The different packing affects the compound porosity; thus, [Co₂(TFMBz)₄(bpy)₂]_n (2), precipitated using low-polarity solvents such as supercritical CO₂ (scCO₂), n-butyl acetate, or heptane and also in acetonitrile, is microporous, with a surface area of 330 m² g^–1, showing the N₂ adsorption/desorption isotherm at 77 K with a gate-opening effect at low relative pressures (P/P₀ = 0.05). The isomer [Co₂(TFMBz)₄(bpy)₂]_n (3), synthesized in ethoxyethanol, presents a surface area of 230 m² g^–1. A third chain packing isomer, [Co₂(TFMBz)₄(bpy)₂]_n (4), is obtained in acetone and has only non-interconnected voids. Finally, precursor 1 is combined with bpy in a highly polar solvent such as water to give [Co(TFMBz)₂(bpy)]_n (5). In this isomer, all the carboxylate units act as bidentate bridging ligands, generating chains that are interlinked by bpy, leading to a 2D network, which after packing yields a non-porous structure. The resolution of structures 2–5 is only possible with the recently developed 3D electron diffraction method based on the collection of diffraction patterns on sub-micron-sized single crystals. The variation of magnetic susceptibility as a function of temperature is also measured. Overall, our work provides insightful information on the complex landscape of metal–organic framework solids that are formed by crystallization using different solvent media.