LiV4O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 9-23°. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 9-31°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to one V(1) and three equivalent V(2) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms.
LiV4O8 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Li(1)-O(1) bond lengths are 1.87 Å. Both Li(1)-O(3) bond lengths are 2.10 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form a mixture of corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 9-23°. The V(1)-O(1) bond length is 2.05 Å. The V(1)-O(2) bond length is 2.07 Å. There is one shorter (1.94 Å) and one longer (2.03 Å) V(1)-O(3) bond length. Both V(1)-O(4) bond lengths are 1.95 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 9-31°. The V(2)-O(1) bond length is 1.72 Å. The V(2)-O(3) bond length is 2.09 Å. The V(2)-O(4) bond length is 1.99 Å. There are two shorter (1.98 Å) and one longer (2.14 Å) V(2)-O(2) bond length. There are four inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the second O site, O(2) is bonded to one V(1) and three equivalent V(2) atoms to form a mixture of corner and edge-sharing OV4 trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a T-shaped geometry to one V(2) and two equivalent V(1) atoms.