Li3V4MnO12 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(3), one O(4), one O(5), and one O(6) atom. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to one O(1), one O(11), one O(12), and one O(2) atom. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. In the third V site, V(3) is bonded to one O(11), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share 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 36-59°. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(6), and one O(8) atom to form VO4 tetrahedra that share 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 36-58°. Mn(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent V(4)O4 tetrahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one Mn(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(2), and one Mn(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(3), and one Mn(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one V(4), and one Mn(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one Mn(1) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(3), one V(4), and one Mn(1) atom.
Li3V4MnO12 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.58 Å. The Li(1)-O(2) bond length is 2.51 Å. The Li(1)-O(3) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.02 Å. The Li(1)-O(5) bond length is 2.39 Å. The Li(1)-O(6) bond length is 2.14 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(3), one O(4), one O(5), and one O(6) atom. The Li(2)-O(3) bond length is 2.57 Å. The Li(2)-O(4) bond length is 2.04 Å. The Li(2)-O(5) bond length is 2.00 Å. The Li(2)-O(6) bond length is 1.99 Å. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to one O(1), one O(11), one O(12), and one O(2) atom. The Li(3)-O(1) bond length is 1.99 Å. The Li(3)-O(11) bond length is 2.43 Å. The Li(3)-O(12) bond length is 2.06 Å. The Li(3)-O(2) bond length is 1.96 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(7), and one O(9) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent V(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The V(1)-O(1) bond length is 1.71 Å. The V(1)-O(3) bond length is 1.67 Å. The V(1)-O(7) bond length is 1.80 Å. The V(1)-O(9) bond length is 1.80 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(4), and one O(8) atom to form VO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra and corners with two equivalent V(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. The V(2)-O(10) bond length is 1.77 Å. The V(2)-O(2) bond length is 1.74 Å. The V(2)-O(4) bond length is 1.71 Å. The V(2)-O(8) bond length is 1.77 Å. In the third V site, V(3) is bonded to one O(11), one O(5), one O(7), and one O(9) atom to form VO4 tetrahedra that share 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 36-59°. The V(3)-O(11) bond length is 1.69 Å. The V(3)-O(5) bond length is 1.71 Å. The V(3)-O(7) bond length is 1.79 Å. The V(3)-O(9) bond length is 1.79 Å. In the fourth V site, V(4) is bonded to one O(10), one O(12), one O(6), and one O(8) atom to form VO4 tetrahedra that share 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 36-58°. The V(4)-O(10) bond length is 1.89 Å. The V(4)-O(12) bond length is 1.75 Å. The V(4)-O(6) bond length is 1.77 Å. The V(4)-O(8) bond length is 1.88 Å. Mn(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom to form MnO6 octahedra that share  a cornercorner with one V(1)O4 tetrahedra,  a cornercorner with one V(2)O4 tetrahedra, corners with two equivalent V(3)O4 tetrahedra, and corners with two equivalent V(4)O4 tetrahedra. The Mn(1)-O(1) bond length is 2.22 Å. The Mn(1)-O(11) bond length is 2.18 Å. The Mn(1)-O(12) bond length is 2.14 Å. The Mn(1)-O(2) bond length is 2.17 Å. The Mn(1)-O(5) bond length is 2.31 Å. The Mn(1)-O(6) bond length is 2.18 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one V(1), and one Mn(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(2), and one Mn(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one V(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one V(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(3), and one Mn(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Li(1), one Li(2), one V(4), and one Mn(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one V(1) and one V(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one V(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one Mn(1) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(3), one V(4), and one Mn(1) atom.