LiV4O10 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(5), one O(7), and one O(8) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), and one O(9) atom to form corner-sharing VO4 tetrahedra. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), and one O(6) atom to form corner-sharing VO4 tetrahedra. In the third V site, V(3) is bonded to one O(1), one O(10), one O(3), one O(4), and one O(7) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one V(4)O5 trigonal bipyramid. In the fourth V site, V(4) is bonded to one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one V(3)O5 trigonal bipyramid. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Li(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom.
LiV4O10 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(5), one O(7), and one O(8) atom. The Li(1)-O(2) bond length is 2.61 Å. The Li(1)-O(5) bond length is 1.97 Å. The Li(1)-O(7) bond length is 1.95 Å. The Li(1)-O(8) bond length is 1.98 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(5), and one O(9) atom to form corner-sharing VO4 tetrahedra. The V(1)-O(1) bond length is 1.80 Å. The V(1)-O(3) bond length is 1.86 Å. The V(1)-O(5) bond length is 1.65 Å. The V(1)-O(9) bond length is 1.71 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), and one O(6) atom to form corner-sharing VO4 tetrahedra. The V(2)-O(10) bond length is 1.80 Å. The V(2)-O(2) bond length is 1.76 Å. The V(2)-O(4) bond length is 1.87 Å. The V(2)-O(6) bond length is 1.62 Å. In the third V site, V(3) is bonded to one O(1), one O(10), one O(3), one O(4), and one O(7) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one V(4)O5 trigonal bipyramid. The V(3)-O(1) bond length is 1.82 Å. The V(3)-O(10) bond length is 1.81 Å. The V(3)-O(3) bond length is 1.96 Å. The V(3)-O(4) bond length is 2.03 Å. The V(3)-O(7) bond length is 1.63 Å. In the fourth V site, V(4) is bonded to one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent V(2)O4 tetrahedra, and  an edgeedge with one V(3)O5 trigonal bipyramid. The V(4)-O(2) bond length is 1.98 Å. The V(4)-O(3) bond length is 2.04 Å. The V(4)-O(4) bond length is 1.99 Å. The V(4)-O(8) bond length is 1.65 Å. The V(4)-O(9) bond length is 1.96 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one V(3) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one V(1), one V(3), and one V(4) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one V(2), one V(3), and one V(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Li(1) and one V(1) atom. In the sixth O site, O(6) is bonded in a single-bond geometry to one V(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Li(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(4) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom.