LiVCrP2(O4F)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), one O(4), one O(7), and one F(2) atom to form distorted LiO4F trigonal bipyramids that share corners with two equivalent Cr(1)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 V(2)O4F2 octahedra, 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(1)O4F2 octahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Cr(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 41°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) 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 two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. In the second Cr site, Cr(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent F(1) atoms to form CrO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 41°. 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 Cr(1)O4F2 octahedra,  a cornercorner with one Cr(2)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Li(1)O4F trigonal bipyramid, and  an edgeedge with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-52°. 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 Cr(1)O4F2 octahedra,  a cornercorner with one Cr(2)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra, and  a cornercorner with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 25-50°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), 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 Cr(2) 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 Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(1), one V(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to 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 bent 150 degrees geometry to one V(2) and one Cr(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Cr(1) atom.
LiVCrP2(O4F)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), one O(4), one O(7), and one F(2) atom to form distorted LiO4F trigonal bipyramids that share corners with two equivalent Cr(1)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 V(2)O4F2 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-60°. The Li(1)-O(1) bond length is 2.12 Å. The Li(1)-O(2) 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 2.16 Å. The Li(1)-F(2) bond length is 1.96 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(1)O4F2 octahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. Both V(1)-O(2) bond lengths are 2.00 Å. Both V(1)-O(8) bond lengths are 1.84 Å. Both V(1)-F(2) bond lengths are 1.99 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(7), and two equivalent F(1) atoms to form VO4F2 octahedra that share corners with two equivalent Cr(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 41°. Both V(2)-O(1) bond lengths are 2.00 Å. Both V(2)-O(7) bond lengths are 1.89 Å. Both V(2)-F(1) bond lengths are 1.93 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) 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 two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent Li(1)O4F trigonal bipyramids. The corner-sharing octahedral tilt angles are 45°. Both Cr(1)-O(4) bond lengths are 2.01 Å. Both Cr(1)-O(5) bond lengths are 1.97 Å. Both Cr(1)-F(2) bond lengths are 1.99 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(3), two equivalent O(6), and two equivalent F(1) atoms to form CrO4F2 octahedra that share corners with two equivalent V(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 41°. Both Cr(2)-O(3) bond lengths are 1.98 Å. Both Cr(2)-O(6) bond lengths are 1.98 Å. Both Cr(2)-F(1) bond lengths are 2.00 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 Cr(1)O4F2 octahedra,  a cornercorner with one Cr(2)O4F2 octahedra, corners with two equivalent V(2)O4F2 octahedra,  a cornercorner with one Li(1)O4F trigonal bipyramid, and  an edgeedge with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-52°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.58 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 Cr(1)O4F2 octahedra,  a cornercorner with one Cr(2)O4F2 octahedra, corners with two equivalent V(1)O4F2 octahedra, and  a cornercorner with one Li(1)O4F trigonal bipyramid. The corner-sharing octahedral tilt angles range from 25-50°. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.51 Å. The P(2)-O(8) bond length is 1.59 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), 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 Cr(2) 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 Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Cr(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(1), one V(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to 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 bent 150 degrees geometry to one V(2) and one Cr(2) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Cr(1) atom.