LiVPO4 crystallizes in the orthorhombic Fdd2 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted VO6 pentagonal pyramids that share corners with four equivalent V(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 pentagonal pyramids and  an edgeedge with one V(1)O6 pentagonal pyramid. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent V(1), and one P(1) atom.
LiVPO4 crystallizes in the orthorhombic Fdd2 space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Li(1)-O(2) bond lengths are 2.29 Å. There are two shorter (2.12 Å) and two longer (2.40 Å) Li(1)-O(1) bond lengths. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form distorted VO6 pentagonal pyramids that share corners with four equivalent V(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.24 Å. There are two shorter (2.13 Å) and two longer (2.29 Å) V(1)-O(2) bond lengths. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with four equivalent V(1)O6 pentagonal pyramids and  an edgeedge with one V(1)O6 pentagonal pyramid. Both P(1)-O(1) bond lengths are 1.55 Å. Both P(1)-O(2) bond lengths are 1.57 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(1), two equivalent V(1), and one P(1) atom.