Li4NbCo5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with three equivalent Nb(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  an edgeedge with one Co(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and  a faceface with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-57°. Nb(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form NbO6 octahedra that share corners with twelve equivalent Li(1)O6 octahedra and edges with six equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. In the second Co site, Co(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with three equivalent Nb(1)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. In the third Co site, Co(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Nb(1), and two equivalent Co(2) atoms to form distorted OLi2NbCo2 trigonal bipyramids that share corners with two equivalent O(2)Li2Co3 square pyramids, corners with two equivalent O(3)Li2Co3 square pyramids, corners with three equivalent O(1)Li2NbCo2 trigonal bipyramids,  an edgeedge with one O(2)Li2Co3 square pyramid, and edges with four equivalent O(1)Li2NbCo2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(3), and two equivalent Co(1) atoms to form OLi2Co3 square pyramids that share corners with two equivalent O(3)Li2Co3 square pyramids, corners with three equivalent O(2)Li2Co3 square pyramids, corners with two equivalent O(1)Li2NbCo2 trigonal bipyramids, edges with three equivalent O(3)Li2Co3 square pyramids, edges with four equivalent O(2)Li2Co3 square pyramids, and  an edgeedge with one O(1)Li2NbCo2 trigonal bipyramid. In the third O site, O(3) is bonded to two equivalent Li(1), one Co(3), and two equivalent Co(1) atoms to form OLi2Co3 square pyramids that share  a cornercorner with one O(3)Li2Co3 square pyramid, corners with four equivalent O(2)Li2Co3 square pyramids, corners with four equivalent O(1)Li2NbCo2 trigonal bipyramids,  an edgeedge with one O(3)Li2Co3 square pyramid, and edges with six equivalent O(2)Li2Co3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Nb(1), and two equivalent Co(2) atoms.
Li4NbCo5O12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Co(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, corners with three equivalent Nb(1)O6 octahedra, corners with three equivalent Co(2)O6 octahedra,  an edgeedge with one Co(3)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and  a faceface with one Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-57°. The Li(1)-O(3) bond length is 2.06 Å. The Li(1)-O(4) bond length is 2.51 Å. There is one shorter (2.15 Å) and one longer (2.49 Å) Li(1)-O(1) bond length. There is one shorter (1.97 Å) and one longer (1.98 Å) Li(1)-O(2) bond length. Nb(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form NbO6 octahedra that share corners with twelve equivalent Li(1)O6 octahedra and edges with six equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-57°. Both Nb(1)-O(4) bond lengths are 2.04 Å. All Nb(1)-O(1) bond lengths are 2.03 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with three equivalent Co(1)O6 octahedra, edges with three equivalent Co(3)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Co(1)-O(3) bond lengths are 1.96 Å. There are two shorter (1.90 Å) and two longer (2.11 Å) Co(1)-O(2) bond lengths. In the second Co site, Co(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with three equivalent Nb(1)O6 octahedra, edges with three equivalent Co(2)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-51°. Both Co(2)-O(4) bond lengths are 1.94 Å. There are two shorter (1.95 Å) and two longer (1.96 Å) Co(2)-O(1) bond lengths. In the third Co site, Co(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form CoO6 octahedra that share corners with four equivalent Li(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Co(1)O6 octahedra. The corner-sharing octahedral tilt angles are 8°. Both Co(3)-O(3) bond lengths are 1.92 Å. All Co(3)-O(2) bond lengths are 2.02 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Nb(1), and two equivalent Co(2) atoms to form distorted OLi2NbCo2 trigonal bipyramids that share corners with two equivalent O(2)Li2Co3 square pyramids, corners with two equivalent O(3)Li2Co3 square pyramids, corners with three equivalent O(1)Li2NbCo2 trigonal bipyramids,  an edgeedge with one O(2)Li2Co3 square pyramid, and edges with four equivalent O(1)Li2NbCo2 trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one Co(3), and two equivalent Co(1) atoms to form OLi2Co3 square pyramids that share corners with two equivalent O(3)Li2Co3 square pyramids, corners with three equivalent O(2)Li2Co3 square pyramids, corners with two equivalent O(1)Li2NbCo2 trigonal bipyramids, edges with three equivalent O(3)Li2Co3 square pyramids, edges with four equivalent O(2)Li2Co3 square pyramids, and  an edgeedge with one O(1)Li2NbCo2 trigonal bipyramid. In the third O site, O(3) is bonded to two equivalent Li(1), one Co(3), and two equivalent Co(1) atoms to form OLi2Co3 square pyramids that share  a cornercorner with one O(3)Li2Co3 square pyramid, corners with four equivalent O(2)Li2Co3 square pyramids, corners with four equivalent O(1)Li2NbCo2 trigonal bipyramids,  an edgeedge with one O(3)Li2Co3 square pyramid, and edges with six equivalent O(2)Li2Co3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Nb(1), and two equivalent Co(2) atoms.