Li3VMn(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 in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(6), one O(7), and one O(9) atom. In the second Li site, Li(2) is bonded to two equivalent O(5), two equivalent O(7), and two equivalent O(9) atoms to form LiO6 octahedra that share 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 faces with two equivalent Mn(1)O6 octahedra. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(5), one O(7), and one O(8) atom. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(4), and two equivalent O(6) atoms. V(1) is bonded to one O(1), one O(10), one O(11), one O(4), one O(6), and one O(8) 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(12), one O(2), one O(3), one O(5), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share 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 faceface with one Li(2)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 19-52°. In the second P site, P(2) is bonded to one O(2), one O(4), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 21-48°. In the third P site, P(3) is bonded to one O(10), one O(12), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 13-53°. 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 V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Mn(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(1) and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(3), one Li(4), one V(1), and one P(1) atom to form distorted corner-sharing OLi3VP trigonal bipyramids. 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 four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(2), one O(6), one O(7), and one O(9) atom. The Li(1)-O(1) bond length is 2.34 Å. The Li(1)-O(11) bond length is 2.47 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(6) bond length is 2.13 Å. The Li(1)-O(7) bond length is 2.38 Å. The Li(1)-O(9) bond length is 2.46 Å. In the second Li site, Li(2) is bonded to two equivalent O(5), two equivalent O(7), and two equivalent O(9) atoms to form LiO6 octahedra that share 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 faces with two equivalent Mn(1)O6 octahedra. Both Li(2)-O(5) bond lengths are 2.14 Å. Both Li(2)-O(7) bond lengths are 2.30 Å. Both Li(2)-O(9) bond lengths are 2.19 Å. In the third Li site, Li(3) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(5), one O(7), and one O(8) atom. The Li(3)-O(11) bond length is 2.40 Å. The Li(3)-O(12) bond length is 2.07 Å. The Li(3)-O(5) bond length is 1.99 Å. The Li(3)-O(7) bond length is 2.26 Å. The Li(3)-O(8) bond length is 2.53 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(4), and two equivalent O(6) atoms. Both Li(4)-O(11) bond lengths are 2.35 Å. Both Li(4)-O(4) bond lengths are 2.33 Å. Both Li(4)-O(6) bond lengths are 2.27 Å. V(1) is bonded to one O(1), one O(10), one O(11), one O(4), one O(6), and one O(8) 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 1.94 Å. The V(1)-O(10) bond length is 1.88 Å. The V(1)-O(11) bond length is 2.00 Å. The V(1)-O(4) bond length is 1.99 Å. The V(1)-O(6) bond length is 2.00 Å. The V(1)-O(8) bond length is 1.94 Å. Mn(1) is bonded to one O(12), one O(2), one O(3), one O(5), one O(7), and one O(9) atom to form distorted MnO6 octahedra that share 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 faceface with one Li(2)O6 octahedra. The Mn(1)-O(12) bond length is 2.17 Å. The Mn(1)-O(2) bond length is 2.16 Å. The Mn(1)-O(3) bond length is 2.01 Å. The Mn(1)-O(5) bond length is 2.21 Å. The Mn(1)-O(7) bond length is 2.22 Å. The Mn(1)-O(9) bond length is 2.22 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 19-52°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(11) bond length is 1.60 Å. The P(1)-O(3) bond length is 1.50 Å. The P(1)-O(5) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 21-48°. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(4) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.58 Å. The P(2)-O(9) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, 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 13-53°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(12) bond length is 1.52 Å. The P(3)-O(6) bond length is 1.57 Å. The P(3)-O(7) bond length is 1.54 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 V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(4), one V(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Li(1), one Li(2), one Li(3), one Mn(1), and one P(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(3), one V(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a linear geometry to one V(1) and one P(3) atom. In the eleventh O site, O(11) is bonded to one Li(1), one Li(3), one Li(4), one V(1), and one P(1) atom to form distorted corner-sharing OLi3VP trigonal bipyramids. 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.