V5CoO12 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-59°. In the second V site, V(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-61°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one Co(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Co(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom.
V5CoO12 crystallizes in the monoclinic C2 space group. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form VO4 tetrahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Co(1)O6 octahedra, and corners with two equivalent V(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 31-59°. The V(1)-O(1) bond length is 1.74 Å. The V(1)-O(2) bond length is 1.69 Å. The V(1)-O(4) bond length is 1.78 Å. The V(1)-O(5) bond length is 1.78 Å. In the second V site, V(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form VO4 tetrahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-61°. The V(2)-O(3) bond length is 1.76 Å. The V(2)-O(4) bond length is 1.82 Å. The V(2)-O(5) bond length is 1.81 Å. The V(2)-O(6) bond length is 1.72 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent V(1)O4 tetrahedra, corners with four equivalent V(2)O4 tetrahedra, and edges with two equivalent Co(1)O6 octahedra. Both V(3)-O(1) bond lengths are 2.13 Å. Both V(3)-O(3) bond lengths are 2.06 Å. Both V(3)-O(6) bond lengths are 1.98 Å. Co(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CoO6 octahedra that share corners with two equivalent V(2)O4 tetrahedra, corners with four equivalent V(1)O4 tetrahedra, and edges with two equivalent V(3)O6 octahedra. Both Co(1)-O(1) bond lengths are 2.15 Å. Both Co(1)-O(2) bond lengths are 2.02 Å. Both Co(1)-O(3) bond lengths are 2.22 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one V(1), one V(3), and one Co(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one V(1) and one Co(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one V(2), one V(3), and one Co(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(1) and one V(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one V(2) and one V(3) atom.