Li2V2P2O11 crystallizes in the orthorhombic P2_12_12 space group. Li(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted VO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra and  a cornercorner with one V(1)O5 trigonal bipyramid. 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)O5 trigonal bipyramids. There are six inequivalent O sites. In the first O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent V(1) atoms. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one P(1) atom. In the third O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the sixth O site, O(5) is bonded in a linear geometry to one Li(1) and one V(1) atom.
Li2V2P2O11 crystallizes in the orthorhombic P2_12_12 space group. Li(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. The Li(1)-O(1) bond length is 1.91 Å. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(5) bond length is 1.99 Å. V(1) is bonded to one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted VO5 trigonal bipyramids that share corners with three equivalent P(1)O4 tetrahedra and  a cornercorner with one V(1)O5 trigonal bipyramid. The V(1)-O(2) bond length is 2.03 Å. The V(1)-O(3) bond length is 1.87 Å. The V(1)-O(4) bond length is 1.86 Å. The V(1)-O(5) bond length is 1.64 Å. The V(1)-O(6) bond length is 1.82 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)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.56 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a bent 120 degrees geometry to two equivalent V(1) atoms. In the second O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one P(1) atom. In the third O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(1) atom. In the fourth O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fifth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the sixth O site, O(5) is bonded in a linear geometry to one Li(1) and one V(1) atom.