Li3V4(PO4)6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(3), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded to two equivalent O(12), two equivalent O(6), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, 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 corner-sharing octahedral tilt angles are 58°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), one O(5), one O(6), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. In the second V site, V(2) is bonded to one O(10), one O(11), one O(3), one O(7), and two equivalent O(9) atoms to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-71°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-59°. In the third P site, P(3) is bonded to one O(10), one O(12), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, and corners with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), 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(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent V(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(3) atom.
Li3V4(PO4)6 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(1), one O(12), one O(3), one O(4), and one O(8) atom. The Li(1)-O(1) bond length is 2.32 Å. The Li(1)-O(12) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.45 Å. The Li(1)-O(4) bond length is 2.18 Å. The Li(1)-O(8) bond length is 1.96 Å. In the second Li site, Li(2) is bonded to two equivalent O(12), two equivalent O(6), and two equivalent O(8) atoms to form distorted LiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, 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 corner-sharing octahedral tilt angles are 58°. Both Li(2)-O(12) bond lengths are 2.05 Å. Both Li(2)-O(6) bond lengths are 2.25 Å. Both Li(2)-O(8) bond lengths are 2.37 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(4), one O(5), one O(6), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. The V(1)-O(1) bond length is 2.00 Å. The V(1)-O(4) bond length is 1.99 Å. The V(1)-O(5) bond length is 1.89 Å. The V(1)-O(6) bond length is 2.08 Å. There is one shorter (2.08 Å) and one longer (2.09 Å) V(1)-O(2) bond length. In the second V site, V(2) is bonded to one O(10), one O(11), one O(3), one O(7), and two equivalent O(9) atoms to form VO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra, and  an edgeedge with one V(2)O6 octahedra. The V(2)-O(10) bond length is 1.92 Å. The V(2)-O(11) bond length is 1.90 Å. The V(2)-O(3) bond length is 1.93 Å. The V(2)-O(7) bond length is 1.88 Å. There is one shorter (2.06 Å) and one longer (2.21 Å) V(2)-O(9) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-71°. The P(1)-O(11) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(1), one O(2), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra, and corners with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-59°. The P(2)-O(1) bond length is 1.55 Å. The P(2)-O(2) bond length is 1.60 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, and corners with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 37-61°. The P(3)-O(10) bond length is 1.56 Å. The P(3)-O(12) bond length is 1.50 Å. The P(3)-O(5) bond length is 1.55 Å. The P(3)-O(9) bond length is 1.59 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one V(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to two equivalent V(1) and one P(2) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), 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(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Li(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to two equivalent V(2) and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted bent 120 degrees geometry to one V(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(3) atom.