Li2V3(P2O7)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), and two equivalent O(10) atoms. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(10), one O(12), and one O(4) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(5), one O(7), one O(9), and two equivalent O(6) atoms to form distorted VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with four equivalent P(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. In the second V site, V(2) is bonded to one O(1), one O(12), one O(14), one O(2), one O(3), and one O(4) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(3)O6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(13), one O(3), one O(5), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-60°. In the second P site, P(2) is bonded to one O(11), one O(14), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-54°. In the third P site, P(3) is bonded to one O(10), one O(12), one O(2), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. In the fourth P site, P(4) is bonded to one O(11), one O(13), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-65°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent V(1) and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(4) atom. In the tenth O site, O(10) is bonded to one Li(2), two equivalent Li(1), and one P(3) atom to form edge-sharing OLi3P trigonal pyramids. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom.
Li2V3(P2O7)2 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(4), and two equivalent O(10) atoms. The Li(1)-O(2) bond length is 2.02 Å. The Li(1)-O(4) bond length is 2.46 Å. There is one shorter (2.12 Å) and one longer (2.29 Å) Li(1)-O(10) bond length. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(10), one O(12), and one O(4) atom. The Li(2)-O(10) bond length is 2.03 Å. The Li(2)-O(12) bond length is 2.09 Å. The Li(2)-O(4) bond length is 2.05 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(5), one O(7), one O(9), and two equivalent O(6) atoms to form distorted VO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with four equivalent P(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. The V(1)-O(13) bond length is 2.19 Å. The V(1)-O(5) bond length is 2.13 Å. The V(1)-O(7) bond length is 2.30 Å. The V(1)-O(9) bond length is 2.15 Å. There is one shorter (2.21 Å) and one longer (2.38 Å) V(1)-O(6) bond length. In the second V site, V(2) is bonded to one O(1), one O(12), one O(14), one O(2), one O(3), and one O(4) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(3)O6 octahedra. The V(2)-O(1) bond length is 2.19 Å. The V(2)-O(12) bond length is 2.19 Å. The V(2)-O(14) bond length is 2.11 Å. The V(2)-O(2) bond length is 2.26 Å. The V(2)-O(3) bond length is 2.20 Å. The V(2)-O(4) bond length is 2.21 Å. In the third V site, V(3) is bonded to one O(1), one O(13), one O(3), one O(5), one O(7), and one O(9) atom to form VO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The V(3)-O(1) bond length is 2.25 Å. The V(3)-O(13) bond length is 2.18 Å. The V(3)-O(3) bond length is 2.19 Å. The V(3)-O(5) bond length is 2.15 Å. The V(3)-O(7) bond length is 2.21 Å. The V(3)-O(9) bond length is 2.18 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-60°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.53 Å. The P(1)-O(8) bond length is 1.62 Å. In the second P site, P(2) is bonded to one O(11), one O(14), one O(3), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-54°. The P(2)-O(11) bond length is 1.60 Å. The P(2)-O(14) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(2), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-54°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(12) bond length is 1.54 Å. The P(3)-O(2) bond length is 1.53 Å. The P(3)-O(8) bond length is 1.62 Å. In the fourth P site, P(4) is bonded to one O(11), one O(13), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent V(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-65°. The P(4)-O(11) bond length is 1.60 Å. The P(4)-O(13) bond length is 1.54 Å. The P(4)-O(6) bond length is 1.53 Å. The P(4)-O(9) bond length is 1.53 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent V(1) and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one V(1), one V(3), and one P(4) atom. In the tenth O site, O(10) is bonded to one Li(2), two equivalent Li(1), and one P(3) atom to form edge-sharing OLi3P trigonal pyramids. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom.