Li2VP2HO8 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and one O(7) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(7), and one O(8) atom. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-52°. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-52°. H(1) is bonded in a linear geometry to one O(4) and one O(7) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one P(1), and one H(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one P(2), and one H(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(1) atom.
Li2VP2HO8 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(5), one O(6), and one O(7) atom. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(4) bond length is 1.97 Å. The Li(1)-O(5) bond length is 2.05 Å. The Li(1)-O(6) bond length is 2.00 Å. The Li(1)-O(7) bond length is 2.44 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(2), one O(3), one O(4), one O(7), and one O(8) atom. The Li(2)-O(2) bond length is 2.07 Å. The Li(2)-O(3) bond length is 1.98 Å. The Li(2)-O(4) bond length is 2.39 Å. The Li(2)-O(7) bond length is 2.03 Å. The Li(2)-O(8) bond length is 1.99 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(8) atom to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. The V(1)-O(1) bond length is 2.03 Å. The V(1)-O(2) bond length is 2.07 Å. The V(1)-O(3) bond length is 2.04 Å. The V(1)-O(5) bond length is 2.10 Å. The V(1)-O(6) bond length is 2.08 Å. The V(1)-O(8) bond length is 2.00 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-52°. The P(1)-O(2) bond length is 1.55 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(8) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-52°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.58 Å. H(1) is bonded in a linear geometry to one O(4) and one O(7) atom. The H(1)-O(4) bond length is 1.40 Å. The H(1)-O(7) bond length is 1.08 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one P(1), and one H(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one P(2), and one H(1) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(2), one V(1), and one P(1) atom.