Li2VMnP2(O4F)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(11), one O(12), 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(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(3)O4F square pyramid, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-59°. In the second Li site, Li(2) is bonded to one O(2), one O(5), two equivalent O(8), and one F(3) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent 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 53-58°. In the third Li site, Li(3) is bonded to one O(12), one O(6), one O(7), one O(9), and one F(1) 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(3)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)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 53-61°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(12), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent P(3)O4 tetrahedra, edges with two equivalent Li(1)O4F square pyramids, and edges with two equivalent Li(3)O4F square pyramids. The corner-sharing octahedral tilt angles are 47°. In the second V site, V(2) is bonded to one O(10), one O(2), one O(3), one O(9), one F(1), and one F(3) 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(2)O4F square pyramids, corners with two equivalent Li(3)O4F square pyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-49°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(11), two equivalent O(4), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. In the second Mn site, Mn(2) is bonded to one O(5), one O(6), one O(7), one O(8), 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(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(3)O4F square pyramid, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles range from 49-51°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Mn(2)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 33-54°. In the second P site, P(2) is bonded to one O(2), one O(4), one O(5), 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 Mn(2)O4F2 octahedra, corners with two equivalent Li(2)O4F square pyramids, and  an edgeedge with one Li(2)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(1), one O(10), one O(11), and one O(12) 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(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 33-54°. There are twelve 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(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), 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 V(2) 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(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(3), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one Mn(2), 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(3) 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(3) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), 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(2), one V(2), and one Mn(2) atom.
Li2VMnP2(O4F)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(11), one O(12), 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(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)O4F2 octahedra,  an edgeedge with one Li(3)O4F square pyramid, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-59°. The Li(1)-O(1) bond length is 2.09 Å. The Li(1)-O(11) bond length is 2.07 Å. The Li(1)-O(12) bond length is 2.21 Å. The Li(1)-O(6) bond length is 2.29 Å. The Li(1)-F(2) bond length is 1.84 Å. In the second Li site, Li(2) is bonded to one O(2), one O(5), two equivalent O(8), and one F(3) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent 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 53-58°. The Li(2)-O(2) bond length is 2.08 Å. The Li(2)-O(5) bond length is 2.12 Å. There is one shorter (2.19 Å) and one longer (2.26 Å) Li(2)-O(8) bond length. The Li(2)-F(3) bond length is 1.88 Å. In the third Li site, Li(3) is bonded to one O(12), one O(6), one O(7), one O(9), and one F(1) 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(3)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(2)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 53-61°. The Li(3)-O(12) bond length is 2.25 Å. The Li(3)-O(6) bond length is 2.17 Å. The Li(3)-O(7) bond length is 2.10 Å. The Li(3)-O(9) bond length is 2.08 Å. The Li(3)-F(1) bond length is 1.91 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(12), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent P(3)O4 tetrahedra, edges with two equivalent Li(1)O4F square pyramids, and edges with two equivalent Li(3)O4F square pyramids. The corner-sharing octahedral tilt angles are 47°. Both V(1)-O(1) bond lengths are 1.98 Å. Both V(1)-O(12) bond lengths are 2.04 Å. Both V(1)-F(1) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to one O(10), one O(2), one O(3), one O(9), one F(1), and one F(3) 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(2)O4F square pyramids, corners with two equivalent Li(3)O4F square pyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-49°. The V(2)-O(10) bond length is 1.99 Å. The V(2)-O(2) bond length is 2.02 Å. The V(2)-O(3) bond length is 2.01 Å. The V(2)-O(9) bond length is 2.02 Å. The V(2)-F(1) bond length is 2.06 Å. The V(2)-F(3) bond length is 2.02 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(11), two equivalent O(4), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. Both Mn(1)-O(11) bond lengths are 1.97 Å. Both Mn(1)-O(4) bond lengths are 1.99 Å. Both Mn(1)-F(2) bond lengths are 2.09 Å. In the second Mn site, Mn(2) is bonded to one O(5), one O(6), one O(7), one O(8), 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(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(3)O4F square pyramid, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles range from 49-51°. The Mn(2)-O(5) bond length is 1.95 Å. The Mn(2)-O(6) bond length is 2.02 Å. The Mn(2)-O(7) bond length is 1.95 Å. The Mn(2)-O(8) bond length is 2.02 Å. The Mn(2)-F(2) bond length is 2.09 Å. The Mn(2)-F(3) bond length is 2.12 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Mn(2)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 33-54°. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(6) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.56 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(4), one O(5), 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 Mn(2)O4F2 octahedra, corners with two equivalent Li(2)O4F square pyramids, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 33-54°. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.58 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(11), and one O(12) 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(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 33-54°. The P(3)-O(1) bond length is 1.55 Å. The P(3)-O(10) bond length is 1.53 Å. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(12) bond length is 1.57 Å. There are twelve 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(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(2), 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 V(2) 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(2) atom. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(3), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(3), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to two equivalent Li(2), one Mn(2), 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(3) 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(3) atom. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one V(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), 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(2), one V(2), and one Mn(2) atom.