Li3V(PO4)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(2), one O(4), 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(2)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-74°. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(2), and one O(5) 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 Li(5)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-76°. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(6), and two equivalent O(9) atoms. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(2), one O(4), and one O(5) atom. In the fifth Li site, Li(5) is bonded to one O(10), one O(11), one O(12), and one O(6) atom to form distorted 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 Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-76°. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(9) atoms to form distorted VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the second V site, V(2) is bonded to one O(12), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one 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(5)O4 tetrahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-55°. In the second P site, P(2) is bonded to one O(10), one O(12), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one 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(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-55°. In the third P site, P(3) is bonded to one O(1), one O(11), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-54°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), and one P(1) atom to form distorted corner-sharing OLi3P tetrahedra. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one Li(5), one V(1), 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(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to 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(1), one Li(3), one V(1), and one P(2) atom. In the tenth O site, O(10) is bonded to one Li(2), one Li(4), one Li(5), and one P(2) atom to form distorted corner-sharing OLi3P tetrahedra. In the eleventh O site, O(11) is bonded to one Li(1), one Li(4), one Li(5), and one P(3) atom to form distorted corner-sharing OLi3P trigonal pyramids. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one V(2), and one P(2) atom.
Li3V(PO4)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(2), one O(4), 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(2)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-74°. The Li(1)-O(11) bond length is 1.97 Å. The Li(1)-O(2) bond length is 2.11 Å. The Li(1)-O(4) bond length is 1.97 Å. The Li(1)-O(9) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(1), one O(10), one O(2), and one O(5) 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 Li(5)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-76°. The Li(2)-O(1) bond length is 2.05 Å. The Li(2)-O(10) bond length is 2.12 Å. The Li(2)-O(2) bond length is 2.01 Å. The Li(2)-O(5) bond length is 1.98 Å. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(6), and two equivalent O(9) atoms. Both Li(3)-O(1) bond lengths are 2.58 Å. Both Li(3)-O(6) bond lengths are 2.64 Å. Both Li(3)-O(9) bond lengths are 2.63 Å. In the fourth Li site, Li(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(2), one O(4), and one O(5) atom. The Li(4)-O(10) bond length is 2.10 Å. The Li(4)-O(11) bond length is 2.07 Å. The Li(4)-O(12) bond length is 2.40 Å. The Li(4)-O(2) bond length is 2.09 Å. The Li(4)-O(4) bond length is 2.54 Å. The Li(4)-O(5) bond length is 2.43 Å. In the fifth Li site, Li(5) is bonded to one O(10), one O(11), one O(12), and one O(6) atom to form distorted 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 Li(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-76°. The Li(5)-O(10) bond length is 2.01 Å. The Li(5)-O(11) bond length is 2.22 Å. The Li(5)-O(12) bond length is 1.97 Å. The Li(5)-O(6) bond length is 2.04 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(9) atoms to form distorted VO6 octahedra that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.12 Å. Both V(1)-O(6) bond lengths are 2.10 Å. Both V(1)-O(9) bond lengths are 2.09 Å. In the second V site, V(2) is bonded to one O(12), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The V(2)-O(12) bond length is 2.11 Å. The V(2)-O(3) bond length is 1.99 Å. The V(2)-O(4) bond length is 2.10 Å. The V(2)-O(5) bond length is 2.11 Å. The V(2)-O(7) bond length is 1.97 Å. The V(2)-O(8) bond length is 1.98 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one 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(5)O4 tetrahedra, and corners with two equivalent Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-55°. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(10), one O(12), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one 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(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-55°. The P(2)-O(10) bond length is 1.55 Å. The P(2)-O(12) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.52 Å. The P(2)-O(9) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(1), one O(11), one O(4), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(5)O4 tetrahedra, and corners with two equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 29-54°. The P(3)-O(1) bond length is 1.57 Å. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(4) bond length is 1.57 Å. The P(3)-O(7) bond length is 1.53 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(3) atom. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), and one P(1) atom to form distorted corner-sharing OLi3P tetrahedra. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Li(4), one V(2), and one P(3) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(2), one Li(4), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(3), one Li(5), one V(1), 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(3) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to 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(1), one Li(3), one V(1), and one P(2) atom. In the tenth O site, O(10) is bonded to one Li(2), one Li(4), one Li(5), and one P(2) atom to form distorted corner-sharing OLi3P tetrahedra. In the eleventh O site, O(11) is bonded to one Li(1), one Li(4), one Li(5), and one P(3) atom to form distorted corner-sharing OLi3P trigonal pyramids. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(4), one Li(5), one V(2), and one P(2) atom.