Li2VO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) 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 two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. In the third Li site, Li(3) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with five equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), three equivalent Li(3), and two equivalent V(1) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(1)Li4V2 octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with four equivalent O(1)Li4V2 octahedra, edges with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form OLi5V octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(1)Li4V2 octahedra, corners with four equivalent O(3)Li5V octahedra, edges with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-7°.
Li2VO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-9°. Both Li(1)-O(1) bond lengths are 2.06 Å. All Li(1)-O(3) bond lengths are 2.12 Å. In the second Li site, Li(2) is bonded to two equivalent O(2) and four equivalent O(3) 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 two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. Both Li(2)-O(2) bond lengths are 2.14 Å. All Li(2)-O(3) bond lengths are 2.09 Å. In the third Li site, Li(3) is bonded to one O(3), two equivalent O(2), and three equivalent O(1) atoms to form LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with five equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. The Li(3)-O(3) bond length is 2.15 Å. Both Li(3)-O(2) bond lengths are 2.23 Å. There is one shorter (2.07 Å) and two longer (2.17 Å) Li(3)-O(1) bond lengths. V(1) is bonded to one O(3), two equivalent O(1), and three equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with five equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. The V(1)-O(3) bond length is 1.76 Å. Both V(1)-O(1) bond lengths are 1.99 Å. There are two shorter (2.05 Å) and one longer (2.07 Å) V(1)-O(2) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), three equivalent Li(3), and two equivalent V(1) atoms to form OLi4V2 octahedra that share  a cornercorner with one O(1)Li4V2 octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(3), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(3)Li5V octahedra, corners with four equivalent O(1)Li4V2 octahedra, edges with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one V(1) atom to form OLi5V octahedra that share  a cornercorner with one O(2)Li3V3 octahedra,  a cornercorner with one O(1)Li4V2 octahedra, corners with four equivalent O(3)Li5V octahedra, edges with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(1)Li4V2 octahedra, and edges with four equivalent O(3)Li5V octahedra. The corner-sharing octahedral tilt angles range from 0-7°.