LiVPO4 is Chalcostibite-derived structured and crystallizes in the trigonal P31c space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent V(1)O5 trigonal bipyramids. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(4) and three equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent V(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(5) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with three equivalent V(1)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(6) and three equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent V(1)O5 trigonal bipyramids. There are six 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(2) 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(1) atom. 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(3) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to three equivalent V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a tetrahedral geometry to three equivalent Li(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one P(3) atom.
LiVPO4 is Chalcostibite-derived structured and crystallizes in the trigonal P31c space group. Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with three equivalent V(1)O5 trigonal bipyramids. The Li(1)-O(1) bond length is 1.99 Å. The Li(1)-O(2) bond length is 2.04 Å. The Li(1)-O(3) bond length is 2.02 Å. The Li(1)-O(5) bond length is 1.96 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(6) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and edges with two equivalent V(1)O5 trigonal bipyramids. The V(1)-O(1) bond length is 2.14 Å. The V(1)-O(2) bond length is 2.18 Å. The V(1)-O(3) bond length is 2.11 Å. The V(1)-O(4) bond length is 2.27 Å. The V(1)-O(6) bond length is 2.24 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(4) and three equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent V(1)O5 trigonal bipyramids. The P(1)-O(4) bond length is 1.61 Å. All P(1)-O(2) bond lengths are 1.54 Å. In the second P site, P(2) is bonded to one O(5) and three equivalent O(1) atoms to form PO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra and corners with three equivalent V(1)O5 trigonal bipyramids. The P(2)-O(5) bond length is 1.55 Å. All P(2)-O(1) bond lengths are 1.57 Å. In the third P site, P(3) is bonded to one O(6) and three equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent V(1)O5 trigonal bipyramids. The P(3)-O(6) bond length is 1.59 Å. All P(3)-O(3) bond lengths are 1.54 Å. There are six 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(2) 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(1) atom. 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(3) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to three equivalent V(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a tetrahedral geometry to three equivalent Li(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to three equivalent V(1) and one P(3) atom.