Li2VFeP2(O4F)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(3), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent V(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 52-60°. 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 four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-54°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one P(1) atom. F(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Fe(1) atom.
Li2VFeP2(O4F)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(3), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent V(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 52-60°. The Li(1)-O(1) bond length is 2.11 Å. The Li(1)-O(3) bond length is 2.08 Å. Both Li(1)-O(4) bond lengths are 2.21 Å. The Li(1)-F(1) bond length is 1.93 Å. 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 four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. Both V(1)-O(1) bond lengths are 1.97 Å. Both V(1)-O(4) bond lengths are 2.05 Å. Both V(1)-F(1) bond lengths are 2.03 Å. Fe(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form FeO4F2 octahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 48°. Both Fe(1)-O(2) bond lengths are 1.98 Å. Both Fe(1)-O(3) bond lengths are 2.02 Å. Both Fe(1)-F(1) bond lengths are 2.02 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Fe(1)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-54°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Fe(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Fe(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one V(1), and one P(1) atom. F(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Fe(1) atom.