Li3V3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(2), one O(3), and one O(8) atom to form distorted LiO5 square pyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, and  an edgeedge with one P(3)O4 tetrahedra. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(3), one O(4), and one O(9) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(10), one O(15), one O(16), and one O(6) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(14), one O(2), one O(5), and one O(9) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. In the second V site, V(2) is bonded to one O(12), one O(16), one O(4), one O(7), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(13), one O(14), one O(15), and one O(6) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one V(1)O5 trigonal bipyramid, and  a cornercorner with one V(2)O5 trigonal bipyramid. In the second P site, P(2) is bonded to one O(10), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one V(1)O5 trigonal bipyramid, and  a cornercorner with one V(2)O5 trigonal bipyramid. In the third P site, P(3) is bonded to one O(12), one O(13), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 square pyramid. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(16), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O5 trigonal bipyramid and corners with two equivalent V(1)O5 trigonal bipyramids. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(3), and one P(1) atom. In the second 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 third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Li(3), one V(3), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(4) atom.
Li3V3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(12), one O(2), one O(3), and one O(8) atom to form distorted LiO5 square pyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, and  an edgeedge with one P(3)O4 tetrahedra. The Li(1)-O(1) bond length is 2.08 Å. The Li(1)-O(12) bond length is 2.14 Å. The Li(1)-O(2) bond length is 2.30 Å. The Li(1)-O(3) bond length is 1.96 Å. The Li(1)-O(8) bond length is 2.43 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(11), one O(3), one O(4), and one O(9) atom. The Li(2)-O(1) bond length is 2.03 Å. The Li(2)-O(11) bond length is 2.56 Å. The Li(2)-O(3) bond length is 2.01 Å. The Li(2)-O(4) bond length is 2.27 Å. The Li(2)-O(9) bond length is 2.08 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(10), one O(15), one O(16), and one O(6) atom. The Li(3)-O(10) bond length is 2.09 Å. The Li(3)-O(15) bond length is 2.01 Å. The Li(3)-O(16) bond length is 2.17 Å. The Li(3)-O(6) bond length is 1.99 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(11), one O(14), one O(2), one O(5), and one O(9) atom to form distorted VO5 trigonal bipyramids that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The V(1)-O(11) bond length is 1.97 Å. The V(1)-O(14) bond length is 2.41 Å. The V(1)-O(2) bond length is 2.06 Å. The V(1)-O(5) bond length is 1.91 Å. The V(1)-O(9) bond length is 1.97 Å. In the second V site, V(2) is bonded to one O(12), one O(16), one O(4), one O(7), and one O(8) atom to form VO5 trigonal bipyramids that share corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The V(2)-O(12) bond length is 1.95 Å. The V(2)-O(16) bond length is 2.16 Å. The V(2)-O(4) bond length is 2.07 Å. The V(2)-O(7) bond length is 1.92 Å. The V(2)-O(8) bond length is 1.92 Å. In the third V site, V(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(13), one O(14), one O(15), and one O(6) atom. The V(3)-O(1) bond length is 2.46 Å. The V(3)-O(10) bond length is 1.94 Å. The V(3)-O(13) bond length is 1.98 Å. The V(3)-O(14) bond length is 2.08 Å. The V(3)-O(15) bond length is 2.26 Å. The V(3)-O(6) bond length is 2.03 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Li(1)O5 square pyramids,  a cornercorner with one V(1)O5 trigonal bipyramid, and  a cornercorner with one V(2)O5 trigonal bipyramid. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O5 square pyramid,  a cornercorner with one V(1)O5 trigonal bipyramid, and  a cornercorner with one V(2)O5 trigonal bipyramid. The P(2)-O(10) bond length is 1.56 Å. The P(2)-O(3) bond length is 1.52 Å. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(12), one O(13), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O5 trigonal bipyramid, corners with two equivalent V(2)O5 trigonal bipyramids, and  an edgeedge with one Li(1)O5 square pyramid. The P(3)-O(12) bond length is 1.55 Å. The P(3)-O(13) bond length is 1.53 Å. The P(3)-O(14) bond length is 1.58 Å. The P(3)-O(8) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(16), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O5 trigonal bipyramid and corners with two equivalent V(1)O5 trigonal bipyramids. The P(4)-O(11) bond length is 1.57 Å. The P(4)-O(15) bond length is 1.54 Å. The P(4)-O(16) bond length is 1.55 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 4-coordinate geometry to one Li(1), one Li(2), one V(3), and one P(1) atom. In the second 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 third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Li(3), one V(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one V(1), and one P(4) atom. In the tenth O site, O(10) is bonded in a trigonal non-coplanar geometry to one Li(3), one V(3), and one P(2) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Li(2), one V(1), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a bent 150 degrees geometry to one V(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(3), one V(2), and one P(4) atom.