Li4Nb3V2Co3O16 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 Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-64°. 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 Nb(2)O6 octahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. In the third Li site, Li(3) is bonded in a 4-coordinate 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 Co(2)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. 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 distorted NbO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. 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 V(1)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, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Co(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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. In the second V site, V(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 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 distorted CoO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. 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 distorted CoO6 octahedra that share corners with two equivalent V(1)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, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one Nb(2), one V(1), and one Co(2) atom to form distorted OLiNbVCo trigonal pyramids that share  a cornercorner with one O(4)LiNbCo2 tetrahedra,  a cornercorner with one O(2)LiVCo2 tetrahedra, corners with three equivalent O(9)LiNbVCo tetrahedra,  a cornercorner with one O(8)LiNb2V trigonal pyramid,  a cornercorner with one O(1)LiNbVCo trigonal pyramid,  an edgeedge with one O(5)LiNb2Co tetrahedra,  an edgeedge with one O(8)LiNb2V trigonal pyramid, and  an edgeedge with one O(1)LiNbVCo trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), one V(1), and two equivalent Co(1) atoms to form distorted OLiVCo2 tetrahedra that share corners with two equivalent O(4)LiNbCo2 tetrahedra,  a cornercorner with one O(8)LiNb2V trigonal pyramid, and corners with two equivalent O(1)LiNbVCo 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 Co(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Nb(1), and two equivalent Co(1) atoms to form OLiNbCo2 tetrahedra that share corners with two equivalent O(2)LiVCo2 tetrahedra,  a cornercorner with one O(8)LiNb2V trigonal pyramid, and corners with two equivalent O(1)LiNbVCo trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Nb(2), and one Co(2) atom to form distorted OLiNb2Co tetrahedra that share corners with four equivalent O(9)LiNbVCo tetrahedra,  an edgeedge with one O(8)LiNb2V trigonal pyramid, and edges with two equivalent O(1)LiNbVCo trigonal pyramids. In the sixth O site, O(6) is bonded in a 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 in a 4-coordinate geometry to one Li(2), one V(2), and two equivalent Co(1) atoms. In the eighth O site, O(8) is bonded to one Li(3), two equivalent Nb(2), and one V(1) atom to form distorted OLiNb2V trigonal pyramids that share  a cornercorner with one O(4)LiNbCo2 tetrahedra,  a cornercorner with one O(2)LiVCo2 tetrahedra, corners with two equivalent O(9)LiNbVCo tetrahedra, corners with two equivalent O(1)LiNbVCo trigonal pyramids,  an edgeedge with one O(5)LiNb2Co tetrahedra, and edges with two equivalent O(1)LiNbVCo trigonal pyramids. 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)LiNb2Co tetrahedra,  a cornercorner with one O(8)LiNb2V 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 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 Nb(1), one V(2), and one Co(1) 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 V(2) atom.
Li4Nb3V2Co3O16 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 Co(1)O6 octahedra, corners with two equivalent Co(2)O6 octahedra, and corners with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-64°. The Li(1)-O(12) bond length is 2.04 Å. The Li(1)-O(3) bond length is 1.95 Å. Both Li(1)-O(9) bond lengths are 2.07 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 Nb(2)O6 octahedra,  an edgeedge with one Nb(1)O6 octahedra, and edges with two equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-66°. The Li(2)-O(5) bond length is 1.82 Å. The Li(2)-O(7) bond length is 2.02 Å. Both Li(2)-O(11) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(4), one O(8), and two equivalent O(1) atoms. The Li(3)-O(4) bond length is 1.89 Å. The Li(3)-O(8) bond length is 2.43 Å. Both Li(3)-O(1) bond lengths are 2.00 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 Nb(1)O6 octahedra, corners with two equivalent Nb(2)O6 octahedra, corners with three equivalent V(1)O6 octahedra, and corners with four equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-63°. The Li(4)-O(10) bond length is 