Li2VFeP2(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(3), one O(4), one O(7), one O(8), and one F(2) atom to form distorted LiO4F square pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Fe(1)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-60°. In the second Li site, Li(2) is bonded to one O(2), one O(6), one O(7), one O(8), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Fe(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-61°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two 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 47°. In the second V site, V(2) 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 Fe(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two 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°. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3), two equivalent O(7), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two 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 47°. In the second Fe site, Fe(2) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent F(2) atoms to form FeO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two 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(3), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)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 31-54°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)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 31-53°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(2), one V(2), and one P(2) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Li(1), one Fe(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one Fe(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one V(2), and one Fe(2) atom.
Li2VFeP2(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(3), one O(4), one O(7), one O(8), and one F(2) atom to form distorted LiO4F square pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Fe(1)O4F2 octahedra,  an edgeedge with one Li(2)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-60°. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 2.08 Å. The Li(1)-O(7) bond length is 2.20 Å. The Li(1)-O(8) bond length is 2.21 Å. The Li(1)-F(2) bond length is 1.92 Å. In the second Li site, Li(2) is bonded to one O(2), one O(6), one O(7), one O(8), and one F(1) atom to form distorted LiO4F square pyramids that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Fe(2)O4F2 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Fe(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-61°. The Li(2)-O(2) bond length is 2.10 Å. The Li(2)-O(6) bond length is 2.08 Å. The Li(2)-O(7) bond length is 2.23 Å. The Li(2)-O(8) bond length is 2.23 Å. The Li(2)-F(1) bond length is 1.92 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two 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 47°. Both V(1)-O(1) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 2.03 Å. Both V(1)-F(1) bond lengths are 2.04 Å. In the second V site, V(2) 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 Fe(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two 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(2)-O(2) bond lengths are 1.98 Å. Both V(2)-O(8) bond lengths are 2.05 Å. Both V(2)-F(2) bond lengths are 2.04 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3), two equivalent O(7), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two 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 47°. Both Fe(1)-O(3) bond lengths are 1.96 Å. Both Fe(1)-O(7) bond lengths are 2.04 Å. Both Fe(1)-F(1) bond lengths are 2.01 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(5), two equivalent O(6), and two equivalent F(2) atoms to form FeO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two 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 Fe(2)-O(5) bond lengths are 1.98 Å. Both Fe(2)-O(6) bond lengths are 2.01 Å. Both Fe(2)-F(2) bond lengths are 2.02 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)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 31-54°. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(8) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one V(2)O4F2 octahedra,  a cornercorner with one Fe(1)O4F2 octahedra,  a cornercorner with one Fe(2)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 31-53°. The P(2)-O(1) bond length is 1.53 Å. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.57 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the second O site, O(2) is bonded in a T-shaped geometry to one Li(2), one V(2), and one P(2) atom. In the third O site, O(3) is bonded in a T-shaped geometry to one Li(1), one Fe(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Fe(2) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Fe(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Fe(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one Fe(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(1), one V(2), and one Fe(2) atom.