LiV3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the third V site, V(3) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. In the fourth V site, V(4) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(3), one V(4), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with three equivalent O(1)Li2V4 octahedra, corners with three equivalent O(2)Li2V4 octahedra,  an edgeedge with one O(1)Li2V4 octahedra, edges with three equivalent O(2)Li2V4 octahedra, and edges with eight equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to two equivalent Li(1), one V(2), one V(3), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with three equivalent O(1)Li2V4 octahedra, corners with three equivalent O(2)Li2V4 octahedra,  an edgeedge with one O(2)Li2V4 octahedra, edges with three equivalent O(1)Li2V4 octahedra, and edges with eight equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(2), one V(4), and two equivalent V(3) atoms to form OLiV5 octahedra that share corners with six equivalent O(3)LiV5 octahedra, edges with four equivalent O(1)Li2V4 octahedra, edges with four equivalent O(2)Li2V4 octahedra, and edges with four equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
LiV3O4 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both Li(1)-O(1) bond lengths are 2.20 Å. Both Li(1)-O(2) bond lengths are 2.21 Å. Both Li(1)-O(3) bond lengths are 2.19 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with four equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both V(1)-O(1) bond lengths are 2.10 Å. Both V(1)-O(2) bond lengths are 2.09 Å. Both V(1)-O(3) bond lengths are 2.15 Å. In the second V site, V(2) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. Both V(2)-O(2) bond lengths are 2.17 Å. All V(2)-O(3) bond lengths are 2.18 Å. In the third V site, V(3) is bonded to one O(1), one O(2), and four equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent V(2)O6 octahedra, corners with three equivalent V(4)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-5°. The V(3)-O(1) bond length is 2.16 Å. The V(3)-O(2) bond length is 2.16 Å. There are two shorter (2.12 Å) and two longer (2.13 Å) V(3)-O(3) bond lengths. In the fourth V site, V(4) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent V(3)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-4°. Both V(4)-O(1) bond lengths are 2.19 Å. All V(4)-O(3) bond lengths are 2.18 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one V(3), one V(4), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with three equivalent O(1)Li2V4 octahedra, corners with three equivalent O(2)Li2V4 octahedra,  an edgeedge with one O(1)Li2V4 octahedra, edges with three equivalent O(2)Li2V4 octahedra, and edges with eight equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to two equivalent Li(1), one V(2), one V(3), and two equivalent V(1) atoms to form OLi2V4 octahedra that share corners with three equivalent O(1)Li2V4 octahedra, corners with three equivalent O(2)Li2V4 octahedra,  an edgeedge with one O(2)Li2V4 octahedra, edges with three equivalent O(1)Li2V4 octahedra, and edges with eight equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(2), one V(4), and two equivalent V(3) atoms to form OLiV5 octahedra that share corners with six equivalent O(3)LiV5 octahedra, edges with four equivalent O(1)Li2V4 octahedra, edges with four equivalent O(2)Li2V4 octahedra, and edges with four equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.