Li4V2(PO4)3 is Esseneite-like structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-68°. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(5), and one O(9) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-69°. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(3), and one O(8) atom to form LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-67°. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(6), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, 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  a cornercorner with one Li(3)O4 trigonal pyramid. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-52°. In the second P site, P(2) is bonded to one O(12), one O(3), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 26-51°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(2), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 20-57°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(2), and one P(1) atom to form distorted corner-sharing OLi2VP tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(2), and one P(3) atom to form corner-sharing OLi2VP tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(2), and one P(2) atom to form distorted corner-sharing OLi2VP tetrahedra. In the fourth O site, O(4) is bonded in a 3-coordinate 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 trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one P(2) atom.
Li4V2(PO4)3 is Esseneite-like structured and crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(4), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-68°. The Li(1)-O(1) bond length is 2.17 Å. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(4) bond length is 1.95 Å. The Li(1)-O(7) bond length is 2.00 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(5), and one O(9) atom to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 62-69°. The Li(2)-O(2) bond length is 2.12 Å. The Li(2)-O(3) bond length is 1.98 Å. The Li(2)-O(5) bond length is 1.99 Å. The Li(2)-O(9) bond length is 1.94 Å. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(3), and one O(8) atom to form LiO4 trigonal pyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-67°. The Li(3)-O(1) bond length is 1.94 Å. The Li(3)-O(11) bond length is 2.05 Å. The Li(3)-O(3) bond length is 1.97 Å. The Li(3)-O(8) bond length is 2.06 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(11), one O(12), one O(6), and one O(8) atom. The Li(4)-O(11) bond length is 2.11 Å. The Li(4)-O(12) bond length is 2.43 Å. The Li(4)-O(6) bond length is 1.99 Å. The Li(4)-O(8) bond length is 2.04 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), and one O(7) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, 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  a cornercorner with one Li(3)O4 trigonal pyramid. The V(1)-O(10) bond length is 1.97 Å. The V(1)-O(11) bond length is 2.16 Å. The V(1)-O(12) bond length is 2.02 Å. The V(1)-O(5) bond length is 2.11 Å. The V(1)-O(6) bond length is 2.08 Å. The V(1)-O(7) bond length is 2.11 Å. In the second V site, V(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one Li(1)O4 tetrahedra,  an edgeedge with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The V(2)-O(1) bond length is 2.16 Å. The V(2)-O(2) bond length is 2.20 Å. The V(2)-O(3) bond length is 2.19 Å. The V(2)-O(4) bond length is 2.15 Å. The V(2)-O(8) bond length is 2.19 Å. The V(2)-O(9) bond length is 2.13 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 28-52°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(12), one O(3), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 26-51°. The P(2)-O(12) bond length is 1.53 Å. The P(2)-O(3) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(2), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 20-57°. The P(3)-O(10) bond length is 1.53 Å. The P(3)-O(11) bond length is 1.58 Å. The P(3)-O(2) bond length is 1.56 Å. The P(3)-O(9) bond length is 1.53 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(2), and one P(1) atom to form distorted corner-sharing OLi2VP tetrahedra. In the second O site, O(2) is bonded to one Li(1), one Li(2), one V(2), and one P(3) atom to form corner-sharing OLi2VP tetrahedra. In the third O site, O(3) is bonded to one Li(2), one Li(3), one V(2), and one P(2) atom to form distorted corner-sharing OLi2VP tetrahedra. In the fourth O site, O(4) is bonded in a 3-coordinate 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 trigonal planar geometry to one Li(2), one V(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Li(2), one V(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one V(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(4), one V(1), and one P(2) atom.