Li2VCO5 crystallizes in the orthorhombic Pbam space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-65°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. V(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-61°. C(1) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(5) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), and two equivalent V(1) atoms to form OLi2V2 tetrahedra that share corners with three equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, and  an edgeedge with one O(2)Li3V2 square pyramid. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(3), and two equivalent V(1) atoms to form OLi3V2 square pyramids that share corners with two equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, edges with three equivalent O(2)Li3V2 square pyramids, and  an edgeedge with one O(1)Li2V2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Li(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one C(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one C(1) atom.
Li2VCO5 crystallizes in the orthorhombic Pbam space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-65°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(2) bond length is 2.09 Å. Both Li(1)-O(3) bond lengths are 2.13 Å. Both Li(1)-O(4) bond lengths are 2.22 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. Both Li(2)-O(1) bond lengths are 2.04 Å. All Li(2)-O(5) bond lengths are 2.16 Å. In the third Li site, Li(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with four equivalent V(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles are 15°. Both Li(3)-O(3) bond lengths are 2.08 Å. All Li(3)-O(2) bond lengths are 2.12 Å. V(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(3)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-61°. The V(1)-O(4) bond length is 2.07 Å. The V(1)-O(5) bond length is 2.08 Å. Both V(1)-O(1) bond lengths are 1.92 Å. Both V(1)-O(2) bond lengths are 1.95 Å. C(1) is bonded in a trigonal planar geometry to one O(3), one O(4), and one O(5) atom. The C(1)-O(3) bond length is 1.27 Å. The C(1)-O(4) bond length is 1.31 Å. The C(1)-O(5) bond length is 1.32 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), and two equivalent V(1) atoms to form OLi2V2 tetrahedra that share corners with three equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, and  an edgeedge with one O(2)Li3V2 square pyramid. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(3), and two equivalent V(1) atoms to form OLi3V2 square pyramids that share corners with two equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(1)Li2V2 tetrahedra, edges with three equivalent O(2)Li3V2 square pyramids, and  an edgeedge with one O(1)Li2V2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Li(1), and one C(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one C(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one V(1), and one C(1) atom.