Li3VMn(PO4)3 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(4), and one O(5) atom. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(5), and one O(6) 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(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-70°. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(12), one O(3), one O(7), and one O(8) atom. V(1) is bonded to one O(1), one O(10), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(2)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  an edgeedge with one Li(2)O4 tetrahedra. Mn(1) is bonded to one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), 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, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-49°. In the second P site, P(2) is bonded to one O(4), one O(5), one O(8), 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, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-52°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-56°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(3), one Mn(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(3), one Mn(1), and one P(3) atom.
Li3VMn(PO4)3 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(4), and one O(5) atom. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(11) bond length is 1.89 Å. The Li(1)-O(4) bond length is 2.08 Å. The Li(1)-O(5) bond length is 2.16 Å. In the second Li site, Li(2) is bonded to one O(10), one O(2), one O(5), and one O(6) 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(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-70°. The Li(2)-O(10) bond length is 1.99 Å. The Li(2)-O(2) bond length is 1.92 Å. The Li(2)-O(5) bond length is 2.04 Å. The Li(2)-O(6) bond length is 2.29 Å. In the third Li site, Li(3) is bonded in a rectangular see-saw-like geometry to one O(12), one O(3), one O(7), and one O(8) atom. The Li(3)-O(12) bond length is 1.97 Å. The Li(3)-O(3) bond length is 2.17 Å. The Li(3)-O(7) bond length is 2.05 Å. The Li(3)-O(8) bond length is 2.01 Å. V(1) is bonded to one O(1), one O(10), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(2)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  an edgeedge with one Li(2)O4 tetrahedra. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(10) bond length is 2.01 Å. The V(1)-O(3) bond length is 1.93 Å. The V(1)-O(4) bond length is 1.92 Å. The V(1)-O(5) bond length is 2.07 Å. The V(1)-O(6) bond length is 1.91 Å. Mn(1) is bonded to one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom to form distorted MnO6 octahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Mn(1)-O(11) bond length is 2.26 Å. The Mn(1)-O(12) bond length is 2.26 Å. The Mn(1)-O(2) bond length is 2.23 Å. The Mn(1)-O(7) bond length is 2.18 Å. The Mn(1)-O(8) bond length is 2.22 Å. The Mn(1)-O(9) bond length is 2.09 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), 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, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-49°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(7) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(4), one O(5), one O(8), 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, and  a cornercorner with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-52°. The P(2)-O(4) bond length is 1.60 Å. The P(2)-O(5) bond length is 1.60 Å. The P(2)-O(8) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 33-56°. The P(3)-O(10) bond length is 1.57 Å. The P(3)-O(11) bond length is 1.53 Å. The P(3)-O(12) bond length is 1.52 Å. The P(3)-O(6) bond length is 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a distorted trigonal non-coplanar geometry to one Li(3), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(3), one Mn(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(3), one Mn(1), and one P(3) atom.