(7), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one V(1), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  a cornercorner with one O(5)LiV4 trigonal bipyramid, corners with two equivalent O(1)Li2V3 trigonal bipyramids,  an edgeedge with one O(1)Li2V3 trigonal bipyramid, edges with three equivalent O(5)LiV4 trigonal bipyramids, and edges with four equivalent O(4)Li2V3 trigonal bipyramids. In the second O site, O(2) is bonded in a linear geometry to one V(1) and one V(3) atom. In the third O site, O(3) is bonded in a square co-planar geometry to one Li(1) and three equivalent V(3) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(5)LiV4 trigonal bipyramid, corners with two equivalent O(4)Li2V3 trigonal bipyramids,  an edgeedge with one O(4)Li2V3 trigonal bipyramid, edges with three equivalent O(5)LiV4 trigonal bipyramids, and edges with four equivalent O(1)Li2V3 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(2), one V(2), and three equivalent V(1) atoms to form distorted OLiV4 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, corners with two equivalent O(5)LiV4 trigonal bipyramids, edges with two equivalent O(5)LiV4 trigonal bipyramids, edges with three equivalent O(1)Li2V3 trigonal bipyramids, and edges with three equivalent O(4)Li2V3 trigonal bipyramids. In the sixth O site, O(6) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent V(3) atoms. In the seventh O site, O(7) is bonded in a linear geometry to one V(2) and one V(3) atom.
Li3V6O13 crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(6) atoms. Both Li(1)-O(3) bond lengths are 2.05 Å. Both Li(1)-O(6) bond lengths are 1.97 Å. In the second Li site, Li(2) is bonded to one O(5), two equivalent O(1), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing LiO5 square pyramids. The Li(2)-O(5) bond length is 2.04 Å. Both Li(2)-O(1) bond lengths are 1.97 Å. There is one shorter (2.01 Å) and one longer (2.07 Å) Li(2)-O(4) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(4), and three equivalent O(5) atoms. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(2) bond length is 1.67 Å. The V(1)-O(4) bond length is 1.99 Å. There are two shorter (2.02 Å) and one longer (2.40 Å) V(1)-O(5) bond length. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(5), one O(7), two equivalent O(1), and two equivalent O(4) atoms. The V(2)-O(5) bond length is 2.02 Å. The V(2)-O(7) bond length is 1.69 Å. There is one shorter (1.94 Å) and one longer (2.31 Å) V(2)-O(1) bond length. Both V(2)-O(4) bond lengths are 2.00 Å. In the third V site, V(3) is bonded to one O(2), one O(6), one O(7), and three equivalent O(3) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. The V(3)-O(2) bond length is 1.99 Å. The V(3)-O(6) bond length is 1.86 Å. The V(3)-O(7) bond length is 1.94 Å. There are two shorter (1.98 Å) and one longer (2.00 Å) V(3)-O(3) bond length. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(2), one V(1), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(4)Li2V3 trigonal bipyramid,  a cornercorner with one O(5)LiV4 trigonal bipyramid, corners with two equivalent O(1)Li2V3 trigonal bipyramids,  an edgeedge with one O(1)Li2V3 trigonal bipyramid, edges with three equivalent O(5)LiV4 trigonal bipyramids, and edges with four equivalent O(4)Li2V3 trigonal bipyramids. In the second O site, O(2) is bonded in a linear geometry to one V(1) and one V(3) atom. In the third O site, O(3) is bonded in a square co-planar geometry to one Li(1) and three equivalent V(3) atoms. In the fourth O site, O(4) is bonded to two equivalent Li(2), one V(1), and two equivalent V(2) atoms to form OLi2V3 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(5)LiV4 trigonal bipyramid, corners with two equivalent O(4)Li2V3 trigonal bipyramids,  an edgeedge with one O(4)Li2V3 trigonal bipyramid, edges with three equivalent O(5)LiV4 trigonal bipyramids, and edges with four equivalent O(1)Li2V3 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Li(2), one V(2), and three equivalent V(1) atoms to form distorted OLiV4 trigonal bipyramids that share  a cornercorner with one O(1)Li2V3 trigonal bipyramid,  a cornercorner with one O(4)Li2V3 trigonal bipyramid, corners with two equivalent O(5)LiV4 trigonal bipyramids, edges with two equivalent O(5)LiV4 trigonal bipyramids, edges with three equivalent O(1)Li2V3 trigonal bipyramids, and edges with three equivalent O(4)Li2V3 trigonal bipyramids. In the sixth O site, O(6) is bonded in a square co-planar geometry to two equivalent Li(1) and two equivalent V(3) atoms. In the seventh O site, O(7) is bonded in a linear geometry to one V(2) and one V(3) atom.