Li2VMnO4 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent Mn(1) atoms to form OLi3Mn2V octahedra that share corners with six equivalent O(1)Li3Mn2V octahedra, edges with four equivalent O(1)Li3Mn2V octahedra, and edges with eight equivalent O(2)Li3MnV2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent V(1), and one Mn(1) atom to form OLi3MnV2 octahedra that share corners with six equivalent O(2)Li3MnV2 octahedra, edges with four equivalent O(2)Li3MnV2 octahedra, and edges with eight equivalent O(1)Li3Mn2V octahedra. The corner-sharing octahedra are not tilted.
Li2VMnO4 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Mn(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Li(1)-O(2) bond lengths are 2.17 Å. There are two shorter (2.17 Å) and two longer (2.18 Å) Li(1)-O(1) bond lengths. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Li(2)-O(1) bond lengths are 2.13 Å. There are two shorter (2.11 Å) and two longer (2.32 Å) Li(2)-O(2) bond lengths. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both V(1)-O(1) bond lengths are 2.03 Å. There are two shorter (2.03 Å) and two longer (2.14 Å) V(1)-O(2) bond lengths. Mn(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra, edges with four equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-6°. Both Mn(1)-O(2) bond lengths are 1.99 Å. There are two shorter (1.96 Å) and two longer (2.28 Å) Mn(1)-O(1) bond lengths. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one V(1), and two equivalent Mn(1) atoms to form OLi3Mn2V octahedra that share corners with six equivalent O(1)Li3Mn2V octahedra, edges with four equivalent O(1)Li3Mn2V octahedra, and edges with eight equivalent O(2)Li3MnV2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), two equivalent V(1), and one Mn(1) atom to form OLi3MnV2 octahedra that share corners with six equivalent O(2)Li3MnV2 octahedra, edges with four equivalent O(2)Li3MnV2 octahedra, and edges with eight equivalent O(1)Li3Mn2V octahedra. The corner-sharing octahedra are not tilted.