Li2VMnP2(O4F)2 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(11), one O(12), one O(19), and one F(5) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(1)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Li(3)O4F square pyramid, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-61°. In the second Li site, Li(2) is bonded to one O(17), one O(23), one O(5), one O(8), and one F(4) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(3)O4F2 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(5)O4F square pyramid, and  an edgeedge with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-62°. In the third Li site, Li(3) is bonded to one O(12), one O(19), one O(7), one O(9), and one F(6) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-60°. In the fourth Li site, Li(4) is bonded to one O(13), one O(16), one O(18), one O(6), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(3)O4F2 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(6)O4F square pyramid, and  an edgeedge with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-63°. In the fifth Li site, Li(5) is bonded to one O(17), one O(2), one O(20), one O(8), and one F(3) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-58°. In the sixth Li site, Li(6) is bonded to one O(13), one O(14), one O(24), one O(6), and one F(2) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(1)O4F2 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-59°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(12), one O(13), one O(24), one F(1), and one F(6) atom to form VO4F2 octahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(1)O4F square pyramid,  an edgeedge with one Li(3)O4F square pyramid,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(6)O4F square pyramid. The corner-sharing octahedral tilt angles are 48°. In the second V site, V(2) is bonded to one O(10), one O(2), one O(22), one O(9), one F(3), and one F(6) atom to form VO4F2 octahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(3)O4F square pyramids, corners with two equivalent Li(5)O4F square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. In the third V site, V(3) is bonded to one O(19), one O(20), one O(7), one O(8), one F(4), and one F(5) atom to form VO4F2 octahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O4F square pyramid,  an edgeedge with one Li(2)O4F square pyramid,  an edgeedge with one Li(3)O4F square pyramid, and  an edgeedge with one Li(5)O4F square pyramid. The corner-sharing octahedral tilt angles are 49°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(11), one O(14), one O(21), one O(4), one F(2), and one F(5) atom to form MnO4F2 octahedra that share  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two equivalent Li(6)O4F square pyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. In the second Mn site, Mn(2) is bonded to one O(17), one O(18), one O(5), one O(6), one F(2), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent P(5)O4 tetrahedra, corners with two equivalent P(6)O4 tetrahedra,  an edgeedge with one Li(2)O4F square pyramid,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and  an edgeedge with one Li(6)O4F square pyramid. The corner-sharing octahedral tilt angles range from 49-50°. In the third Mn site, Mn(3) is bonded to one O(15), one O(16), one O(23), one O(3), one F(1), and one F(4) atom to form MnO4F2 octahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra, corners with two equivalent Li(2)O4F square pyramids, corners with two equivalent Li(4)O4F square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(19), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(3)O4F square pyramid, and  an edgeedge with one Li(3)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-54°. In the second P site, P(2) is bonded to one O(2), one O(20), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(5)O4F square pyramid, and  an edgeedge with one Li(5)O4F square pyramid. The corner-sharing octahedral tilt angles range from 33-54°. In the third P site, P(3) is bonded to one O(10), one O(13), one O(14), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Li(6)O4F square pyramid, and  an edgeedge with one Li(6)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-53°. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(12), and one O(15) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(3)O4F square pyramid, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-53°. In the fifth P site, P(5) is bonded to one O(17), one O(21), one O(23), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(5)O4F square pyramid, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 33-53°. In the sixth P site, P(6) is bonded to one O(16), one O(18), one O(22), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Li(6)O4F square pyramid, and  an edgeedge with one Li(4)O4F square pyramid. The corner-sharing octahedral tilt angles range from 33-53°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(5), one V(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(2), and one P(5) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(4), one Li(6), one Mn(2), and one P(6) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(3), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one V(3), 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(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) 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(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(4), one Li(6), one V(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(6), one Mn(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(3), and one P(6) atom. In the seventeenth O site, O(17) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Mn(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a T-shaped geometry to one Li(4), one Mn(2), and one P(6) atom. In the nineteenth O site, O(19) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one V(3), and one P(1) atom. In the twentieth O site, O(20) is bonded in a T-shaped geometry to one Li(5), one V(3), and one P(2) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one V(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(3), and one P(5) atom. In the twenty-fourth O site, O(24) is bonded in a T-shaped geometry to one Li(6), one V(1), and one P(3) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one Mn(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(6), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(5), one V(2), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(2) atom.
