Li2V5O10 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(3), one O(4), and one O(7) atom to form distorted LiO5 square pyramids that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-34°. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(8), and one O(9) atom. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 20°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 15-22°. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(5), one O(7), one O(9), and two equivalent O(3) atoms. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(6), one O(8), and two equivalent O(4) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 15°. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 22°. In the sixth V site, V(6) is bonded to one O(1), one O(10), one O(2), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 20°. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(2), one V(4), one V(5), and one V(6) atom to form OLiV4 square pyramids that share  a cornercorner with one O(1)LiV4 square pyramid,  a cornercorner with one O(3)Li2V2 tetrahedra,  a cornercorner with one O(4)Li2V2 tetrahedra, corners with two equivalent O(5)V4 trigonal pyramids,  an edgeedge with one O(2)LiV4 square pyramid,  an edgeedge with one O(4)Li2V2 tetrahedra, and  an edgeedge with one O(5)V4 trigonal pyramid. In the second O site, O(2) is bonded to one Li(2), one V(1), one V(3), one V(5), and one V(6) atom to form distorted OLiV4 square pyramids that share  a cornercorner with one O(2)LiV4 square pyramid,  a cornercorner with one O(3)Li2V2 tetrahedra,  a cornercorner with one O(4)Li2V2 tetrahedra,  a cornercorner with one O(5)V4 trigonal pyramid,  an edgeedge with one O(1)LiV4 square pyramid,  an edgeedge with one O(3)Li2V2 tetrahedra, and  an edgeedge with one O(5)V4 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), and two equivalent V(3) atoms to form OLi2V2 tetrahedra that share  a cornercorner with one O(1)LiV4 square pyramid,  a cornercorner with one O(2)LiV4 square pyramid, corners with two equivalent O(5)V4 trigonal pyramids,  an edgeedge with one O(2)LiV4 square pyramid,  an edgeedge with one O(3)Li2V2 tetrahedra, and  an edgeedge with one O(4)Li2V2 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), and two equivalent V(4) atoms to form OLi2V2 tetrahedra that share  a cornercorner with one O(1)LiV4 square pyramid,  a cornercorner with one O(2)LiV4 square pyramid,  an edgeedge with one O(1)LiV4 square pyramid,  an edgeedge with one O(3)Li2V2 tetrahedra, and  an edgeedge with one O(4)Li2V2 tetrahedra. In the fifth O site, O(5) is bonded to one V(2), one V(3), one V(5), and one V(6) atom to form distorted OV4 trigonal pyramids that share  a cornercorner with one O(2)LiV4 square pyramid, corners with two equivalent O(1)LiV4 square pyramids, corners with two equivalent O(3)Li2V2 tetrahedra,  a cornercorner with one O(5)V4 trigonal pyramid,  an edgeedge with one O(1)LiV4 square pyramid, and  an edgeedge with one O(2)LiV4 square pyramid. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), one V(5), and one V(6) atom. In the seventh O site, O(7) is bonded in a see-saw-like geometry to one Li(1), one V(2), one V(3), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(1), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one V(5) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(4), and one V(6) atom.
Li2V5O10 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(3), one O(4), and one O(7) atom to form distorted LiO5 square pyramids that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and  an edgeedge with one V(6)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-34°. The Li(1)-O(1) bond length is 2.41 Å. The Li(1)-O(10) bond length is 2.07 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-O(4) bond length is 2.00 Å. The Li(1)-O(7) bond length is 2.10 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(8), and one O(9) atom. The Li(2)-O(2) bond length is 2.54 Å. The Li(2)-O(3) bond length is 1.96 Å. The Li(2)-O(4) bond length is 2.06 Å. The Li(2)-O(8) bond length is 2.17 Å. The Li(2)-O(9) bond length is 2.03 Å. There are six inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles are 20°. Both V(1)-O(2) bond lengths are 2.02 Å. Both V(1)-O(6) bond lengths are 2.04 Å. Both V(1)-O(8) bond lengths are 2.09 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(5), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent V(4)O6 octahedra, corners with two equivalent V(5)O6 octahedra, edges with two