Li4Nb3V3(CoO8)2 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 Nb(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. 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 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 V(2)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent Co(1)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-61°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. In the second Nb site, Nb(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 NbO6 octahedra that share corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are two inequivalent V sites. In the first V site, V(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 VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Nb(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. In the second Co site, Co(2) is bonded in a 6-coordinate geometry to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Nb(2), one V(2), and one Co(1) atom to form distorted OLiNbVCo trigonal pyramids that share  a cornercorner with one O(4)LiNbV2 tetrahedra,  a cornercorner with one O(2)LiV2Co tetrahedra, corners with three equivalent O(9)LiNbVCo tetrahedra,  a cornercorner with one O(1)LiNbVCo trigonal pyramid,  an edgeedge with one O(5)LiNb2V tetrahedra, and  an edgeedge with one O(1)LiNbVCo trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), two equivalent V(1), and one Co(1) atom to form distorted OLiV2Co tetrahedra that share corners with two equivalent O(4)LiNbV2 tetrahedra, corners with two equivalent O(1)LiNbVCo trigonal pyramids, and corners with two equivalent O(7)LiV2Co trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(1), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Nb(1), and two equivalent V(1) atoms to form distorted OLiNbV2 tetrahedra that share corners with two equivalent O(2)LiV2Co tetrahedra, corners with two equivalent O(1)LiNbVCo trigonal pyramids, and  an edgeedge with one O(7)LiV2Co trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Nb(2), and one V(2) atom to form distorted OLiNb2V tetrahedra that share corners with four equivalent O(9)LiNbVCo tetrahedra,  a cornercorner with one O(7)LiV2Co trigonal pyramid, and edges with two equivalent O(1)LiNbVCo trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Nb(1), one V(1), and one Co(1) atom. In the seventh O site, O(7) is bonded to one Li(2), two equivalent V(1), and one Co(2) atom to form distorted OLiV2Co trigonal pyramids that share  a cornercorner with one O(5)LiNb2V tetrahedra, corners with two equivalent O(9)LiNbVCo tetrahedra, corners with two equivalent O(2)LiV2Co tetrahedra, and  an edgeedge with one O(4)LiNbV2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Nb(2), and one Co(1) atom. In the ninth O site, O(9) is bonded to one Li(1), one Nb(2), one V(2), and one Co(2) atom to form distorted OLiNbVCo tetrahedra that share  a cornercorner with one O(9)LiNbVCo tetrahedra, corners with two equivalent O(5)LiNb2V tetrahedra,  a cornercorner with one O(7)LiV2Co trigonal pyramid, corners with three equivalent O(1)LiNbVCo trigonal pyramids, and  an edgeedge with one O(9)LiNbVCo tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent Nb(2), and one V(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one V(1), and one Co(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Nb(2), and one Co(2) atom.
Li4Nb3V3(CoO8)2 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 Nb(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-59°. The Li(1)-O(12) bond length is 1.99 Å. The Li(1)-O(3) bond length is 1.94 Å. Both Li(1)-O(9) bond lengths are 2.04 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 1.92 Å. Both Li(2)-O(11) bond lengths are 1.98 Å. In the third Li site, Li(3) is bonded in a 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 1.76 Å. The Li(3)-O(8) bond length is 2.07 Å. Both Li(3)-O(1) bond lengths are 1.95 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 V(2)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent Co(1)O6 octahedra, and corners with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-61°. The Li(4)-O(10) bond length is 2.07 Å. The Li(4)-O(2) bond length is 2.00 Å. Both Li(4)-O(6) bond lengths are 1.98 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(3), one O(4), two equivalent O(11), and two equivalent O(6) atoms to form NbO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The Nb(1)-O(3) bond length is 2.00 Å. The Nb(1)-O(4) bond length is 1.98 Å. Both Nb(1)-O(11) bond lengths are 2.07 Å. Both Nb(1)-O(6) bond lengths are 2.00 Å. In the second Nb site, Nb(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 