Li2VOP2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with four P(1,1)O4 tetrahedra;  an edgeedge with one V(1)O6 octahedra; and  an edgeedge with one Li(1)O4 tetrahedra. In the second Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with four P(1,1)O4 tetrahedra;  an edgeedge with one V(1)O6 octahedra; and  an edgeedge with one Li(1)O4 tetrahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six P(1,1)O4 tetrahedra and edges with two equivalent Li(1)O4 tetrahedra. In the second V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six P(1,1)O4 tetrahedra and edges with two equivalent Li(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, 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 V(1,1)O6 octahedra and corners with four Li(1,1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-41°. In the second P site, 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 V(1,1)O6 octahedra and corners with four Li(1,1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-41°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the third 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 fourth 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 fifth O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one P(1) atom. In the seventh O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the eighth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.
Li2VOP2O7 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with four P(1,1)O4 tetrahedra;  an edgeedge with one V(1)O6 octahedra; and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(2) bond length is 1.95 Å. There is one shorter (1.79 Å) and one longer (1.89 Å) Li(1)-O(3) bond length. In the second Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with four P(1,1)O4 tetrahedra;  an edgeedge with one V(1)O6 octahedra; and  an edgeedge with one Li(1)O4 tetrahedra. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(2) bond length is 1.95 Å. There is one shorter (1.79 Å) and one longer (1.89 Å) Li(1)-O(3) bond length. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six P(1,1)O4 tetrahedra and edges with two equivalent Li(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.00 Å. Both V(1)-O(2) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 1.98 Å. In the second V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms to form VO6 octahedra that share corners with six P(1,1)O4 tetrahedra and edges with two equivalent Li(1)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.00 Å. Both V(1)-O(2) bond lengths are 1.99 Å. Both V(1)-O(4) bond lengths are 1.98 Å. There are two inequivalent P sites. In the first P site, 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 V(1,1)O6 octahedra and corners with four Li(1,1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-41°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.58 Å. In the second P site, 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 V(1,1)O6 octahedra and corners with four Li(1,1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 36-41°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.58 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the second O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one V(1), and one P(1) atom. In the third 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 fourth 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 fifth O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted T-shaped geometry to two equivalent Li(1) and one P(1) atom. In the seventh O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the eighth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.