VCo2BO5 crystallizes in the orthorhombic Pbam space group. V(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  an edgeedge with one Co(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-62°. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. In the second Co site, Co(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. In the third Co site, Co(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. B(1) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(5) atom. There are five inequivalent O sites. In the first O site, O(5) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent Co(1), and one B(1) atom. In the second O site, O(1) is bonded to two equivalent V(1), one Co(1), and one Co(2) atom to form OV2Co2 tetrahedra that share corners with three equivalent O(3)V2Co3 square pyramids, corners with three equivalent O(1)V2Co2 tetrahedra, and  an edgeedge with one O(3)V2Co3 square pyramid. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Co(3), two equivalent Co(2), and one B(1) atom. In the fourth O site, O(3) is bonded to two equivalent V(1), one Co(2), and two equivalent Co(3) atoms to form OV2Co3 square pyramids that share corners with two equivalent O(3)V2Co3 square pyramids, corners with three equivalent O(1)V2Co2 tetrahedra, edges with three equivalent O(3)V2Co3 square pyramids, and  an edgeedge with one O(1)V2Co2 tetrahedra. In the fifth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent Co(2), and one B(1) atom.
VCo2BO5 crystallizes in the orthorhombic Pbam space group. V(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form VO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, corners with two equivalent Co(3)O6 octahedra,  an edgeedge with one Co(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with two equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-62°. The V(1)-O(4) bond length is 2.11 Å. The V(1)-O(5) bond length is 2.12 Å. Both V(1)-O(1) bond lengths are 2.01 Å. Both V(1)-O(3) bond lengths are 2.08 Å. There are three inequivalent Co sites. In the first Co site, Co(1) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form CoO6 octahedra that share corners with two equivalent Co(2)O6 octahedra, edges with two equivalent Co(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. Both Co(1)-O(1) bond lengths are 2.05 Å. All Co(1)-O(5) bond lengths are 2.16 Å. In the second Co site, Co(2) is bonded to one O(1), one O(3), two equivalent O(2), and two equivalent O(4) atoms to form CoO6 octahedra that share  a cornercorner with one Co(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(2)O6 octahedra, and edges with two equivalent Co(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. The Co(2)-O(1) bond length is 1.99 Å. The Co(2)-O(3) bond length is 2.08 Å. Both Co(2)-O(2) bond lengths are 2.17 Å. Both Co(2)-O(4) bond lengths are 2.19 Å. In the third Co site, Co(3) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form CoO6 octahedra that share corners with four equivalent V(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent Co(3)O6 octahedra, and edges with four equivalent Co(2)O6 octahedra. The corner-sharing octahedral tilt angles are 16°. Both Co(3)-O(2) bond lengths are 2.10 Å. All Co(3)-O(3) bond lengths are 2.13 Å. B(1) is bonded in a trigonal planar geometry to one O(2), one O(4), and one O(5) atom. The B(1)-O(2) bond length is 1.39 Å. The B(1)-O(4) bond length is 1.39 Å. The B(1)-O(5) bond length is 1.39 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded in a rectangular see-saw-like geometry to one V(1), two equivalent Co(1), and one B(1) atom. In the second O site, O(1) is bonded to two equivalent V(1), one Co(1), and one Co(2) atom to form OV2Co2 tetrahedra that share corners with three equivalent O(3)V2Co3 square pyramids, corners with three equivalent O(1)V2Co2 tetrahedra, and  an edgeedge with one O(3)V2Co3 square pyramid. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Co(3), two equivalent Co(2), and one B(1) atom. In the fourth O site, O(3) is bonded to two equivalent V(1), one Co(2), and two equivalent Co(3) atoms to form OV2Co3 square pyramids that share corners with two equivalent O(3)V2Co3 square pyramids, corners with three equivalent O(1)V2Co2 tetrahedra, edges with three equivalent O(3)V2Co3 square pyramids, and  an edgeedge with one O(1)V2Co2 tetrahedra. In the fifth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one V(1), two equivalent Co(2), and one B(1) atom.