Li2V4MnFeO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a see-saw-like 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 two inequivalent V sites. In the first V site, V(1) 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 Fe(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-61°. In the second V site, V(2) 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 Fe(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-60°. 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(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Mn(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 Mn(1), and one Fe(1) atom to form a mixture of distorted edge and corner-sharing OLiMnVFe 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 Fe(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one Mn(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one Mn(1) atom.
Li2V4MnFeO12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(1)-O(2) bond lengths are 2.27 Å. Both Li(1)-O(3) bond lengths are 2.05 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 2.38 Å. There are two inequivalent V sites. In the first V site, V(1) 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 Fe(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-61°. The V(1)-O(1) bond length is 1.79 Å. The V(1)-O(2) bond length is 1.73 Å. The V(1)-O(4) bond length is 1.89 Å. The V(1)-O(5) bond length is 1.89 Å. In the second V site, V(2) 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 Fe(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-60°. The V(2)-O(3) bond length is 1.75 Å. The V(2)-O(4) bond length is 1.76 Å. The V(2)-O(5) bond length is 1.76 Å. The V(2)-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(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Fe(1)O6 octahedra. Both Mn(1)-O(1) bond lengths are 2.21 Å. Both Mn(1)-O(3) bond lengths are 2.27 Å. Both Mn(1)-O(6) bond lengths are 2.14 Å. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. Both Fe(1)-O(1) bond lengths are 2.18 Å. Both Fe(1)-O(2) bond lengths are 2.10 Å. Both Fe(1)-O(3) bond lengths are 2.25 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one V(1), one Mn(1), and one Fe(1) atom to form a mixture of distorted edge and corner-sharing OLiMnVFe 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 Fe(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(2), one Mn(1), and one Fe(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(2), and one Mn(1) atom.