Li3V(PO4)2 crystallizes in the monoclinic P2_1/c 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(3), one O(4), and two equivalent O(2) atoms. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent O(4) atoms. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form distorted OLi3P trigonal pyramids that share  a cornercorner with one O(2)Li3P trigonal pyramid, corners with three equivalent O(4)Li2VP trigonal pyramids,  an edgeedge with one O(4)Li2VP trigonal pyramid, and  an edgeedge with one O(2)Li3P trigonal pyramid. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(4)Li2VP trigonal pyramids, corners with three equivalent O(2)Li3P trigonal pyramids, and  an edgeedge with one O(2)Li3P trigonal pyramid.
Li3V(PO4)2 crystallizes in the monoclinic P2_1/c 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(3), one O(4), and two equivalent O(2) atoms. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-O(3) bond length is 2.23 Å. The Li(1)-O(4) bond length is 2.24 Å. There is one shorter (2.04 Å) and one longer (2.33 Å) Li(1)-O(2) bond length. In the second Li site, Li(2) is bonded in a square co-planar geometry to two equivalent O(2) and two equivalent O(4) atoms. Both Li(2)-O(2) bond lengths are 1.97 Å. Both Li(2)-O(4) bond lengths are 2.05 Å. V(1) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.03 Å. Both V(1)-O(3) bond lengths are 2.03 Å. Both V(1)-O(4) bond lengths are 2.14 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), and one P(1) atom to form distorted OLi3P trigonal pyramids that share  a cornercorner with one O(2)Li3P trigonal pyramid, corners with three equivalent O(4)Li2VP trigonal pyramids,  an edgeedge with one O(4)Li2VP trigonal pyramid, and  an edgeedge with one O(2)Li3P trigonal pyramid. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), and one P(1) atom to form distorted OLi2VP trigonal pyramids that share corners with two equivalent O(4)Li2VP trigonal pyramids, corners with three equivalent O(2)Li3P trigonal pyramids, and  an edgeedge with one O(2)Li3P trigonal pyramid.