Li2VCrP2(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 Cr(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 52-62°. 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 Cr(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 Cr(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 51-60°. 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 Cr(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 Cr(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 Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent F(1) atoms to form CrO4F2 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 Cr site, Cr(2) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent F(2) atoms to form CrO4F2 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 Cr(2)O4F2 octahedra, corners with two equivalent Cr(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 33-54°. 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 Cr(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 32-54°. 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 Cr(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 distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar 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 Cr(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 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 trigonal planar geometry to one Li(1), one V(2), and one Cr(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one Cr(2) atom.
Li2VCrP2(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 Cr(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 52-62°. The Li(1)-O(1) bond length is 2.21 Å. The Li(1)-O(2) bond length is 2.20 Å. The Li(1)-O(6) bond length is 2.08 Å. The Li(1)-O(8) bond length is 2.10 Å. The Li(1)-F(1) bond length is 1.92 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 Cr(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 Cr(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 51-60°. The Li(2)-O(1) bond length is 2.19 Å. The Li(2)-O(2) bond length is 2.21 Å. The Li(2)-O(4) bond length is 2.07 Å. The Li(2)-O(7) bond length is 2.09 Å. The Li(2)-F(2) bond length is 1.94 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 Cr(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 2.05 Å. Both V(1)-O(8) bond lengths are 1.97 Å. Both V(1)-F(2) bond lengths are 2.04 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 Cr(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 2.00 Å. Both V(2)-O(6) bond lengths are 2.01 Å. Both V(2)-F(1) bond lengths are 2.05 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent F(1) atoms to form CrO4F2 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 Cr(1)-O(1) bond lengths are 2.04 Å. Both Cr(1)-O(7) bond lengths are 1.98 Å. Both Cr(1)-F(1) bond lengths are 1.98 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(4), two equivalent O(5), and two equivalent F(2) atoms to form CrO4F2 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 Cr(2)-O(4) bond lengths are 2.01 Å. Both Cr(2)-O(5) bond lengths are 1.99 Å. Both Cr(2)-F(2) bond lengths are 1.98 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 Cr(2)O4F2 octahedra, corners with two equivalent Cr(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 33-54°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.55 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 Cr(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 32-54°. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.56 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 Cr(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 distorted trigonal planar geometry to one Li(2), one Cr(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar 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 Cr(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a 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 trigonal planar geometry to one Li(1), one V(2), and one Cr(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one Cr(2) atom.