Li2VMnP2(O4F)2 crystallizes in the triclinic P1 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(11), one O(12), one O(19), and one F(5) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(1)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Li(3)O4F square pyramid, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-61°. The Li(1)-O(1) bond length is 2.09 Å. The Li(1)-O(11) bond length is 2.08 Å. The Li(1)-O(12) bond length is 2.20 Å. The Li(1)-O(19) bond length is 2.27 Å. The Li(1)-F(5) bond length is 1.88 Å. In the second Li site, Li(2) is bonded to one O(17), one O(23), one O(5), one O(8), and one F(4) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(3)O4F2 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(5)O4F square pyramid, and  an edgeedge with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-62°. The Li(2)-O(17) bond length is 2.20 Å. The Li(2)-O(23) bond length is 2.08 Å. The Li(2)-O(5) bond length is 2.09 Å. The Li(2)-O(8) bond length is 2.26 Å. The Li(2)-F(4) bond length is 1.88 Å. In the third Li site, Li(3) is bonded to one O(12), one O(19), one O(7), one O(9), and one F(6) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-60°. The Li(3)-O(12) bond length is 2.26 Å. The Li(3)-O(19) bond length is 2.17 Å. The Li(3)-O(7) bond length is 2.09 Å. The Li(3)-O(9) bond length is 2.08 Å. The Li(3)-F(6) bond length is 1.92 Å. In the fourth Li site, Li(4) is bonded to one O(13), one O(16), one O(18), one O(6), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(3)O4F2 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(6)O4F square pyramid, and  an edgeedge with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-63°. The Li(4)-O(13) bond length is 2.25 Å. The Li(4)-O(16) bond length is 2.08 Å. The Li(4)-O(18) bond length is 2.08 Å. The Li(4)-O(6) bond length is 2.19 Å. The Li(4)-F(1) bond length is 1.89 Å. In the fifth Li site, Li(5) is bonded to one O(17), one O(2), one O(20), one O(8), and one F(3) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra,  an edgeedge with one V(3)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-58°. The Li(5)-O(17) bond length is 2.26 Å. The Li(5)-O(2) bond length is 2.08 Å. The Li(5)-O(20) bond length is 2.10 Å. The Li(5)-O(8) bond length is 2.17 Å. The Li(5)-F(3) bond length is 1.90 Å. In the sixth Li site, Li(6) is bonded to one O(13), one O(14), one O(24), one O(6), and one F(2) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(1)O4F2 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(6)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-59°. The Li(6)-O(13) bond length is 2.19 Å. The Li(6)-O(14) bond length is 2.07 Å. The Li(6)-O(24) bond length is 2.07 Å. The Li(6)-O(6) bond length is 2.27 Å. The Li(6)-F(2) bond length is 1.86 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(12), one O(13), one O(24), one F(1), and one F(6) atom to form VO4F2 octahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(1)O4F square pyramid,  an edgeedge with one Li(3)O4F square pyramid,  an edgeedge with one Li(4)O4F square pyramid, and  an edgeedge with one Li(6)O4F square pyramid. The corner-sharing octahedral tilt angles are 48°. The V(1)-O(1) bond length is 1.98 Å. The V(1)-O(12) bond length is 2.06 Å. The V(1)-O(13) bond length is 2.05 Å. The V(1)-O(24) bond length is 1.99 Å. The V(1)-F(1) bond length is 1.99 Å. The V(1)-F(6) bond length is 2.02 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(22), one O(9), one F(3), and one F(6) atom to form VO4F2 octahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(3)O4F square pyramids, corners with two equivalent Li(5)O4F square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The V(2)-O(10) bond length is 1.99 Å. The V(2)-O(2) bond length is 2.00 Å. The V(2)-O(22) bond length is 2.01 Å. The V(2)-O(9) bond length is 2.00 Å. The V(2)-F(3) bond length is 2.02 Å. The V(2)-F(6) bond length is 2.07 Å. In the third V site, V(3) is bonded to one O(19), one O(20), one O(7), one O(8), one F(4), and one F(5) atom to form VO4F2 octahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(1)O4F square pyramid,  an edgeedge with one Li(2)O4F square pyramid,  an edgeedge with one Li(3)O4F square pyramid, and  an edgeedge with one Li(5)O4F square pyramid. The corner-sharing octahedral tilt angles are 49°. The V(3)-O(19) bond length is 2.07 Å. The V(3)-O(20) bond length is 1.97 Å. The V(3)-O(7) bond length is 1.98 Å. The V(3)-O(8) bond length is 2.06 Å. The V(3)-F(4) bond length is 2.00 Å. The V(3)-F(5) bond length is 1.99 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(11), one O(14), one O(21), one O(4), one F(2), and one F(5) atom to form MnO4F2 octahedra that share  a cornercorner with one V(3)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two equivalent Li(6)O4F square pyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and  a cornercorner with one P(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-50°. The Mn(1)-O(11) bond length is 1.98 Å. The Mn(1)-O(14) bond length is 1.97 Å. The Mn(1)-O(21) bond length is 1.98 Å. The Mn(1)-O(4) bond length is 1.96 Å. The Mn(1)-F(2) bond length is 2.10 Å. The Mn(1)-F(5) bond length is 2.15 Å. In the second Mn site, Mn(2) is bonded to one O(17), one O(18), one O(5), one O(6), one F(2), and one F(3) atom to form MnO4F2 octahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent