Li2VMnO4 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second Li site, Li(2) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(2)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 4-8°. 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. There are two inequivalent Mn sites. In the first Mn site, 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(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)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 4-8°. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)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 4-8°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one V(1), one Mn(1), and one Mn(2) atom to form OLi3Mn2V octahedra that share corners with six equivalent O(1)Li3Mn2V octahedra, edges with four equivalent O(1)Li3Mn2V octahedra, edges with four equivalent O(2)Li3MnV2 octahedra, and edges with four equivalent O(3)Li3MnV2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent V(1), and one Mn(1) atom to form OLi3MnV2 octahedra that share corners with three equivalent O(2)Li3MnV2 octahedra, corners with three equivalent O(3)Li3MnV2 octahedra,  an edgeedge with one O(2)Li3MnV2 octahedra, edges with three equivalent O(3)Li3MnV2 octahedra, and edges with eight equivalent O(1)Li3Mn2V octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent V(1), and one Mn(2) atom to form OLi3MnV2 octahedra that share corners with three equivalent O(2)Li3MnV2 octahedra, corners with three equivalent O(3)Li3MnV2 octahedra,  an edgeedge with one O(3)Li3MnV2 octahedra, edges with three equivalent O(2)Li3MnV2 octahedra, and edges with eight equivalent O(1)Li3Mn2V octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li2VMnO4 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. Both Li(1)-O(1) bond lengths are 2.33 Å. Both Li(1)-O(2) bond lengths are 2.12 Å. Both Li(1)-O(3) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), and four equivalent O(1) atoms to form LiO6 octahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Li(2)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 4-8°. The Li(2)-O(2) bond length is 2.17 Å. The Li(2)-O(3) bond length is 2.19 Å. There are two shorter (2.17 Å) and two longer (2.18 Å) Li(2)-O(1) bond lengths. 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 Mn(1)O6 octahedra, edges with two equivalent Mn(2)O6 octahedra, and edges with four equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. Both V(1)-O(1) bond lengths are 2.12 Å. Both V(1)-O(2) bond lengths are 2.03 Å. Both V(1)-O(3) bond lengths are 2.02 Å. There are two inequivalent Mn sites. In the first Mn site, 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(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(2)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 4-8°. Both Mn(1)-O(2) bond lengths are 2.27 Å. All Mn(1)-O(1) bond lengths are 1.98 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form MnO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mn(1)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 4-8°. Both Mn(2)-O(3) bond lengths are 2.25 Å. All Mn(2)-O(1) bond lengths are 1.98 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(2), one V(1), one Mn(1), and one Mn(2) atom to form OLi3Mn2V octahedra that share corners with six equivalent O(1)Li3Mn2V octahedra, edges with four equivalent O(1)Li3Mn2V octahedra, edges with four equivalent O(2)Li3MnV2 octahedra, and edges with four equivalent O(3)Li3MnV2 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), two equivalent V(1), and one Mn(1) atom to form OLi3MnV2 octahedra that share corners with three equivalent O(2)Li3MnV2 octahedra, corners with three equivalent O(3)Li3MnV2 octahedra,  an edgeedge with one O(2)Li3MnV2 octahedra, edges with three equivalent O(3)Li3MnV2 octahedra, and edges with eight equivalent O(1)Li3Mn2V octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent V(1), and one Mn(2) atom to form OLi3MnV2 octahedra that share corners with three equivalent O(2)Li3MnV2 octahedra, corners with three equivalent O(3)Li3MnV2 octahedra,  an edgeedge with one O(3)Li3MnV2 octahedra, edges with three equivalent O(2)Li3MnV2 octahedra, and edges with eight equivalent O(1)Li3Mn2V octahedra. The corner-sharing octahedral tilt angles range from 0-1°.