Li2V5MnO12 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(6) 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(3) atoms to form VO6 octahedra that share corners with two equivalent V(3)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-64°. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-62°. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing OLiMnV2 tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(3), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing OLiMnV2 trigonal pyramids. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one Mn(1) atom.
Li2V5MnO12 is Esseneite-like structured and crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(1)-O(2) bond lengths are 2.37 Å. Both Li(1)-O(3) bond lengths are 2.06 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(6) atoms. Both Li(2)-O(1) bond lengths are 2.04 Å. Both Li(2)-O(6) bond lengths are 2.39 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(3) atoms to form VO6 octahedra that share corners with two equivalent V(3)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. Both V(1)-O(1) bond lengths are 2.09 Å. Both V(1)-O(2) bond lengths are 1.98 Å. Both V(1)-O(3) bond lengths are 2.15 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-64°. The V(2)-O(1) bond length is 1.82 Å. The V(2)-O(2) bond length is 1.77 Å. The V(2)-O(4) bond length is 1.83 Å. The V(2)-O(5) bond length is 1.85 Å. In the third V site, V(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-62°. The V(3)-O(3) bond length is 1.81 Å. The V(3)-O(4) bond length is 1.79 Å. The V(3)-O(5) bond length is 1.79 Å. The V(3)-O(6) bond length is 1.72 Å. Mn(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(3)O4 tetrahedra, and edges with two equivalent V(1)O6 octahedra. Both Mn(1)-O(1) bond lengths are 2.24 Å. Both Mn(1)-O(3) bond lengths are 2.22 Å. Both Mn(1)-O(6) bond lengths are 2.11 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one V(2), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing OLiMnV2 tetrahedra. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one V(2) atom. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(3), and one Mn(1) atom to form a mixture of distorted corner and edge-sharing OLiMnV2 trigonal pyramids. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(2) and one V(3) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one Mn(1) atom.