1.96 Å. The Li(4)-O(2) bond length is 1.92 Å. Both Li(4)-O(6) bond lengths are 1.99 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 distorted NbO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with four equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The Nb(1)-O(3) bond length is 1.97 Å. The Nb(1)-O(4) bond length is 1.96 Å. Both Nb(1)-O(11) bond lengths are 2.36 Å. Both Nb(1)-O(6) bond lengths are 1.90 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 V(1)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, edges with two equivalent Nb(2)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-51°. The Nb(2)-O(1) bond length is 2.03 Å. The Nb(2)-O(10) bond length is 2.01 Å. The Nb(2)-O(12) bond length is 2.06 Å. The Nb(2)-O(5) bond length is 2.05 Å. The Nb(2)-O(8) bond length is 2.07 Å. The Nb(2)-O(9) bond length is 2.01 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(2), one O(8), two equivalent O(1), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Co(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 Co(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-55°. The V(1)-O(2) bond length is 1.96 Å. The V(1)-O(8) bond length is 2.19 Å. Both V(1)-O(1) bond lengths are 2.02 Å. Both V(1)-O(6) bond lengths are 2.17 Å. In the second V site, V(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 V(2)-O(12) bond length is 2.37 Å. The V(2)-O(7) bond length is 1.75 Å. Both V(2)-O(11) bond lengths are 1.84 Å. Both V(2)-O(9) bond lengths are 2.03 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 distorted CoO6 octahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The Co(1)-O(11) bond length is 2.15 Å. The Co(1)-O(2) bond length is 2.02 Å. The Co(1)-O(3) bond length is 2.04 Å. The Co(1)-O(4) bond length is 2.03 Å. The Co(1)-O(6) bond length is 2.21 Å. The Co(1)-O(7) bond length is 2.27 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 distorted CoO6 octahedra that share corners with two equivalent V(1)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, and edges with four equivalent Nb(2)O6 octahedra. The corner-sharing octahedral tilt angles are 55°. The Co(2)-O(10) bond length is 2.06 Å. The Co(2)-O(5) bond length is 2.21 Å. Both Co(2)-O(1) bond lengths are 2.29 Å. Both Co(2)-O(9) bond lengths are 2.09 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(1), and one Co(2) atom to form distorted OLiNbVCo trigonal pyramids that share  a cornercorner with one O(4)LiNbCo2 tetrahedra,  a cornercorner with one O(2)LiVCo2 tetrahedra, corners with three equivalent O(9)LiNbVCo tetrahedra,  a cornercorner with one O(8)LiNb2V trigonal pyramid,  a cornercorner with one O(1)LiNbVCo trigonal pyramid,  an edgeedge with one O(5)LiNb2Co tetrahedra,  an edgeedge with one O(8)LiNb2V trigonal pyramid, and  an edgeedge with one O(1)LiNbVCo trigonal pyramid. In the second O site, O(2) is bonded to one Li(4), one V(1), and two equivalent Co(1) atoms to form distorted OLiVCo2 tetrahedra that share corners with two equivalent O(4)LiNbCo2 tetrahedra,  a cornercorner with one O(8)LiNb2V trigonal pyramid, and corners with two equivalent O(1)LiNbVCo 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 Co(1) atoms. In the fourth O site, O(4) is bonded to one Li(3), one Nb(1), and two equivalent Co(1) atoms to form OLiNbCo2 tetrahedra that share corners with two equivalent O(2)LiVCo2 tetrahedra,  a cornercorner with one O(8)LiNb2V trigonal pyramid, and corners with two equivalent O(1)LiNbVCo trigonal pyramids. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Nb(2), and one Co(2) atom to form distorted OLiNb2Co tetrahedra that share corners with four equivalent O(9)LiNbVCo tetrahedra,  an edgeedge with one O(8)LiNb2V trigonal pyramid, and edges with two equivalent O(1)LiNbVCo trigonal pyramids. In the sixth O site, O(6) is bonded in a 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 in a 4-coordinate geometry to one Li(2), one V(2), and two equivalent Co(1) atoms. In the eighth O site, O(8) is bonded to one Li(3), two equivalent Nb(2), and one V(1) atom to form distorted OLiNb2V trigonal pyramids that share  a cornercorner with one O(4)LiNbCo2 tetrahedra,  a cornercorner with one O(2)LiVCo2 tetrahedra, corners with two equivalent O(9)LiNbVCo tetrahedra, corners with two equivalent O(1)LiNbVCo trigonal pyramids,  an edgeedge with one O(5)LiNb2Co tetrahedra, and edges with two equivalent O(1)LiNbVCo trigonal pyramids. 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)LiNb2Co tetrahedra,  a cornercorner with one O(8)LiNb2V 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 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 Nb(1), one V(2), and one Co(1) 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 V(2) atom.