LiVOPO4 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one O(5) atom. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and  an edgeedge with one P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and  an edgeedge with one V(1)O5 trigonal bipyramid. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom.
LiVOPO4 crystallizes in the orthorhombic P2_12_12_1 space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(3), one O(4), and one O(5) atom. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(3) bond length is 1.94 Å. The Li(1)-O(4) bond length is 2.43 Å. The Li(1)-O(5) bond length is 2.16 Å. V(1) is bonded to one O(1), one O(2), one O(3), one O(4), and one O(5) atom to form distorted VO5 trigonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra and  an edgeedge with one P(1)O4 tetrahedra. The V(1)-O(1) bond length is 1.97 Å. The V(1)-O(2) bond length is 1.64 Å. The V(1)-O(3) bond length is 2.00 Å. The V(1)-O(4) bond length is 2.05 Å. The V(1)-O(5) bond length is 2.02 Å. P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O5 trigonal bipyramids and  an edgeedge with one V(1)O5 trigonal bipyramid. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(5) bond length is 1.55 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Li(1) and one V(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(1) atom.