Li2VCrP2(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(5), one O(8), two equivalent O(11), and one F(3) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent 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 52-62°. In the second Li site, Li(2) is bonded to one O(12), one O(3), one O(6), one O(7), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Cr(1)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 52-62°. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(7), one O(9), 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(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(2)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 51-60°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(12), one O(4), one O(5), one F(1), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent Cr(1)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two equivalent Li(2)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 are 48°. In the second V site, V(2) is bonded to two equivalent O(6), two equivalent O(7), 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(3)O4 tetrahedra, edges with two equivalent Li(2)O4F square pyramids, and edges with two equivalent Li(3)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(11), one O(3), one O(8), one O(9), one F(1), and one F(3) atom to form CrO4F2 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,  an edgeedge with one Li(2)O4F square pyramid,  an edgeedge with one Li(3)O4F square pyramid, and edges with two equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form CrO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent Li(3)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 48°. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Cr(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 33-54°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Cr(2)O4F2 octahedra, corners with two equivalent Cr(1)O4F2 octahedra,  a cornercorner with one Li(2)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 third P site, P(3) is bonded to one O(1), one O(12), 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 Cr(2)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(3)O4F square pyramid, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-54°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Li(2), one V(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a T-shaped geometry to one Li(3), one Cr(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Cr(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), 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 trigonal planar geometry to one Li(2), one V(1), and one Cr(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one Cr(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Cr(1) atom.
Li2VCrP2(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(5), one O(8), two equivalent O(11), and one F(3) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent 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 52-62°. The Li(1)-O(5) bond length is 2.08 Å. The Li(1)-O(8) bond length is 2.09 Å. There is one shorter (2.18 Å) and one longer (2.21 Å) Li(1)-O(11) bond length. The Li(1)-F(3) bond length is 1.93 Å. In the second Li site, Li(2) is bonded to one O(12), one O(3), one O(6), one O(7), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent V(1)O4F2 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(2)O4F2 octahedra,  an edgeedge with one Cr(1)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 52-62°. The Li(2)-O(12) bond length is 2.08 Å. The Li(2)-O(3) bond length is 2.20 Å. The Li(2)-O(6) bond length is 2.09 Å. The Li(2)-O(7) bond length is 2.19 Å. The Li(2)-F(1) bond length is 1.92 Å. In the third Li site, Li(3) is bonded to one O(2), one O(3), one O(7), one O(9), 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(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one V(2)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 51-60°. The Li(3)-O(2) bond length is 2.08 Å. The Li(3)-O(3) bond length is 2.18 Å. The Li(3)-O(7) bond length is 2.20 Å. The Li(3)-O(9) bond length is 2.09 Å. The Li(3)-F(2) bond length is 1.94 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(12), one O(4), one O(5), one F(1), and one F(3) atom to form VO4F2 octahedra that share corners with two equivalent Cr(1)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, corners with two equivalent Li(2)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 are 48°. The V(1)-O(10) bond length is 1.99 Å. The V(1)-O(12) bond length is 2.01 Å. The V(1)-O(4) bond length is 1.99 Å. The V(1)-O(5) bond length is 2.02 Å. The V(1)-F(1) bond length is 2.04 Å. The V(1)-F(3) bond length is 2.04 Å. In the second V site, V(2) is bonded to two equivalent O(6), two equivalent O(7), 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(3)O4 tetrahedra, edges with two equivalent Li(2)O4F square pyramids, and edges with two equivalent Li(3)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. Both V(2)-O(6) bond lengths are 1.98 Å. Both V(2)-O(7) bond lengths are 2.05 Å. Both V(2)-F(2) bond lengths are 2.03 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(11), one O(3), one O(8), one O(9), one F(1), and one F(3) atom to form CrO4F2 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,  an edgeedge with one Li(2)O4F square pyramid,  an edgeedge with one Li(3)O4F square pyramid, and edges with two equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 48°. The Cr(1)-O(11) bond length is 2.04 Å. The Cr(1)-O(3) bond length is 2.03 Å. The Cr(1)-O(8) bond length is 1.98 Å. The Cr(1)-O(9) bond length is 1.98 Å. The Cr(1)-F(1) bond length is 1.97 Å. The Cr(1)-F(3) bond length is 1.97 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent F(2) atoms to form CrO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with four equivalent Li(3)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 48°. Both Cr(2)-O(1) bond lengths are 1.99 Å. Both Cr(2)-O(2) bond lengths are 2.01 Å. Both Cr(2)-F(2) bond lengths are 1.98 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O4F2 octahedra, corners with two equivalent Cr(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 33-54°. The P(1)-O(10) bond length is 1.53 Å. The P(1)-O(11) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(8) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O4F2 octahedra,  a cornercorner with one Cr(2)O4F2 octahedra, corners with two equivalent Cr(1)O4F2 octahedra,  a cornercorner with one Li(2)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(2)-O(2) bond length is 1.55 Å. The P(2)-O(3) bond length is 1.58 Å. The P(2)-O(4) bond length is 1.53 Å. The P(2)-O(9) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(1), one O(12), 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 Cr(2)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Li(2)O4F square pyramid,  a cornercorner with one Li(3)O4F square pyramid, and  an edgeedge with one Li(2)O4F square pyramid. The corner-sharing octahedral tilt angles range from 32-54°. The P(3)-O(1) bond length is 1.53 Å. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(6) bond length is 1.56 Å. The P(3)-O(7) bond length is 1.57 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Cr(2) and one P(3) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(3), one Cr(2), and one P(2) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Cr(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a T-shaped geometry to one Li(2), one V(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one V(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a T-shaped geometry to one Li(3), one Cr(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to two equivalent Li(1), one Cr(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(2), 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 trigonal planar geometry to one Li(2), one V(1), and one Cr(1) atom. In the second F site, F(2) is bonded in a trigonal planar geometry to one Li(3), one V(2), and one Cr(2) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one Cr(1) atom.