Li4V3MnO12 is Ilmenite-derived structured and crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form distorted LiO6 pentagonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted LiO6 pentagonal pyramids that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Li(3)O6 pentagonal pyramids, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 43°. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(3)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 43°. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Li(3)O6 pentagonal pyramids, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Li(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 43°. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Li(3)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 43°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(1), and one Mn(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(2), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing OLi2MnV trigonal pyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(1), and one V(3) atom. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one V(2), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing OLi2MnV tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one V(3) atom.
Li4V3MnO12 is Ilmenite-derived structured and crystallizes in the monoclinic P2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms. Both Li(1)-O(2) bond lengths are 1.96 Å. Both Li(1)-O(3) bond lengths are 2.36 Å. Both Li(1)-O(6) bond lengths are 2.23 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form distorted LiO6 pentagonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent V(2)O6 octahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-57°. Both Li(2)-O(2) bond lengths are 2.25 Å. Both Li(2)-O(3) bond lengths are 2.00 Å. Both Li(2)-O(6) bond lengths are 2.19 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form distorted LiO6 pentagonal pyramids that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 47-56°. Both Li(3)-O(1) bond lengths are 2.23 Å. Both Li(3)-O(4) bond lengths are 1.95 Å. Both Li(3)-O(5) bond lengths are 2.18 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms. Both Li(4)-O(1) bond lengths are 2.21 Å. Both Li(4)-O(4) bond lengths are 2.43 Å. Both Li(4)-O(5) bond lengths are 1.95 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form distorted VO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with four equivalent Li(3)O6 pentagonal pyramids, edges with two equivalent V(3)O6 octahedra, and  an edgeedge with one Li(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 43°. Both V(1)-O(1) bond lengths are 1.79 Å. Both V(1)-O(2) bond lengths are 2.05 Å. Both V(1)-O(4) bond lengths are 1.90 Å. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent Mn(1)O6 octahedra, and  an edgeedge with one Li(3)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles are 43°. Both V(2)-O(3) bond lengths are 1.90 Å. Both V(2)-O(5) bond lengths are 2.03 Å. Both V(2)-O(6) bond lengths are 1.78 Å. In the third V site, V(3) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with two equivalent Li(3)O6 pentagonal pyramids, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Li(2)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 43°. Both V(3)-O(2) bond lengths are 1.82 Å. Both V(3)-O(4) bond lengths are 1.85 Å. Both V(3)-O(6) bond lengths are 2.04 Å. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Li(2)O6 pentagonal pyramids, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Li(3)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 43°. Both Mn(1)-O(1) bond lengths are 2.00 Å. Both Mn(1)-O(3) bond lengths are 1.90 Å. Both Mn(1)-O(5) bond lengths are 1.89 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(1), and one Mn(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one V(3) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one V(2), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing OLi2MnV trigonal pyramids. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(1), and one V(3) atom. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one V(2), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing OLi2MnV tetrahedra. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one V(3) atom.