Li4V5Co3O16 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(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form LiO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(4)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-66°. 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 trigonal pyramids that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-68°. 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 Co(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-66°. There are four inequivalent V sites. In the first V site, V(1) 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 corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 53-54°. In the second V site, V(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. In the third V site, V(3) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(2)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. In the fourth V site, V(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. There are two inequivalent Co sites. In the first Co site, Co(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 CoO6 octahedra that share corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. In the second Co site, Co(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form CoO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 46°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), one V(2), and one Co(2) atom. In the second O site, O(2) is bonded to one Li(4), one V(2), and two equivalent Co(1) atoms to form distorted corner-sharing OLiVCo2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(3), and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(3), and two equivalent Co(1) atoms to form corner-sharing OLiVCo2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(1), and one Co(2) atom to form OLiV2Co tetrahedra that share corners with two equivalent O(12)LiV3 tetrahedra and corners with four equivalent O(9)LiV2Co tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(4), one V(2), one V(3), and one Co(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(4), and two equivalent Co(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), and two equivalent V(1) atoms. In the ninth O site, O(9) is bonded to one Li(1), one V(1), one V(4), and one Co(2) atom to form distorted OLiV2Co tetrahedra that share  a cornercorner with one O(9)LiV2Co tetrahedra,  a cornercorner with one O(12)LiV3 tetrahedra, corners with two equivalent O(5)LiV2Co tetrahedra,  an edgeedge with one O(9)LiV2Co tetrahedra, and  an edgeedge with one O(12)LiV3 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(1), and one Co(2) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(3), one V(4), and one Co(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one V(4), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra.
Li4V5Co3O16 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(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, corners with three equivalent V(4)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-65°. The Li(1)-O(12) bond length is 1.99 Å. The Li(1)-O(3) bond length is 1.97 Å. Both Li(1)-O(9) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to one O(5), one O(7), and two equivalent O(11) atoms to form LiO4 tetrahedra that share  a cornercorner with one Co(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with three equivalent V(4)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-66°. The Li(2)-O(5) bond length is 1.83 Å. The Li(2)-O(7) bond length is 2.00 Å. Both Li(2)-O(11) bond lengths are 2.03 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 trigonal pyramids that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with three equivalent V(2)O6 octahedra,  an edgeedge with one Co(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-68°. The Li(3)-O(4) bond length is 1.84 Å. The Li(3)-O(8) bond length is 2.03 Å. Both Li(3)-O(1) bond lengths are 2.04 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 Co(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, corners with three equivalent V(2)O6 octahedra, and corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-66°. The Li(4)-O(10) bond length is 1.95 Å. The Li(4)-O(2) bond length is 1.98 Å. Both Li(4)-O(6) bond lengths are 1.96 Å. There are four inequivalent V sites. In the first V site, V(1) 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 corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles range from 53-54°. The V(1)-O(1) bond length is 2.21 Å. The V(1)-O(10) bond length is 1.92 Å. The V(1)-O(12) bond length is 2.00 Å. The V(1)-O(5) bond length is 1.96 Å. The V(1)-O(8) bond length is 2.03 Å. The V(1)-O(9) bond length is 1.83 Å. In the second V site, V(2) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(3)O4 trigonal pyramids,  an edgeedge with one V(3)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-54°. The V(2)-O(2) bond length is 1.81 Å. The V(2)-O(8) bond length is 2.21 Å. Both V(2)-O(1) bond lengths are 1.82 Å. Both V(2)-O(6) bond lengths are 2.06 Å. In the third V site, V(3) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form distorted VO6 octahedra that share corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(2)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 50°. The V(3)-O(3) bond length is 1.86 Å. The V(3)-O(4) bond length is 1.87 Å. Both V(3)-O(11) bond lengths are 2.27 Å. Both V(3)-O(6) bond lengths are 1.90 Å. In the fourth V site, V(4) is bonded to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form distorted VO6 octahedra that share corners with two equivalent V(3)O6 octahedra, corners with four equivalent Co(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra,  an edgeedge with one Co(2)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-52°. The V(4)-O(12) bond length is 2.09 Å. The V(4)-O(7) bond length is 1.80 Å. Both V(4)-O(11) bond lengths are 1.79 Å. Both V(4)-O(9) bond lengths are 2.16 Å. There are two inequivalent Co sites. In the first Co site, Co(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 CoO6 octahedra that share corners with two equivalent V(4)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  a cornercorner with one Li(3)O4 trigonal pyramid,  an edgeedge with one V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-52°. The Co(1)-O(11) bond length is 2.20 Å. The Co(1)-O(2) bond length is 2.12 Å. The Co(1)-O(3) bond length is 2.01 Å. The Co(1)-O(4) bond length is 1.98 Å. The Co(1)-O(6) bond length is 2.15 Å. The Co(1)-O(7) bond length is 2.14 Å. In the second Co site, Co(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form CoO6 octahedra that share corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra,  an edgeedge with one V(4)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(3)O4 trigonal pyramid. The corner-sharing octahedral tilt angles are 46°. The Co(2)-O(10) bond length is 2.05 Å. The Co(2)-O(5) bond length is 2.00 Å. Both Co(2)-O(1) bond lengths are 2.13 Å. Both Co(2)-O(9) bond lengths are 2.13 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one V(1), one V(2), and one Co(2) atom. In the second O site, O(2) is bonded to one Li(4), one V(2), and two equivalent Co(1) atoms to form distorted corner-sharing OLiVCo2 tetrahedra. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one V(3), and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one V(3), and two equivalent Co(1) atoms to form corner-sharing OLiVCo2 tetrahedra. In the fifth O site, O(5) is bonded to one Li(2), two equivalent V(1), and one Co(2) atom to form OLiV2Co tetrahedra that share corners with two equivalent O(12)LiV3 tetrahedra and corners with four equivalent O(9)LiV2Co tetrahedra. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to one Li(4), one V(2), one V(3), and one Co(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(4), and two equivalent Co(1) atoms. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), one V(2), and two equivalent V(1) atoms. In the ninth O site, O(9) is bonded to one Li(1), one V(1), one V(4), and one Co(2) atom to form distorted OLiV2Co tetrahedra that share  a cornercorner with one O(9)LiV2Co tetrahedra,  a cornercorner with one O(12)LiV3 tetrahedra, corners with two equivalent O(5)LiV2Co tetrahedra,  an edgeedge with one O(9)LiV2Co tetrahedra, and  an edgeedge with one O(12)LiV3 tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent V(1), and one Co(2) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one V(3), one V(4), and one Co(1) atom. In the twelfth O site, O(12) is bonded to one Li(1), one V(4), and two equivalent V(1) atoms to form a mixture of distorted edge and corner-sharing OLiV3 tetrahedra.