Li2VCrP2(HO5)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(5) atoms to form distorted LiO5 square pyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-64°. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. Cr(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 52°. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 38-54°. H(1) is bonded in a single-bond geometry to one O(1) atom. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one V(1), one Cr(1), and one H(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cr(1), and one P(1) atom.
Li2VCrP2(HO5)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(3), one O(4), and two equivalent O(5) atoms to form distorted LiO5 square pyramids that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Cr(1)O6 octahedra,  an edgeedge with one Li(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 52-64°. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(3) bond length is 2.15 Å. The Li(1)-O(4) bond length is 2.10 Å. There is one shorter (2.06 Å) and one longer (2.20 Å) Li(1)-O(5) bond length. V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. Both V(1)-O(1) bond lengths are 2.08 Å. Both V(1)-O(2) bond lengths are 2.06 Å. Both V(1)-O(3) bond lengths are 2.02 Å. Cr(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles are 52°. Both Cr(1)-O(1) bond lengths are 2.03 Å. Both Cr(1)-O(4) bond lengths are 1.99 Å. Both Cr(1)-O(5) bond lengths are 2.05 Å. P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Li(1)O5 square pyramids, and  an edgeedge with one Li(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 38-54°. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.56 Å. H(1) is bonded in a single-bond geometry to one O(1) atom. The H(1)-O(1) bond length is 0.99 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one V(1), one Cr(1), and one H(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1), one Cr(1), and one P(1) atom.