Li7V3Ni(PO4)6 crystallizes in the trigonal R3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(4), one O(7), and two equivalent O(6) atoms. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to three equivalent O(6) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(3) and three equivalent O(8) atoms to form 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(2) and three equivalent O(5) atoms to form VO6 octahedra that share 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(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. Ni(1) is bonded to three equivalent O(4) and three equivalent O(6) atoms to form distorted NiO6 octahedra that share 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, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-38°. 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, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-43°. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one P(2) atom. In the second O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(1) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Ni(1), and one P(1) atom. In the seventh O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) atom. In the eighth O site, O(6) is bonded to one Li(3), two equivalent Li(2), one Ni(1), and one P(2) atom to form distorted face-sharing OLi3NiP square pyramids.
Li7V3Ni(PO4)6 crystallizes in the trigonal R3 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(5), and two equivalent O(3) atoms. The Li(1)-O(2) bond length is 2.25 Å. The Li(1)-O(5) bond length is 2.07 Å. There is one shorter (2.06 Å) and one longer (2.35 Å) Li(1)-O(3) bond length. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(4), one O(7), and two equivalent O(6) atoms. The Li(2)-O(4) bond length is 1.98 Å. The Li(2)-O(7) bond length is 2.08 Å. There is one shorter (2.20 Å) and one longer (2.30 Å) Li(2)-O(6) bond length. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to three equivalent O(6) atoms. All Li(3)-O(6) bond lengths are 2.07 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(3) and three equivalent O(8) 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(3) bond lengths are 2.03 Å. All V(1)-O(8) bond lengths are 1.97 Å. In the second V site, V(2) is bonded to three equivalent O(2) and three equivalent O(5) 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(2)-O(2) bond lengths are 2.04 Å. All V(2)-O(5) bond lengths are 2.05 Å. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(7) 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(3)-O(1) bond lengths are 2.01 Å. All V(3)-O(7) bond lengths are 2.08 Å. Ni(1) is bonded to three equivalent O(4) and three equivalent O(6) atoms to form distorted NiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All Ni(1)-O(4) bond lengths are 2.00 Å. All Ni(1)-O(6) bond lengths are 2.14 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, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-38°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.54 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, and  a cornercorner with one Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-43°. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.52 Å. There are eight inequivalent O sites. In the first O site, O(7) is bonded in a distorted T-shaped geometry to one Li(2), one V(3), and one P(2) atom. In the second O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom. In the third O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(1) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Li(2), one Ni(1), and one P(1) atom. In the seventh O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one P(2) atom. In the eighth O site, O(6) is bonded to one Li(3), two equivalent Li(2), one Ni(1), and one P(2) atom to form distorted face-sharing OLi3NiP square pyramids.