Li7V4(PO4)6 crystallizes in the trigonal R3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(4), one O(6), and one O(7) atom. In the third Li site, Li(3) is bonded in a distorted T-shaped geometry to three equivalent O(6) atoms. There are four inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(6) atoms to form distorted VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. In the second V site, V(2) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. In the third V site, V(3) is bonded to three equivalent O(2) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. In the fourth V site, V(4) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, and corners with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-52°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-50°. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(4), and one P(2) atom. In the second O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(1) atom. In the third O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one V(3), and one P(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one P(1) atom. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the seventh O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(6) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(2) atom.
Li7V4(PO4)6 crystallizes in the trigonal R3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 64-67°. The Li(1)-O(1) bond length is 2.00 Å. The Li(1)-O(2) bond length is 1.97 Å. The Li(1)-O(3) bond length is 1.98 Å. The Li(1)-O(8) bond length is 2.15 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(4), one O(6), and one O(7) atom. The Li(2)-O(4) bond length is 1.96 Å. The Li(2)-O(6) bond length is 2.01 Å. The Li(2)-O(7) bond length is 1.97 Å. In the third Li site, Li(3) is bonded in a distorted T-shaped geometry to three equivalent O(6) atoms. All Li(3)-O(6) bond lengths are 2.05 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(6) atoms to form distorted VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All V(1)-O(4) bond lengths are 2.12 Å. All V(1)-O(6) bond lengths are 2.20 Å. In the second V site, V(2) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. All V(2)-O(3) bond lengths are 2.10 Å. All V(2)-O(5) bond lengths are 2.04 Å. In the third V site, V(3) is bonded to three equivalent O(2) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. All V(3)-O(2) bond lengths are 2.04 Å. All V(3)-O(8) bond lengths are 2.03 Å. In the fourth V site, V(4) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. All V(4)-O(1) bond lengths are 2.05 Å. All V(4)-O(7) bond lengths are 2.07 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, and corners with three equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 38-52°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra, and  a cornercorner with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 23-50°. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.56 Å. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one V(4), and one P(2) atom. In the second O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one V(1), and one P(1) atom. In the third O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one V(3), and one P(2) atom. In the fourth O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one V(4), and one P(1) atom. In the fifth O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(3), and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(1) atom. In the seventh O site, O(5) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the eighth O site, O(6) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one V(1), and one P(2) atom.