Li2VP2HO8 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(3), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-59°. In the second Li site, Li(2) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-70°. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-54°. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. H(1) is bonded in a linear geometry to one O(5) and one O(7) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), 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 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 trigonal planar geometry to one Li(2), 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(2), one P(1), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one P(1), and one H(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(2) atom.
Li2VP2HO8 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(3), and one O(6) atom to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-59°. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 1.91 Å. The Li(1)-O(3) bond length is 2.21 Å. The Li(1)-O(6) bond length is 1.90 Å. In the second Li site, Li(2) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form LiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-70°. The Li(2)-O(4) bond length is 2.17 Å. The Li(2)-O(5) bond length is 1.97 Å. The Li(2)-O(6) bond length is 1.97 Å. The Li(2)-O(8) bond length is 1.95 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(7), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The V(1)-O(1) bond length is 2.10 Å. The V(1)-O(2) bond length is 1.99 Å. The V(1)-O(3) bond length is 2.01 Å. The V(1)-O(4) bond length is 2.04 Å. The V(1)-O(7) bond length is 2.24 Å. The V(1)-O(8) bond length is 2.13 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(5), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-54°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.52 Å. The P(1)-O(7) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 47°. The P(2)-O(2) bond length is 1.59 Å. The P(2)-O(4) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.57 Å. H(1) is bonded in a linear geometry to one O(5) and one O(7) atom. The H(1)-O(5) bond length is 1.59 Å. The H(1)-O(7) bond length is 1.03 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one V(1), 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 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 trigonal planar geometry to one Li(2), 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(2), one P(1), and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one V(1), one P(1), and one H(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(2) atom.