Planarity-Driven Structure–Morphology Correlations in a Co(II) Benzoylacetonate: Comparative Insights across the [M(bzac) 2 ] Family

Advancing structure–packing–morphology correlations in β-diketonate complexes provides a rigorous framework for how local coordination geometry propagates into supramolecular organization and ultimately governs macroscopic form. Within this context, we report the synthesis, single-crystal and powder X-ray diffraction analysis, targeted CSD mining, BFDH morphology modeling, and complementary quantum calculations of a new cobalt(II) benzoylacetonate, [Co(bzac) 2 ]. Accurate SC-XRD data at 100 K establish a centrosymmetric trans-CoO 4 chromophore in P 2 1 / n with a quasi square-planar coordination environment, while PXRD confirms phase purity. In the solid state, [Co(bzac) 2 ] forms directionally coherent zigzag stacks consistent with its experimentally observed acicular habit. A comparative CSD-survey across [M(bzac) 2 ] (M= Pb, Sn, Pd̂trans, Pd̂cis, Cu) reveals metal-dependent variations in stereochemistry, chelate planarity, and packing, positioning the cobalt complex at the most planar and structurally coherent limit. BFDH analysis uncovers a monotonic increase in growth anisotropy culminating in [Co(bzac) 2 ], whose short π–π, metal−π, and C–H···π contacts rationalize its needle-like morphology. FTIR confirms enolization and O,O′-chelation, while UV–vis spectra display ligand-centered π → π* and n → π* transitions. DFT reproduces the experimental symmetry and electronic partitioning, and TD-DFT recovers the absorption envelope. Overall, the integrated SC-XRD ↔ CSD ↔ BFDH ↔ DFT workflow establishes [Co(bzac) 2 ] as a crystallographic, morphological, and electronic benchmark within the family.