LiVOPO4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), and two equivalent O(1) atoms. V(1) is bonded to one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form VO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra and  an edgeedge with one V(1)O5 trigonal bipyramid. 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 three equivalent V(1)O5 trigonal bipyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom.
LiVOPO4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), and two equivalent O(1) atoms. The Li(1)-O(2) bond length is 2.27 Å. The Li(1)-O(4) bond length is 2.14 Å. There is one shorter (1.97 Å) and one longer (2.03 Å) Li(1)-O(1) bond length. V(1) is bonded to one O(3), one O(4), one O(5), and two equivalent O(2) atoms to form VO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra and  an edgeedge with one V(1)O5 trigonal bipyramid. The V(1)-O(3) bond length is 1.94 Å. The V(1)-O(4) bond length is 1.96 Å. The V(1)-O(5) bond length is 1.91 Å. There is one shorter (1.71 Å) and one longer (2.04 Å) V(1)-O(2) bond length. 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 three equivalent V(1)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.59 Å. The P(1)-O(5) bond length is 1.56 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Li(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom.