Li3V3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(9) atom. In the second Li site, Li(2) is bonded to one O(15), one O(2), one O(3), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-71°. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to one O(10), one O(2), one O(3), and one O(7) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(14), one O(5), one O(8), and two equivalent O(12) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 67°. In the second V site, V(2) is bonded to one O(11), one O(13), one O(4), one O(6), and two equivalent O(16) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-67°. In the third V site, V(3) is bonded to one O(1), one O(10), one O(11), one O(15), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-50°. In the second P site, P(2) is bonded to one O(1), one O(12), one O(15), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-62°. In the third P site, P(3) is bonded to one O(10), one O(16), one O(2), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-58°. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-59°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one P(4) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one V(3), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(3), one V(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one V(1), one V(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) atom.
Li3V3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(9) atom. The Li(1)-O(1) bond length is 2.18 Å. The Li(1)-O(3) bond length is 2.05 Å. The Li(1)-O(4) bond length is 1.99 Å. The Li(1)-O(9) bond length is 2.18 Å. In the second Li site, Li(2) is bonded to one O(15), one O(2), one O(3), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 61-71°. The Li(2)-O(15) bond length is 2.21 Å. The Li(2)-O(2) bond length is 1.96 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(6) bond length is 2.28 Å. The Li(2)-O(8) bond length is 2.43 Å. In the third Li site, Li(3) is bonded in a distorted see-saw-like geometry to one O(10), one O(2), one O(3), and one O(7) atom. The Li(3)-O(10) bond length is 2.14 Å. The Li(3)-O(2) bond length is 1.92 Å. The Li(3)-O(3) bond length is 2.05 Å. The Li(3)-O(7) bond length is 2.00 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(13), one O(14), one O(5), one O(8), and two equivalent O(12) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 67°. The V(1)-O(13) bond length is 2.21 Å. The V(1)-O(14) bond length is 2.03 Å. The V(1)-O(5) bond length is 1.99 Å. The V(1)-O(8) bond length is 1.99 Å. There is one shorter (2.09 Å) and one longer (2.29 Å) V(1)-O(12) bond length. In the second V site, V(2) is bonded to one O(11), one O(13), one O(4), one O(6), and two equivalent O(16) atoms to form distorted VO6 octahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-67°. The V(2)-O(11) bond length is 2.28 Å. The V(2)-O(13) bond length is 2.15 Å. The V(2)-O(4) bond length is 2.00 Å. The V(2)-O(6) bond length is 1.98 Å. There is one shorter (2.01 Å) and one longer (2.12 Å) V(2)-O(16) bond length. In the third V site, V(3) is bonded to one O(1), one O(10), one O(11), one O(15), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. The V(3)-O(1) bond length is 2.11 Å. The V(3)-O(10) bond length is 1.96 Å. The V(3)-O(11) bond length is 2.13 Å. The V(3)-O(15) bond length is 2.09 Å. The V(3)-O(7) bond length is 2.08 Å. The V(3)-O(9) bond length is 1.99 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-50°. The P(1)-O(11) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(1), one O(12), one O(15), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 49-62°. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(12) bond length is 1.57 Å. The P(2)-O(15) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(16), one O(2), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 24-58°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(16) bond length is 1.61 Å. The P(3)-O(2) bond length is 1.49 Å. The P(3)-O(8) bond length is 1.55 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(3), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 29-59°. The P(4)-O(13) bond length is 1.59 Å. The P(4)-O(14) bond length is 1.53 Å. The P(4)-O(3) bond length is 1.54 Å. The P(4)-O(9) bond length is 1.57 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Li(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted tetrahedral geometry to one Li(1), one Li(2), one Li(3), and one P(4) atom. In the fourth O site, O(4) is bonded in a trigonal non-coplanar geometry to one Li(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one V(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(1), one V(3), and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted T-shaped geometry to one Li(3), one V(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one V(2), one V(3), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one V(1), one V(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a trigonal planar geometry to one Li(2), one V(3), and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent V(2) and one P(3) atom.