Three binuclear and one mononuclear cobalt(III) dioximates with the compositions [Co₂(dmgH)₄(bpy)Cl₂]·1.5dmf (1), [Co₂(nioxH)₄(bpy)Cl₂]·0.5H₂O (2), [Co₂(dmgH)₄(bpe)Cl₂]·0.5H₂O (3), and [Co(dmgH)₂(bpy)Cl]·H₂O (4) (where dmgH₂ = dimethylglyoxime, nioxH₂ = 1,2-cyclohexanedionedioxime, bpy = 4,4′-bipyridine, bpe = 1,2-bis(4-pyridyl)ethane, and dmf = N,N-dimethylformamide) were prepared by replacement of water molecule in Co(III) mononuclear dioximates by bpy and bpe ligands. All compounds were characterized by single-crystal X-ray diffraction and spectroscopic techniques. In all complexes Co(III) atoms have an identical octahedral N₅Cl environment formulated by four nitrogen atoms of two mono-deprotonated oxime ligands in a square planar mode, and the nitrogen atom of the bpy/bpe molecules and chloride atom in the axial positions. In 1-3 bpy/bpe exobidentate spacer ligands serve as bridging "rods" and unite two planar cobalt(III) bis-dioximates in binuclear complex with wheel-and-axle topology. The packing of bulky binuclear complexes results in formation of porous structure with hourglass-like channels of diameter ca. 0.6-1.3 nm in the crystal of compound 1 and smaller cavities in 2. The sorption properties for 1 were also measured. The π⋯π stacking interaction between monodentate bpy ligands of mononuclear complexes 4 emulate supramolecular binuclear assembly with wheel-and-axle topology.