equivalent V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 15-22°. Both V(2)-O(1) bond lengths are 2.09 Å. Both V(2)-O(5) bond lengths are 2.02 Å. Both V(2)-O(7) bond lengths are 2.01 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(2), one O(5), one O(7), one O(9), and two equivalent O(3) atoms. The V(3)-O(2) bond length is 2.10 Å. The V(3)-O(5) bond length is 2.28 Å. The V(3)-O(7) bond length is 2.04 Å. The V(3)-O(9) bond length is 1.79 Å. There is one shorter (1.87 Å) and one longer (1.95 Å) V(3)-O(3) bond length. In the fourth V site, V(4) is bonded to one O(1), one O(10), one O(6), one O(8), and two equivalent O(4) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one V(5)O6 octahedra, edges with two equivalent V(6)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 15°. The V(4)-O(1) bond length is 2.06 Å. The V(4)-O(10) bond length is 1.79 Å. The V(4)-O(6) bond length is 2.15 Å. The V(4)-O(8) bond length is 2.18 Å. There is one shorter (1.87 Å) and one longer (1.93 Å) V(4)-O(4) bond length. In the fifth V site, V(5) is bonded to one O(1), one O(2), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, and edges with two equivalent V(6)O6 octahedra. The corner-sharing octahedral tilt angles are 22°. The V(5)-O(1) bond length is 2.18 Å. The V(5)-O(2) bond length is 2.09 Å. The V(5)-O(5) bond length is 2.02 Å. The V(5)-O(6) bond length is 2.09 Å. The V(5)-O(7) bond length is 1.95 Å. The V(5)-O(9) bond length is 1.98 Å. In the sixth V site, V(6) is bonded to one O(1), one O(10), one O(2), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with two equivalent V(5)O6 octahedra, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles are 20°. The V(6)-O(1) bond length is 2.04 Å. The V(6)-O(10) bond length is 1.97 Å. The V(6)-O(2) bond length is 2.13 Å. The V(6)-O(5) bond length is 1.97 Å. The V(6)-O(6) bond length is 1.99 Å. The V(6)-O(8) bond length is 1.82 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(2), one V(4), one V(5), and one V(6) atom to form OLiV4 square pyramids that share  a cornercorner with one O(1)LiV4 square pyramid,  a cornercorner with one O(3)Li2V2 tetrahedra,  a cornercorner with one O(4)Li2V2 tetrahedra, corners with two equivalent O(5)V4 trigonal pyramids,  an edgeedge with one O(2)LiV4 square pyramid,  an edgeedge with one O(4)Li2V2 tetrahedra, and  an edgeedge with one O(5)V4 trigonal pyramid. In the second O site, O(2) is bonded to one Li(2), one V(1), one V(3), one V(5), and one V(6) atom to form distorted OLiV4 square pyramids that share  a cornercorner with one O(2)LiV4 square pyramid,  a cornercorner with one O(3)Li2V2 tetrahedra,  a cornercorner with one O(4)Li2V2 tetrahedra,  a cornercorner with one O(5)V4 trigonal pyramid,  an edgeedge with one O(1)LiV4 square pyramid,  an edgeedge with one O(3)Li2V2 tetrahedra, and  an edgeedge with one O(5)V4 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), and two equivalent V(3) atoms to form OLi2V2 tetrahedra that share  a cornercorner with one O(1)LiV4 square pyramid,  a cornercorner with one O(2)LiV4 square pyramid, corners with two equivalent O(5)V4 trigonal pyramids,  an edgeedge with one O(2)LiV4 square pyramid,  an edgeedge with one O(3)Li2V2 tetrahedra, and  an edgeedge with one O(4)Li2V2 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), and two equivalent V(4) atoms to form OLi2V2 tetrahedra that share  a cornercorner with one O(1)LiV4 square pyramid,  a cornercorner with one O(2)LiV4 square pyramid,  an edgeedge with one O(1)LiV4 square pyramid,  an edgeedge with one O(3)Li2V2 tetrahedra, and  an edgeedge with one O(4)Li2V2 tetrahedra. In the fifth O site, O(5) is bonded to one V(2), one V(3), one V(5), and one V(6) atom to form distorted OV4 trigonal pyramids that share  a cornercorner with one O(2)LiV4 square pyramid, corners with two equivalent O(1)LiV4 square pyramids, corners with two equivalent O(3)Li2V2 tetrahedra,  a cornercorner with one O(5)V4 trigonal pyramid,  an edgeedge with one O(1)LiV4 square pyramid, and  an edgeedge with one O(2)LiV4 square pyramid. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one V(1), one V(4), one V(5), and one V(6) atom. In the seventh O site, O(7) is bonded in a see-saw-like geometry to one Li(1), one V(2), one V(3), and one V(5) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(1), one V(4), and one V(6) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one V(5) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(1), one V(4), and one V(6) atom.