Li3VMn(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(7) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(4), one O(5), and one O(6) atom. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(12), one O(2), one O(5), one O(8), and one O(9) atom. V(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share 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. Mn(1) is bonded to one O(10), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form MnO6 octahedra that share 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(4) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-50°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-48°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-47°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Mn(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), 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(1), one V(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one P(3) atom.
Li3VMn(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(11), and one O(7) atom. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(11) bond length is 2.02 Å. The Li(1)-O(7) bond length is 2.01 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(10), one O(2), one O(4), one O(5), and one O(6) atom. The Li(2)-O(10) bond length is 1.96 Å. The Li(2)-O(2) bond length is 2.63 Å. The Li(2)-O(4) bond length is 2.03 Å. The Li(2)-O(5) bond length is 2.07 Å. The Li(2)-O(6) bond length is 2.45 Å. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(12), one O(2), one O(5), one O(8), and one O(9) atom. The Li(3)-O(1) bond length is 2.63 Å. The Li(3)-O(10) bond length is 2.54 Å. The Li(3)-O(12) bond length is 2.11 Å. The Li(3)-O(2) bond length is 2.26 Å. The Li(3)-O(5) bond length is 2.27 Å. The Li(3)-O(8) bond length is 2.62 Å. The Li(3)-O(9) bond length is 2.31 Å. V(1) is bonded to one O(1), one O(11), one O(12), one O(3), one O(5), and one O(6) atom to form VO6 octahedra that share 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 V(1)-O(1) bond length is 2.04 Å. The V(1)-O(11) bond length is 2.05 Å. The V(1)-O(12) bond length is 2.03 Å. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(5) bond length is 2.11 Å. The V(1)-O(6) bond length is 2.01 Å. Mn(1) is bonded to one O(10), one O(2), one O(4), one O(7), one O(8), and one O(9) atom to form MnO6 octahedra that share 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(10) bond length is 2.20 Å. The Mn(1)-O(2) bond length is 2.02 Å. The Mn(1)-O(4) bond length is 2.05 Å. The Mn(1)-O(7) bond length is 2.11 Å. The Mn(1)-O(8) bond length is 1.91 Å. The Mn(1)-O(9) bond length is 1.96 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(4) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-50°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-48°. The P(2)-O(5) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-47°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(11) bond length is 1.54 Å. The P(3)-O(12) bond length is 1.57 Å. The P(3)-O(8) bond length is 1.55 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(2), one Li(3), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal pyramidal geometry to one Li(2), one Li(3), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Mn(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(3), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), 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(1), one V(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one P(3) atom.