Li8VNi3(PO4)6 crystallizes in the trigonal R3 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(3), one O(8), and two equivalent O(4) atoms. In the second Li site, Li(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ni(1)O6 octahedra, and  a faceface with one Ni(3)O6 octahedra. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to three equivalent O(3) atoms. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(6), and two equivalent O(7) atoms. V(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. In the second Ni site, Ni(2) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. In the third Ni site, Ni(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. 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 Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-51°. 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 Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-46°. There are eight inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(2) atom. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(2) atom. In the third O site, O(7) is bonded to one Li(2), two equivalent Li(4), one Ni(3), and one P(2) atom to form distorted face-sharing OLi3NiP square pyramids. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Ni(2), and one P(1) atom. In the fifth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Ni(1), and one P(2) atom. In the sixth O site, O(4) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Ni(1), and one P(1) atom. In the seventh O site, O(1) is bonded in a 3-coordinate geometry to one Li(4), one Ni(3), and one P(1) atom. In the eighth O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.
Li8VNi3(PO4)6 crystallizes in the trigonal R3 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(3), one O(8), and two equivalent O(4) atoms. The Li(1)-O(3) bond length is 2.02 Å. The Li(1)-O(8) bond length is 2.04 Å. There is one shorter (2.03 Å) and one longer (2.35 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted LiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ni(1)O6 octahedra, and  a faceface with one Ni(3)O6 octahedra. All Li(2)-O(4) bond lengths are 2.25 Å. All Li(2)-O(7) bond lengths are 2.25 Å. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to three equivalent O(3) atoms. All Li(3)-O(3) bond lengths are 2.08 Å. In the fourth Li site, Li(4) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(6), and two equivalent O(7) atoms. The Li(4)-O(1) bond length is 1.95 Å. The Li(4)-O(6) bond length is 2.07 Å. There is one shorter (2.08 Å) and one longer (2.20 Å) Li(4)-O(7) bond length. V(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form 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(2) bond lengths are 1.91 Å. All V(1)-O(6) bond lengths are 2.00 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. All Ni(1)-O(4) bond lengths are 2.16 Å. All Ni(1)-O(8) bond lengths are 2.03 Å. In the second Ni site, Ni(2) is bonded to three equivalent O(3) and three equivalent O(5) atoms to form NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All Ni(2)-O(3) bond lengths are 2.12 Å. All Ni(2)-O(5) bond lengths are 1.98 Å. In the third Ni site, Ni(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Li(2)O6 octahedra. All Ni(3)-O(1) bond lengths are 2.00 Å. All Ni(3)-O(7) bond lengths are 2.10 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 Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-51°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.56 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 Li(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Ni(1)O6 octahedra,  a cornercorner with one Ni(2)O6 octahedra, and  a cornercorner with one Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 31-46°. The P(2)-O(5) bond length is 1.50 Å. The P(2)-O(6) 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 1.54 Å. There are eight inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Ni(2) and one P(2) atom. In the second O site, O(6) is bonded in a 3-coordinate geometry to one Li(4), one V(1), and one P(2) atom. In the third O site, O(7) is bonded to one Li(2), two equivalent Li(4), one Ni(3), and one P(2) atom to form distorted face-sharing OLi3NiP square pyramids. In the fourth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(3), one Ni(2), and one P(1) atom. In the fifth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Ni(1), and one P(2) atom. In the sixth O site, O(4) is bonded in a 5-coordinate geometry to one Li(2), two equivalent Li(1), one Ni(1), and one P(1) atom. In the seventh O site, O(1) is bonded in a 3-coordinate geometry to one Li(4), one Ni(3), and one P(1) atom. In the eighth O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom.