Li4V3Ni2Sb3O16 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-63°. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra,  an edgeedge with one Sb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-65°. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Sb(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-59°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and edges with four equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Sb(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 6-coordinate geometry to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms. In the second Ni site, Ni(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form NiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form SbO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. In the second Sb site, Sb(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form SbO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), one Ni(1), and one Sb(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(4), one Ni(1), and two equivalent Sb(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Sb(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(1), and two equivalent Sb(1) atoms to form a mixture of distorted edge and corner-sharing OLiVSb2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(2), and one Sb(2) atom to form distorted OLiV2Sb tetrahedra that share corners with two equivalent O(12)LiV2Ni tetrahedra and corners with two equivalent O(11)LiVNiSb trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Ni(1), and one Sb(1) atom to form distorted OLiVNiSb tetrahedra that share  a cornercorner with one O(6)LiVNiSb tetrahedra, corners with two equivalent O(4)LiVSb2 tetrahedra, corners with three equivalent O(11)LiVNiSb trigonal pyramids, and  an edgeedge with one O(6)LiVNiSb tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ni(2), and two equivalent Sb(1) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent V(2), and one Ni(1) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one Ni(2), and one Sb(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(2), and one Sb(2) atom. In the eleventh O site, O(11) is bonded to one Li(2), one V(1), one Ni(2), and one Sb(1) atom to form distorted OLiVNiSb trigonal pyramids that share  a cornercorner with one O(12)LiV2Ni tetrahedra,  a cornercorner with one O(5)LiV2Sb tetrahedra, corners with three equivalent O(6)LiVNiSb tetrahedra,  a cornercorner with one O(11)LiVNiSb trigonal pyramid,  an edgeedge with one O(4)LiVSb2 tetrahedra, and  an edgeedge with one O(11)LiVNiSb trigonal pyramid. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Ni(2) atom to form distorted OLiV2Ni tetrahedra that share corners with two equivalent O(5)LiV2Sb tetrahedra and corners with two equivalent O(11)LiVNiSb trigonal pyramids.
Li4V3Ni2Sb3O16 is Spinel-derived structured and crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(12), one O(3), and two equivalent O(9) atoms to form LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra, corners with two equivalent Sb(2)O6 octahedra, corners with three equivalent Ni(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-63°. The Li(1)-O(12) bond length is 1.96 Å. The Li(1)-O(3) bond length is 2.23 Å. Both Li(1)-O(9) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(5), one O(7), and two equivalent O(11) atoms. The Li(2)-O(5) bond length is 1.75 Å. The Li(2)-O(7) bond length is 2.05 Å. Both Li(2)-O(11) bond lengths are 1.98 Å. In the third Li site, Li(3) is bonded to one O(4), one O(8), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent Sb(1)O6 octahedra,  an edgeedge with one Sb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-65°. The Li(3)-O(4) bond length is 1.82 Å. The Li(3)-O(8) bond length is 1.90 Å. Both Li(3)-O(1) bond lengths are 1.96 Å. In the fourth Li site, Li(4) is bonded to one O(10), one O(2), and two equivalent O(6) atoms to form LiO4 tetrahedra that share  a cornercorner with one Sb(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-59°. The Li(4)-O(10) bond length is 1.99 Å. The Li(4)-O(2) bond length is 2.09 Å. Both Li(4)-O(6) bond lengths are 2.04 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, and edges with four equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 52°. The V(1)-O(3) bond length is 2.12 Å. The V(1)-O(4) bond length is 2.10 Å. Both V(1)-O(11) bond lengths are 2.04 Å. Both V(1)-O(6) bond lengths are 2.03 Å. In the second V site, V(2) is bonded to one O(1), one O(10), one O(12), one O(5), one O(8), and one O(9) atom to form VO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent Sb(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The V(2)-O(1) bond length is 2.10 Å. The V(2)-O(10) bond length is 2.09 Å. The V(2)-O(12) bond length is 2.02 Å. The V(2)-O(5) bond length is 2.06 Å. The V(2)-O(8) bond length is 2.04 Å. The V(2)-O(9) bond length is 2.10 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 6-coordinate geometry to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms. The Ni(1)-O(2) bond length is 2.42 Å. The Ni(1)-O(8) bond length is 2.01 Å. Both Ni(1)-O(1) bond lengths are 2.08 Å. Both Ni(1)-O(6) bond lengths are 2.38 Å. In the second Ni site, Ni(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form NiO6 octahedra that share corners with two equivalent V(1)O6 octahedra, corners with four equivalent Sb(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Sb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-53°. The Ni(2)-O(12) bond length is 2.05 Å. The Ni(2)-O(7) bond length is 2.36 Å. Both Ni(2)-O(11) bond lengths are 2.27 Å. Both Ni(2)-O(9) bond lengths are 2.10 Å. There are two inequivalent Sb sites. In the first Sb site, Sb(1) is bonded to one O(11), one O(2), one O(3), one O(4), one O(6), and one O(7) atom to form SbO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent Sb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 53°. The Sb(1)-O(11) bond length is 2.00 Å. The Sb(1)-O(2) bond length is 2.04 Å. The Sb(1)-O(3) bond length is 2.05 Å. The Sb(1)-O(4) bond length is 2.05 Å. The Sb(1)-O(6) bond length is 1.98 Å. The Sb(1)-O(7) bond length is 2.05 Å. In the second Sb site, Sb(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form SbO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one Ni(2)O6 octahedra, edges with four equivalent V(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The Sb(2)-O(10) bond length is 2.02 Å. The Sb(2)-O(5) bond length is 2.01 Å. Both Sb(2)-O(1) bond lengths are 2.05 Å. Both Sb(2)-O(9) bond lengths are 2.03 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), one Ni(1), and one Sb(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Li(4), one Ni(1), and two equivalent Sb(1) atoms. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(1), and two equivalent Sb(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(1), and two equivalent Sb(1) atoms to form a mixture of distorted edge and corner-sharing OLiVSb2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(2), and one Sb(2) atom to form distorted OLiV2Sb tetrahedra that share corners with two equivalent O(12)LiV2Ni tetrahedra and corners with two equivalent O(11)LiVNiSb trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Ni(1), and one Sb(1) atom to form distorted OLiVNiSb tetrahedra that share  a cornercorner with one O(6)LiVNiSb tetrahedra, corners with two equivalent O(4)LiVSb2 tetrahedra, corners with three equivalent O(11)LiVNiSb trigonal pyramids, and  an edgeedge with one O(6)LiVNiSb tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Ni(2), and two equivalent Sb(1) atoms. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), two equivalent V(2), and one Ni(1) atom. In the ninth O site, O(9) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(2), one Ni(2), and one Sb(2) atom. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(2), and one Sb(2) atom. In the eleventh O site, O(11) is bonded to one Li(2), one V(1), one Ni(2), and one Sb(1) atom to form distorted OLiVNiSb trigonal pyramids that share  a cornercorner with one O(12)LiV2Ni tetrahedra,  a cornercorner with one O(5)LiV2Sb tetrahedra, corners with three equivalent O(6)LiVNiSb tetrahedra,  a cornercorner with one O(11)LiVNiSb trigonal pyramid,  an edgeedge with one O(4)LiVSb2 tetrahedra, and  an edgeedge with one O(11)LiVNiSb trigonal pyramid. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Ni(2) atom to form distorted OLiV2Ni tetrahedra that share corners with two equivalent O(5)LiV2Sb tetrahedra and corners with two equivalent O(11)LiVNiSb trigonal pyramids.