NbO6 octahedra that share corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Nb(2)-O(1) bond length is 2.06 Å. The Nb(2)-O(10) bond length is 2.04 Å. The Nb(2)-O(12) bond length is 2.03 Å. The Nb(2)-O(5) bond length is 2.05 Å. The Nb(2)-O(8) bond length is 2.04 Å. The Nb(2)-O(9) bond length is 1.95 Å. There are two inequivalent V sites. In the first V site, V(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 VO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one Co(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The V(1)-O(11) bond length is 2.05 Å. The V(1)-O(2) bond length is 1.98 Å. The V(1)-O(3) bond length is 2.09 Å. The V(1)-O(4) bond length is 2.06 Å. The V(1)-O(6) bond length is 2.06 Å. The V(1)-O(7) bond length is 2.03 Å. In the second V site, V(2) is bonded to one O(10), one O(5), two equivalent O(1), and two equivalent O(9) atoms to form VO6 octahedra that share corners with two equivalent Co(1)O6 octahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 51°. The V(2)-O(10) bond length is 2.11 Å. The V(2)-O(5) bond length is 2.09 Å. Both V(2)-O(1) bond lengths are 2.01 Å. Both V(2)-O(9) bond lengths are 2.02 Å. There are two inequivalent Co sites. In the first Co site, Co(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form CoO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent Nb(2)O6 octahedra, corners with three equivalent Li(4)O4 tetrahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-54°. The Co(1)-O(2) bond length is 2.09 Å. The Co(1)-O(8) bond length is 2.26 Å. Both Co(1)-O(1) bond lengths are 2.17 Å. Both Co(1)-O(6) bond lengths are 2.15 Å. In the second Co site, Co(2) is bonded in a 6-coordinate geometry to one O(12), one O(7), two equivalent O(11), and two equivalent O(9) atoms. The Co(2)-O(12) bond length is 2.45 Å. The Co(2)-O(7) bond length is 2.01 Å. Both Co(2)-O(11) bond lengths are 2.01 Å. Both Co(2)-O(9) bond lengths are 2.45 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Nb(2), one V(2), and one Co(1) atom to form distorted OLiNbVCo trigonal pyramids that share  a cornercorner with one O(4)LiNbV2 tetrahedra,  a cornercorner with one O(2)LiV2Co tetrahedra, corners with three equivalent O(9)LiNbVCo tetrahedra,  a cornercorner with one O(1)LiNbVCo trigonal pyramid,  an edgeedge with one O(5)LiNb2V tetrahedra, and  an edgeedge with one O(1)LiNbVCo trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), two equivalent V(1), and one Co(1) atom to form distorted OLiV2Co tetrahedra that share corners with two equivalent O(4)LiNbV2 tetrahedra, corners with two equivalent O(1)LiNbVCo trigonal pyramids, and corners with two equivalent O(7)LiV2Co trigonal pyramids. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(1), one Nb(1), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Nb(1), and two equivalent V(1) atoms to form distorted OLiNbV2 tetrahedra that share corners with two equivalent O(2)LiV2Co tetrahedra, corners with two equivalent O(1)LiNbVCo trigonal pyramids, and  an edgeedge with one O(7)LiV2Co trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Nb(2), and one V(2) atom to form distorted OLiNb2V tetrahedra that share corners with four equivalent O(9)LiNbVCo tetrahedra,  a cornercorner with one O(7)LiV2Co trigonal pyramid, and edges with two equivalent O(1)LiNbVCo trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(4), one Nb(1), one V(1), and one Co(1) atom. In the seventh O site, O(7) is bonded to one Li(2), two equivalent V(1), and one Co(2) atom to form distorted OLiV2Co trigonal pyramids that share  a cornercorner with one O(5)LiNb2V tetrahedra, corners with two equivalent O(9)LiNbVCo tetrahedra, corners with two equivalent O(2)LiV2Co tetrahedra, and  an edgeedge with one O(4)LiNbV2 tetrahedra. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(3), two equivalent Nb(2), and one Co(1) atom. In the ninth O site, O(9) is bonded to one Li(1), one Nb(2), one V(2), and one Co(2) atom to form distorted OLiNbVCo tetrahedra that share  a cornercorner with one O(9)LiNbVCo tetrahedra, corners with two equivalent O(5)LiNb2V tetrahedra,  a cornercorner with one O(7)LiV2Co trigonal pyramid, corners with three equivalent O(1)LiNbVCo trigonal pyramids, and  an edgeedge with one O(9)LiNbVCo tetrahedra. In the tenth O site, O(10) is bonded in a rectangular see-saw-like geometry to one Li(4), two equivalent Nb(2), and one V(2) atom. In the eleventh O site, O(11) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(1), one V(1), and one Co(2) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), two equivalent Nb(2), and one Co(2) atom.