Li3V5O10 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and two equivalent V(2) atoms to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one V(3), and two equivalent V(1) atoms to form a mixture of edge and corner-sharing OLi2V3 square pyramids.
Li3V5O10 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. Both Li(1)-O(2) bond lengths are 2.19 Å. Both Li(1)-O(3) bond lengths are 2.16 Å. Both Li(1)-O(5) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-11°. Both Li(2)-O(1) bond lengths are 2.23 Å. Both Li(2)-O(2) bond lengths are 2.21 Å. Both Li(2)-O(4) bond lengths are 2.14 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Both Li(3)-O(1) bond lengths are 2.16 Å. Both Li(3)-O(4) bond lengths are 2.20 Å. Both Li(3)-O(5) bond lengths are 2.18 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-13°. The V(1)-O(1) bond length is 2.06 Å. The V(1)-O(2) bond length is 2.06 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(4) bond length is 2.03 Å. There is one shorter (2.04 Å) and one longer (2.11 Å) V(1)-O(5) bond length. In the second V site, V(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. The V(2)-O(1) bond length is 2.02 Å. The V(2)-O(3) bond length is 1.99 Å. There is one shorter (2.00 Å) and one longer (2.05 Å) V(2)-O(2) bond length. There is one shorter (1.98 Å) and one longer (2.05 Å) V(2)-O(4) bond length. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 10°. Both V(3)-O(1) bond lengths are 2.04 Å. Both V(3)-O(3) bond lengths are 2.01 Å. Both V(3)-O(5) bond lengths are 1.90 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(3) atom to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(1), and two equivalent V(2) atoms to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one V(3) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one V(1), and two equivalent V(2) atoms to form a mixture of edge and corner-sharing OLi2V3 square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(3), one V(3), and two equivalent V(1) atoms to form a mixture of edge and corner-sharing OLi2V3 square pyramids.