Li3VCrP2(HO5)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-68°. In the second Li site, Li(2) is bonded to one O(10), one O(5), one O(8), and one O(9) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-71°. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one H(1), one O(10), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. V(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 53°. Cr(1) is bonded to one O(1), one O(10), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 53°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 37-56°. In the second P site, P(2) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-50°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one Li(3) and one O(10) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. There are ten 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(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(3), 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(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Cr(1), and one P(1) atom to form corner-sharing OLi2CrP tetrahedra. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Cr(1), and one P(2) atom to form distorted corner-sharing OLi2CrP trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Li(2), one Li(3), one V(1), one Cr(1), and one H(1) atom.
Li3VCrP2(HO5)2 crystallizes in the triclinic P1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(3), one O(5), one O(6), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one Li(2)O4 trigonal pyramid, edges with two equivalent Cr(1)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-68°. The Li(1)-O(1) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.18 Å. The Li(1)-O(5) bond length is 2.24 Å. The Li(1)-O(6) bond length is 2.10 Å. The Li(1)-O(7) bond length is 2.17 Å. In the second Li site, Li(2) is bonded to one O(10), one O(5), one O(8), and one O(9) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-71°. The Li(2)-O(10) bond length is 2.05 Å. The Li(2)-O(5) bond length is 2.02 Å. The Li(2)-O(8) bond length is 2.10 Å. The Li(2)-O(9) bond length is 1.97 Å. In the third Li site, Li(3) is bonded in a 7-coordinate geometry to one H(1), one O(10), one O(2), one O(4), one O(6), one O(7), and one O(8) atom. The Li(3)-H(1) bond length is 2.14 Å. The Li(3)-O(10) bond length is 2.16 Å. The Li(3)-O(2) bond length is 2.09 Å. The Li(3)-O(4) bond length is 2.61 Å. The Li(3)-O(6) bond length is 2.21 Å. The Li(3)-O(7) bond length is 1.98 Å. The Li(3)-O(8) bond length is 1.97 Å. V(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(1)O5 trigonal bipyramids,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(2)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 53°. The V(1)-O(1) bond length is 2.15 Å. The V(1)-O(10) bond length is 2.25 Å. The V(1)-O(2) bond length is 2.17 Å. The V(1)-O(3) bond length is 2.15 Å. The V(1)-O(8) bond length is 2.25 Å. The V(1)-O(9) bond length is 2.17 Å. Cr(1) is bonded to one O(1), one O(10), one O(4), one O(5), one O(6), and one O(7) atom to form CrO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent Li(2)O4 trigonal pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 53°. The Cr(1)-O(1) bond length is 1.99 Å. The Cr(1)-O(10) bond length is 2.08 Å. The Cr(1)-O(4) bond length is 1.98 Å. The Cr(1)-O(5) bond length is 2.08 Å. The Cr(1)-O(6) bond length is 2.06 Å. The Cr(1)-O(7) bond length is 2.02 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and corners with two equivalent Li(2)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 37-56°. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(3), one O(6), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O4 trigonal pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 40-50°. The P(2)-O(3) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.58 Å. The P(2)-O(9) bond length is 1.54 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one Li(3) and one O(10) atom. The H(1)-O(10) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(1) atom. The H(2)-O(1) bond length is 0.99 Å. There are ten 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(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(3), 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(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Li(3), one Cr(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Cr(1), and one P(1) atom to form corner-sharing OLi2CrP tetrahedra. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Cr(1), and one P(2) atom to form distorted corner-sharing OLi2CrP trigonal pyramids. In the seventh O site, O(7) is bonded in a distorted see-saw-like geometry to one Li(1), one Li(3), one Cr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted single-bond geometry to one Li(2), one Li(3), one V(1), one Cr(1), and one H(1) atom.