Li3V2MnO6 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(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 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 4-9°. In the second Li site, Li(2) 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 Mn(1)O6 octahedra, corners with five equivalent V(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 3-6°. 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(1)O6 octahedra, corners with five equivalent Li(2)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 3-6°. Mn(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four 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 5-9°. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent V(1), and one Mn(1) atom to form OLi3MnV2 octahedra that share  a cornercorner with one O(3)Li3Mn2V octahedra,  a cornercorner with one O(1)Li3MnV2 octahedra, corners with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(1)Li3MnV2 octahedra, and edges with four equivalent O(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(3)Li3Mn2V octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with four equivalent O(1)Li3MnV2 octahedra, edges with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(1)Li3MnV2 octahedra, and edges with four equivalent O(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) 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  a cornercorner with one O(1)Li3MnV2 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(1)Li3MnV2 octahedra, and edges with four equivalent O(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li3V2MnO6 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(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 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 4-9°. Both Li(1)-O(2) bond lengths are 2.24 Å. All Li(1)-O(3) bond lengths are 2.18 Å. In the second Li site, Li(2) 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 Mn(1)O6 octahedra, corners with five equivalent V(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 3-6°. The Li(2)-O(3) bond length is 2.39 Å. Both Li(2)-O(2) bond lengths are 2.17 Å. There is one shorter (2.11 Å) and two longer (2.12 Å) Li(2)-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(1)O6 octahedra, corners with five equivalent Li(2)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 3-6°. The V(1)-O(3) bond length is 2.11 Å. Both V(1)-O(1) bond lengths are 2.02 Å. There are two shorter (2.04 Å) and one longer (2.11 Å) V(1)-O(2) bond length. Mn(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four 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 5-9°. Both Mn(1)-O(1) bond lengths are 2.22 Å. All Mn(1)-O(3) bond lengths are 2.00 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to three equivalent Li(2), two equivalent V(1), and one Mn(1) atom to form OLi3MnV2 octahedra that share  a cornercorner with one O(3)Li3Mn2V octahedra,  a cornercorner with one O(1)Li3MnV2 octahedra, corners with four equivalent O(2)Li3V3 octahedra, edges with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(1)Li3MnV2 octahedra, and edges with four equivalent O(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the second O site, O(2) is bonded to one Li(1), two equivalent Li(2), and three equivalent V(1) atoms to form OLi3V3 octahedra that share  a cornercorner with one O(3)Li3Mn2V octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with four equivalent O(1)Li3MnV2 octahedra, edges with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(1)Li3MnV2 octahedra, and edges with four equivalent O(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) 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  a cornercorner with one O(1)Li3MnV2 octahedra,  a cornercorner with one O(2)Li3V3 octahedra, corners with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(3)Li3Mn2V octahedra, edges with four equivalent O(1)Li3MnV2 octahedra, and edges with four equivalent O(2)Li3V3 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.