Li4VNi3O8 is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent Ni(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form LiO6 octahedra that share corners with six equivalent Ni(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. V(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form NiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form NiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. In the third Ni site, Ni(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form NiO6 octahedra that share corners with six equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one V(1), one Ni(2), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(6)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one V(1), one Ni(1), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(7)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Ni(1), and one Ni(2) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(8)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(7)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Li(4), one V(1), one Ni(2), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Li(4), one V(1), one Ni(1), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Ni(1), and one Ni(2) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(7)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.
Li4VNi3O8 is Caswellsilverite-derived structured and crystallizes in the triclinic P1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent V(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. The Li(1)-O(2) bond length is 2.21 Å. The Li(1)-O(3) bond length is 2.28 Å. The Li(1)-O(5) bond length is 2.24 Å. The Li(1)-O(6) bond length is 2.24 Å. The Li(1)-O(7) bond length is 2.19 Å. The Li(1)-O(8) bond length is 2.23 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. The Li(2)-O(1) bond length is 2.19 Å. The Li(2)-O(3) bond length is 2.09 Å. The Li(2)-O(4) bond length is 2.15 Å. The Li(2)-O(5) bond length is 2.10 Å. The Li(2)-O(7) bond length is 2.08 Å. The Li(2)-O(8) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form LiO6 octahedra that share corners with six equivalent Ni(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. The Li(3)-O(1) bond length is 2.18 Å. The Li(3)-O(2) bond length is 2.07 Å. The Li(3)-O(4) bond length is 2.18 Å. The Li(3)-O(5) bond length is 2.08 Å. The Li(3)-O(6) bond length is 2.11 Å. The Li(3)-O(8) bond length is 2.08 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form LiO6 octahedra that share corners with six equivalent Ni(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. The Li(4)-O(1) bond length is 2.15 Å. The Li(4)-O(2) bond length is 2.09 Å. The Li(4)-O(3) bond length is 2.07 Å. The Li(4)-O(4) bond length is 2.19 Å. The Li(4)-O(6) bond length is 2.09 Å. The Li(4)-O(7) bond length is 2.11 Å. V(1) is bonded to one O(2), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-2°. The V(1)-O(2) bond length is 1.95 Å. The V(1)-O(3) bond length is 1.92 Å. The V(1)-O(5) bond length is 1.92 Å. The V(1)-O(6) bond length is 1.91 Å. The V(1)-O(7) bond length is 1.92 Å. The V(1)-O(8) bond length is 1.93 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(3), one O(4), one O(5), one O(7), and one O(8) atom to form NiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. The Ni(1)-O(1) bond length is 1.99 Å. The Ni(1)-O(3) bond length is 2.09 Å. The Ni(1)-O(4) bond length is 2.00 Å. The Ni(1)-O(5) bond length is 2.08 Å. The Ni(1)-O(7) bond length is 2.08 Å. The Ni(1)-O(8) bond length is 2.08 Å. In the second Ni site, Ni(2) is bonded to one O(1), one O(2), one O(4), one O(5), one O(6), and one O(8) atom to form NiO6 octahedra that share corners with six equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. The Ni(2)-O(1) bond length is 1.98 Å. The Ni(2)-O(2) bond length is 2.07 Å. The Ni(2)-O(4) bond length is 1.98 Å. The Ni(2)-O(5) bond length is 2.09 Å. The Ni(2)-O(6) bond length is 2.08 Å. The Ni(2)-O(8) bond length is 2.08 Å. In the third Ni site, Ni(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form NiO6 octahedra that share corners with six equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Ni(1)O6 octahedra, and edges with two equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. The Ni(3)-O(1) bond length is 2.00 Å. The Ni(3)-O(2) bond length is 2.07 Å. The Ni(3)-O(3) bond length is 2.08 Å. The Ni(3)-O(4) bond length is 2.00 Å. The Ni(3)-O(6) bond length is 2.08 Å. The Ni(3)-O(7) bond length is 2.08 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Li(4), one V(1), one Ni(2), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(6)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(4), one V(1), one Ni(1), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(7)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fourth O site, O(4) is bonded to one Li(2), one Li(3), one Li(4), one Ni(1), one Ni(2), and one Ni(3) atom to form OLi3Ni3 octahedra that share corners with six equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Ni(1), and one Ni(2) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(8)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(7)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the sixth O site, O(6) is bonded to one Li(1), one Li(3), one Li(4), one V(1), one Ni(2), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(7)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one Li(4), one V(1), one Ni(1), and one Ni(3) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(8)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the eighth O site, O(8) is bonded to one Li(1), one Li(2), one Li(3), one V(1), one Ni(1), and one Ni(2) atom to form OLi3VNi2 octahedra that share corners with six equivalent O(5)Li3VNi2 octahedra, edges with two equivalent O(1)Li3Ni3 octahedra, edges with two equivalent O(4)Li3Ni3 octahedra, edges with two equivalent O(2)Li3VNi2 octahedra, edges with two equivalent O(3)Li3VNi2 octahedra, edges with two equivalent O(6)Li3VNi2 octahedra, and edges with two equivalent O(7)Li3VNi2 octahedra. The corner-sharing octahedral tilt angles range from 0-2°.