Li4V3Co2Sb3O16 is Hausmannite-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 Co(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. 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 in a distorted rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. 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 56-58°. 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 Co(2)O6 octahedra,  a cornercorner with one Li(1)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 51°. 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 Co(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. There are two inequivalent Co sites. In the first Co site, Co(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 Co site, Co(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form CoO6 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 51-54°. 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 Co(2)O6 octahedra,  a cornercorner with one Li(1)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 range from 53-54°. 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 Co(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. 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 Co(1), and one Sb(2) atom. In the second O site, O(2) is bonded to one Li(4), one Co(1), and two equivalent Sb(1) atoms to form distorted OLiCoSb2 tetrahedra that share corners with two equivalent O(6)LiVCoSb tetrahedra, corners with two equivalent O(4)LiVSb2 tetrahedra, corners with two equivalent O(11)LiVCoSb trigonal pyramids, and edges with two equivalent O(6)LiVCoSb tetrahedra. 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 distorted OLiVSb2 tetrahedra that share corners with two equivalent O(2)LiCoSb2 tetrahedra, corners with four equivalent O(6)LiVCoSb tetrahedra, and edges with two equivalent O(11)LiVCoSb trigonal pyramids. 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)LiV2Co tetrahedra and corners with two equivalent O(11)LiVCoSb trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Co(1), and one Sb(1) atom to form distorted OLiVCoSb tetrahedra that share  a cornercorner with one O(2)LiCoSb2 tetrahedra,  a cornercorner with one O(6)LiVCoSb tetrahedra, corners with two equivalent O(4)LiVSb2 tetrahedra, corners with three equivalent O(11)LiVCoSb trigonal pyramids,  an edgeedge with one O(2)LiCoSb2 tetrahedra, and  an edgeedge with one O(6)LiVCoSb tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Co(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 Co(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 Co(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 Co(2), and one Sb(1) atom to form distorted OLiVCoSb trigonal pyramids that share  a cornercorner with one O(2)LiCoSb2 tetrahedra,  a cornercorner with one O(12)LiV2Co tetrahedra,  a cornercorner with one O(5)LiV2Sb tetrahedra, corners with three equivalent O(6)LiVCoSb tetrahedra,  a cornercorner with one O(11)LiVCoSb trigonal pyramid,  an edgeedge with one O(4)LiVSb2 tetrahedra, and  an edgeedge with one O(11)LiVCoSb trigonal pyramid. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Co(2) atom to form distorted OLiV2Co tetrahedra that share corners with two equivalent O(5)LiV2Sb tetrahedra and corners with two equivalent O(11)LiVCoSb trigonal pyramids.
Li4V3Co2Sb3O16 is Hausmannite-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 Co(2)O6 octahedra, and corners with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. The Li(1)-O(12) bond length is 1.99 Å. The Li(1)-O(3) bond length is 2.21 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 1.76 Å. The Li(2)-O(7) bond length is 2.06 Å. Both Li(2)-O(11) bond lengths are 1.97 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(4), one O(8), and two equivalent O(1) atoms. 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 56-58°. The Li(4)-O(10) bond length is 1.99 Å. The Li(4)-O(2) bond length is 2.10 Å. Both Li(4)-O(6) bond lengths are 2.05 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 Co(2)O6 octahedra,  a cornercorner with one Li(1)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 51°. The V(1)-O(3) bond length is 2.13 Å. The V(1)-O(4) bond length is 2.10 Å. Both V(1)-O(11) bond lengths are 2.05 Å. Both V(1)-O(6) bond lengths are 2.02 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 Co(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent Sb(2)O6 octahedra. The V(2)-O(1) bond length is 2.08 Å. The V(2)-O(10) bond length is 2.10 Å. The V(2)-O(12) bond length is 2.02 Å. The V(2)-O(5) bond length is 2.07 Å. The V(2)-O(8) bond length is 2.04 Å. The V(2)-O(9) bond length is 2.08 Å. There are two inequivalent Co sites. In the first Co site, Co(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 Co(1)-O(2) bond length is 2.50 Å. The Co(1)-O(8) bond length is 2.00 Å. Both Co(1)-O(1) bond lengths are 2.07 Å. Both Co(1)-O(6) bond lengths are 2.48 Å. In the second Co site, Co(2) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form CoO6 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 51-54°. The Co(2)-O(12) bond length is 2.07 Å. The Co(2)-O(7) bond length is 2.38 Å. Both Co(2)-O(11) bond lengths are 2.25 Å. Both Co(2)-O(9) bond lengths are 2.15 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 Co(2)O6 octahedra,  a cornercorner with one Li(1)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 range from 53-54°. 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 2.06 Å. The Sb(1)-O(4) bond length is 2.06 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 Co(2)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The Sb(2)-O(10) bond length is 2.02 Å. The Sb(2)-O(5) bond length is 2.00 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 Co(1), and one Sb(2) atom. In the second O site, O(2) is bonded to one Li(4), one Co(1), and two equivalent Sb(1) atoms to form distorted OLiCoSb2 tetrahedra that share corners with two equivalent O(6)LiVCoSb tetrahedra, corners with two equivalent O(4)LiVSb2 tetrahedra, corners with two equivalent O(11)LiVCoSb trigonal pyramids, and edges with two equivalent O(6)LiVCoSb tetrahedra. 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 distorted OLiVSb2 tetrahedra that share corners with two equivalent O(2)LiCoSb2 tetrahedra, corners with four equivalent O(6)LiVCoSb tetrahedra, and edges with two equivalent O(11)LiVCoSb trigonal pyramids. 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)LiV2Co tetrahedra and corners with two equivalent O(11)LiVCoSb trigonal pyramids. In the sixth O site, O(6) is bonded to one Li(4), one V(1), one Co(1), and one Sb(1) atom to form distorted OLiVCoSb tetrahedra that share  a cornercorner with one O(2)LiCoSb2 tetrahedra,  a cornercorner with one O(6)LiVCoSb tetrahedra, corners with two equivalent O(4)LiVSb2 tetrahedra, corners with three equivalent O(11)LiVCoSb trigonal pyramids,  an edgeedge with one O(2)LiCoSb2 tetrahedra, and  an edgeedge with one O(6)LiVCoSb tetrahedra. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Co(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 Co(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 Co(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 Co(2), and one Sb(1) atom to form distorted OLiVCoSb trigonal pyramids that share  a cornercorner with one O(2)LiCoSb2 tetrahedra,  a cornercorner with one O(12)LiV2Co tetrahedra,  a cornercorner with one O(5)LiV2Sb tetrahedra, corners with three equivalent O(6)LiVCoSb tetrahedra,  a cornercorner with one O(11)LiVCoSb trigonal pyramid,  an edgeedge with one O(4)LiVSb2 tetrahedra, and  an edgeedge with one O(11)LiVCoSb trigonal pyramid. In the twelfth O site, O(12) is bonded to one Li(1), two equivalent V(2), and one Co(2) atom to form distorted OLiV2Co tetrahedra that share corners with two equivalent O(5)LiV2Sb tetrahedra and corners with two equivalent O(11)LiVCoSb trigonal pyramids.