Li4VMn(PO4)3 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(2), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-67°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(12), one O(4), one O(5), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(11), one O(3), one O(6), and one O(7) atom. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. Mn(1) is bonded to one O(10), one O(11), one O(12), one O(6), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(12), one O(3), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 32-53°. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 22-58°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-54°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form corner-sharing OLi2VP trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(1), and one P(2) atom to form corner-sharing OLi2VP tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one V(1), and one P(3) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(4), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(4), one Mn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Li(3), one Mn(1), and one P(1) atom.
Li4VMn(PO4)3 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(10), one O(2), and one O(4) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-67°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(10) bond length is 1.90 Å. The Li(1)-O(2) bond length is 1.93 Å. The Li(1)-O(4) bond length is 2.18 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-O(3) bond length is 2.06 Å. The Li(2)-O(5) bond length is 1.97 Å. The Li(2)-O(6) bond length is 1.95 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(12), one O(4), one O(5), and one O(9) atom. The Li(3)-O(12) bond length is 1.90 Å. The Li(3)-O(4) bond length is 1.96 Å. The Li(3)-O(5) bond length is 2.35 Å. The Li(3)-O(9) bond length is 1.93 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to one O(11), one O(3), one O(6), and one O(7) atom. The Li(4)-O(11) bond length is 1.92 Å. The Li(4)-O(3) bond length is 2.17 Å. The Li(4)-O(6) bond length is 2.11 Å. The Li(4)-O(7) bond length is 2.16 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 trigonal pyramid. The V(1)-O(1) bond length is 2.09 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 2.07 Å. The V(1)-O(4) bond length is 2.13 Å. The V(1)-O(5) bond length is 2.04 Å. The V(1)-O(9) bond length is 2.03 Å. Mn(1) is bonded to one O(10), one O(11), one O(12), one O(6), one O(7), and one O(8) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. The Mn(1)-O(10) bond length is 2.27 Å. The Mn(1)-O(11) bond length is 2.27 Å. The Mn(1)-O(12) bond length is 2.25 Å. The Mn(1)-O(6) bond length is 2.30 Å. The Mn(1)-O(7) bond length is 2.15 Å. The Mn(1)-O(8) bond length is 2.08 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(12), one O(3), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 32-53°. The P(1)-O(1) bond length is 1.59 Å. The P(1)-O(12) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(7) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 22-58°. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(5), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, and  a cornercorner with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 31-54°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(11) bond length is 1.52 Å. The P(3)-O(5) bond length is 1.59 Å. The P(3)-O(9) bond length is 1.57 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form corner-sharing OLi2VP trigonal pyramids. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(3), one V(1), and one P(2) atom to form corner-sharing OLi2VP tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one V(1), and one P(3) atom to form distorted corner-sharing OLi2VP trigonal pyramids. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(4), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(4), one Mn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a trigonal planar geometry to one Li(3), one Mn(1), and one P(1) atom.