Li2V3(P2O7)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO4 trigonal pyramids that share corners with three equivalent V(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-70°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. In the second V site, V(2) is bonded to one O(1), one O(3), one O(6), one O(7), and two equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-65°. In the second P site, P(2) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 48-65°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) 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 distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one V(1), one V(2), and one P(2) atom to form distorted corner-sharing OLiV2P tetrahedra.
Li2V3(P2O7)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form distorted LiO4 trigonal pyramids that share corners with three equivalent V(2)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-70°. The Li(1)-O(3) bond length is 2.09 Å. The Li(1)-O(4) bond length is 2.03 Å. The Li(1)-O(6) bond length is 2.07 Å. The Li(1)-O(7) bond length is 2.09 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Li(1)O4 trigonal pyramids. Both V(1)-O(1) bond lengths are 2.22 Å. Both V(1)-O(4) bond lengths are 2.25 Å. Both V(1)-O(7) bond lengths are 2.23 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(6), one O(7), and two equivalent O(2) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids,  an edgeedge with one V(1)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The V(2)-O(1) bond length is 2.28 Å. The V(2)-O(3) bond length is 2.23 Å. The V(2)-O(6) bond length is 2.23 Å. The V(2)-O(7) bond length is 2.40 Å. There is one shorter (2.14 Å) and one longer (2.19 Å) V(2)-O(2) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 52-65°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.63 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(1), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 48-65°. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(3) bond length is 1.52 Å. The P(2)-O(5) bond length is 1.60 Å. The P(2)-O(7) bond length is 1.55 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) 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 distorted bent 150 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the seventh O site, O(7) is bonded to one Li(1), one V(1), one V(2), and one P(2) atom to form distorted corner-sharing OLiV2P tetrahedra.