P(5)O4 tetrahedra, corners with two equivalent P(6)O4 tetrahedra,  an edgeedge with one Li(2)O4F square pyramid,  an edgeedge with one Li(4)O4F square pyramid,  an edgeedge with one Li(5)O4F square pyramid, and  an edgeedge with one Li(6)O4F square pyramid. The corner-sharing octahedral tilt angles range from 49-50°. The Mn(2)-O(17) bond length is 2.05 Å. The Mn(2)-O(18) bond length is 1.96 Å. The Mn(2)-O(5) bond length is 1.96 Å. The Mn(2)-O(6) bond length is 2.05 Å. The Mn(2)-F(2) bond length is 2.06 Å. The Mn(2)-F(3) bond length is 2.11 Å. In the third Mn site, Mn(3) is bonded to one O(15), one O(16), one O(23), one O(3), one F(1), and one F(4) atom to form MnO4F2 octahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(3)O4F2 octahedra, corners with two equivalent Li(2)O4F square pyramids, corners with two equivalent Li(4)O4F square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one P(5)O4 tetrahedra, and  a cornercorner with one P(6)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-49°. The Mn(3)-O(15) bond length is 1.97 Å. The Mn(3)-O(16) bond length is 1.99 Å. The Mn(3)-O(23) bond length is 1.99 Å. The Mn(3)-O(3) bond length is 1.96 Å. The Mn(3)-F(1) bond length is 2.14 Å. The Mn(3)-F(4) bond length is 2.14 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded to one O(19), one O(3), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(3)O4F square pyramid, and  an edgeedge with one Li(3)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-54°. The P(1)-O(19) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(2), one O(20), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent V(3)O4F2 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(5)O4F square pyramid, and  an edgeedge with one Li(5)O4F square pyramid. The corner-sharing octahedral tilt angles range from 33-54°. The P(2)-O(2) bond length is 1.55 Å. The P(2)-O(20) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(13), one O(14), and one O(24) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(1)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Li(6)O4F square pyramid, and  an edgeedge with one Li(6)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-53°. The P(3)-O(10) bond length is 1.52 Å. The P(3)-O(13) bond length is 1.57 Å. The P(3)-O(14) bond length is 1.56 Å. The P(3)-O(24) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(1), one O(11), one O(12), and one O(15) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(3)O4F square pyramid, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-53°. The P(4)-O(1) bond length is 1.55 Å. The P(4)-O(11) bond length is 1.56 Å. The P(4)-O(12) bond length is 1.56 Å. The P(4)-O(15) bond length is 1.54 Å. In the fifth P site, P(5) is bonded to one O(17), one O(21), one O(23), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(5)O4F square pyramid, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 33-53°. The P(5)-O(17) bond length is 1.58 Å. The P(5)-O(21) bond length is 1.53 Å. The P(5)-O(23) bond length is 1.56 Å. The P(5)-O(5) bond length is 1.57 Å. In the sixth P site, P(6) is bonded to one O(16), one O(18), one O(22), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(3)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra,  a cornercorner with one Li(4)O4F square pyramid,  a cornercorner with one Li(6)O4F square pyramid, and  an edgeedge with one Li(4)O4F square pyramid. The corner-sharing octahedral tilt angles range from 33-53°. The P(6)-O(16) bond length is 1.56 Å. The P(6)-O(18) bond length is 1.57 Å. The P(6)-O(22) bond length is 1.52 Å. The P(6)-O(6) bond length is 1.57 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(4) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(5), one V(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(2), and one P(5) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(4), one Li(6), one Mn(2), and one P(6) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(3), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one V(3), 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(2), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) 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(4) atom. In the twelfth O site, O(12) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one V(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded in a rectangular see-saw-like geometry to one Li(4), one Li(6), one V(1), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(6), one Mn(1), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(3), and one P(6) atom. In the seventeenth O site, O(17) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(5), one Mn(2), and one P(5) atom. In the eighteenth O site, O(18) is bonded in a T-shaped geometry to one Li(4), one Mn(2), and one P(6) atom. In the nineteenth O site, O(19) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one V(3), and one P(1) atom. In the twentieth O site, O(20) is bonded in a T-shaped geometry to one Li(5), one V(3), and one P(2) atom. In the twenty-first O site, O(21) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(5) atom. In the twenty-second O site, O(22) is bonded in a bent 150 degrees geometry to one V(2) and one P(6) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(3), and one P(5) atom. In the twenty-fourth O site, O(24) is bonded in a T-shaped geometry to one Li(6), one V(1), and one P(3) atom. There are six inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(4), one V(1), and one Mn(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(6), one Mn(1), and one Mn(2) atom. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Li(5), one V(2), and one Mn(2) atom. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Li(2), one V(3), and one Mn(3) atom. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one Mn(1) atom. In the sixth F site, F(6) is bonded in a trigonal planar geometry to one Li(3), one V(1), and one V(2) atom.