Li2V3(PO4)3 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(12), two equivalent O(4), and two equivalent O(7) atoms. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(10), and two equivalent O(8) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and one O(8) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a faceface with one V(2)O6 octahedra, and  a faceface with one V(3)O6 octahedra. In the second V site, V(2) is bonded to one O(12), one O(4), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. In the third V site, V(3) is bonded to one O(1), one O(10), one O(11), one O(2), one O(3), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  a faceface with one 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(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-45°. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-49°. In the third P site, P(3) is bonded to two equivalent O(6) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-51°. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(12), 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, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-51°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one V(1), one V(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(2) and one P(4) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one V(1), one V(3), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(3), one V(1), one V(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(4) atom.
Li2V3(PO4)3 crystallizes in the monoclinic C2 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(12), two equivalent O(4), and two equivalent O(7) atoms. Both Li(1)-O(12) bond lengths are 2.16 Å. Both Li(1)-O(4) bond lengths are 2.59 Å. Both Li(1)-O(7) bond lengths are 2.10 Å. In the second Li site, Li(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(10), and two equivalent O(8) atoms. Both Li(2)-O(1) bond lengths are 2.27 Å. Both Li(2)-O(10) bond lengths are 2.60 Å. Both Li(2)-O(8) bond lengths are 2.14 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(10), one O(11), one O(2), one O(3), and one O(8) atom. The Li(3)-O(10) bond length is 2.18 Å. The Li(3)-O(11) bond length is 2.13 Å. The Li(3)-O(2) bond length is 2.31 Å. The Li(3)-O(3) bond length is 2.26 Å. The Li(3)-O(8) bond length is 2.61 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(10), one O(11), one O(4), one O(5), one O(7), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a faceface with one V(2)O6 octahedra, and  a faceface with one V(3)O6 octahedra. The V(1)-O(10) bond length is 2.27 Å. The V(1)-O(11) bond length is 2.24 Å. The V(1)-O(4) bond length is 2.20 Å. The V(1)-O(5) bond length is 2.17 Å. The V(1)-O(7) bond length is 2.21 Å. The V(1)-O(8) bond length is 2.22 Å. In the second V site, V(2) is bonded to one O(12), one O(4), one O(5), one O(6), one O(7), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. The V(2)-O(12) bond length is 2.06 Å. The V(2)-O(4) bond length is 2.07 Å. The V(2)-O(5) bond length is 2.03 Å. The V(2)-O(6) bond length is 1.98 Å. The V(2)-O(7) bond length is 2.05 Å. The V(2)-O(9) bond length is 2.00 Å. In the third V site, V(3) is bonded to one O(1), one O(10), one O(11), one O(2), one O(3), and one O(8) atom to form distorted VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. The V(3)-O(1) bond length is 2.12 Å. The V(3)-O(10) bond length is 2.21 Å. The V(3)-O(11) bond length is 2.20 Å. The V(3)-O(2) bond length is 2.11 Å. The V(3)-O(3) bond length is 2.11 Å. The V(3)-O(8) bond length is 2.20 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-45°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.57 Å. In the second P site, P(2) is bonded to two equivalent O(2) and two equivalent O(7) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-49°. Both P(2)-O(2) bond lengths are 1.52 Å. Both P(2)-O(7) bond lengths are 1.59 Å. In the third P site, P(3) is bonded to two equivalent O(6) and two equivalent O(8) atoms to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-51°. Both P(3)-O(6) bond lengths are 1.52 Å. Both P(3)-O(8) bond lengths are 1.58 Å. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(12), 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, and corners with two equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-51°. The P(4)-O(10) bond length is 1.58 Å. The P(4)-O(11) bond length is 1.58 Å. The P(4)-O(12) bond length is 1.54 Å. The P(4)-O(9) bond length is 1.52 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one V(3), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(3), one V(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one V(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one V(1), one V(2), and one P(1) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one V(1), one V(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(2) and one P(4) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Li(2), one Li(3), one V(1), one V(3), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Li(3), one V(1), one V(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one V(2), and one P(4) atom.