LiV3O4 is Caswellsilverite-like structured and crystallizes in the tetragonal I4mm space group. Li(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with eight equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with eight equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second V site, V(2) 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 V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent V(1), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with six equivalent O(1)Li2V4 octahedra, edges with four equivalent O(1)Li2V4 octahedra, edges with four equivalent O(2)LiV5 octahedra, and edges with four equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(1), one V(1), and four equivalent V(2) atoms to form OLiV5 octahedra that share corners with two equivalent O(3)LiV5 octahedra, corners with four equivalent O(2)LiV5 octahedra, edges with four equivalent O(3)LiV5 octahedra, and edges with eight equivalent O(1)Li2V4 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), and four equivalent V(2) atoms to form OLiV5 octahedra that share corners with two equivalent O(2)LiV5 octahedra, corners with four equivalent O(3)LiV5 octahedra, edges with four equivalent O(2)LiV5 octahedra, and edges with eight equivalent O(1)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
LiV3O4 is Caswellsilverite-like structured and crystallizes in the tetragonal I4mm space group. Li(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with eight equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. The Li(1)-O(2) bond length is 2.16 Å. The Li(1)-O(3) bond length is 2.33 Å. All Li(1)-O(1) bond lengths are 2.14 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with eight equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. The V(1)-O(2) bond length is 2.12 Å. The V(1)-O(3) bond length is 2.14 Å. All V(1)-O(1) bond lengths are 2.14 Å. In the second V site, V(2) 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 V(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There is one shorter (2.18 Å) and one longer (2.19 Å) V(2)-O(1) bond length. Both V(2)-O(2) bond lengths are 2.14 Å. Both V(2)-O(3) bond lengths are 2.14 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent V(1), and two equivalent V(2) atoms to form OLi2V4 octahedra that share corners with six equivalent O(1)Li2V4 octahedra, edges with four equivalent O(1)Li2V4 octahedra, edges with four equivalent O(2)LiV5 octahedra, and edges with four equivalent O(3)LiV5 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(1), one V(1), and four equivalent V(2) atoms to form OLiV5 octahedra that share corners with two equivalent O(3)LiV5 octahedra, corners with four equivalent O(2)LiV5 octahedra, edges with four equivalent O(3)LiV5 octahedra, and edges with eight equivalent O(1)Li2V4 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), and four equivalent V(2) atoms to form OLiV5 octahedra that share corners with two equivalent O(2)LiV5 octahedra, corners with four equivalent O(3)LiV5 octahedra, edges with four equivalent O(2)LiV5 octahedra, and edges with eight equivalent O(1)Li2V4 octahedra. The corner-sharing octahedral tilt angles range from 0-7°.