Li2VMnP2(O4F)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(6), one O(8), 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(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(1)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 52-53°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(7), and one F(2) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(1)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 51-63°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(2), two equivalent O(8), and two equivalent F(2) atoms to form VO4F2 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent P(2)O4 tetrahedra, edges with two equivalent Li(1)O4F square pyramids, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Li(1)O4F square pyramids, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. In the second Mn site, Mn(2) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent Li(2)O4F square pyramids, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 29-53°. In the second P site, P(2) is bonded to one O(2), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 31-53°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), 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 3-coordinate geometry to one Li(2), one Mn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(2), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one Mn(2) atom.
Li2VMnP2(O4F)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(6), one O(8), 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(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(1)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 52-53°. The Li(1)-O(1) bond length is 2.24 Å. The Li(1)-O(2) bond length is 2.24 Å. The Li(1)-O(6) bond length is 2.16 Å. The Li(1)-O(8) bond length is 2.08 Å. The Li(1)-F(1) bond length is 1.95 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(7), and one F(2) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(1)O4F2 octahedra,  an edgeedge with one Mn(1)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 51-63°. The Li(2)-O(1) bond length is 2.22 Å. The Li(2)-O(2) bond length is 2.31 Å. The Li(2)-O(4) bond length is 2.10 Å. The Li(2)-O(7) bond length is 2.08 Å. The Li(2)-F(2) 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(2), two equivalent O(8), and two equivalent F(2) atoms to form VO4F2 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent P(2)O4 tetrahedra, edges with two equivalent Li(1)O4F square pyramids, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. Both V(1)-O(2) bond lengths are 2.08 Å. Both V(1)-O(8) bond lengths are 2.01 Å. Both V(1)-F(2) bond lengths are 1.96 Å. In the second V site, V(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. Both V(2)-O(3) bond lengths are 1.94 Å. Both V(2)-O(6) bond lengths are 1.94 Å. Both V(2)-F(1) bond lengths are 1.94 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, edges with two equivalent Li(1)O4F square pyramids, and edges with two equivalent Li(2)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. Both Mn(1)-O(1) bond lengths are 2.08 Å. Both Mn(1)-O(7) bond lengths are 2.01 Å. Both Mn(1)-F(1) bond lengths are 2.20 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent F(2) atoms to form MnO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent Li(2)O4F square pyramids, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. Both Mn(2)-O(4) bond lengths are 2.00 Å. Both Mn(2)-O(5) bond lengths are 1.99 Å. Both Mn(2)-F(2) bond lengths are 2.18 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent Mn(1)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 29-53°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(5), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Mn(2)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one Li(1)O4F square pyramid,  a cornercorner with one Li(2)O4F square pyramid, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 31-53°. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(5) bond length is 1.52 Å. The P(2)-O(6) bond length is 1.59 Å. The P(2)-O(8) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), 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 3-coordinate geometry to one Li(2), one Mn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(2), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(2) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Mn(1) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one Mn(2) atom.