Li3VP2H2O9 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(5), one O(7), and two equivalent O(4) atoms. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. V(1) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, 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 55-56°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. In the second P site, P(2) is bonded to one O(2), one O(5), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(1) and one O(3) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(7) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(3), one P(1), and one H(1) atom to form edge-sharing OLi2PH tetrahedra. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one H(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(2), and one P(2) atom to form distorted OLi3P trigonal pyramids that share  a cornercorner with one O(7)LiV2H tetrahedra and corners with two equivalent O(5)Li3P trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one P(2) atom. In the seventh O site, O(7) is bonded to one Li(1), two equivalent V(1), and one H(2) atom to form distorted OLiV2H tetrahedra that share corners with two equivalent O(7)LiV2H tetrahedra and  a cornercorner with one O(5)Li3P trigonal pyramid.
Li3VP2H2O9 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(2), one O(5), one O(7), and two equivalent O(4) atoms. The Li(1)-O(2) bond length is 1.88 Å. The Li(1)-O(5) bond length is 1.93 Å. The Li(1)-O(7) bond length is 2.19 Å. Both Li(1)-O(4) bond lengths are 2.45 Å. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. Both Li(2)-O(4) bond lengths are 2.16 Å. Both Li(2)-O(5) bond lengths are 2.22 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(6) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. Both Li(3)-O(1) bond lengths are 2.42 Å. Both Li(3)-O(2) bond lengths are 2.44 Å. Both Li(3)-O(6) bond lengths are 2.09 Å. V(1) is bonded to two equivalent O(4), two equivalent O(6), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, 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 55-56°. Both V(1)-O(4) bond lengths are 2.05 Å. Both V(1)-O(6) bond lengths are 2.01 Å. Both V(1)-O(7) bond lengths are 2.03 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with two equivalent Li(3)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-65°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.59 Å. Both P(1)-O(4) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(2), one O(5), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and edges with two equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(5) bond length is 1.55 Å. Both P(2)-O(6) bond lengths are 1.58 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(1) and one O(3) atom. The H(1)-O(1) bond length is 1.43 Å. The H(1)-O(3) bond length is 1.05 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(7) atom. The H(2)-O(7) bond length is 0.98 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(3), one P(1), and one H(1) atom to form edge-sharing OLi2PH tetrahedra. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one P(2) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one H(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded to one Li(1), two equivalent Li(2), and one P(2) atom to form distorted OLi3P trigonal pyramids that share  a cornercorner with one O(7)LiV2H tetrahedra and corners with two equivalent O(5)Li3P trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(3), one V(1), and one P(2) atom. In the seventh O site, O(7) is bonded to one Li(1), two equivalent V(1), and one H(2) atom to form distorted OLiV2H tetrahedra that share corners with two equivalent O(7)LiV2H tetrahedra and  a cornercorner with one O(5)Li3P trigonal pyramid.