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Hydroquinone (benzene-1,4-diol or quinol) is reported here to form co-crystals in different ratios with propan-2-ol, N,N-dimethylacetamide (DMA) and N,N-diethylformamide (DEF). Investigation of intermolecular interactions and crystal packing via Hirshfeld surface analysis reveals that more than two-thirds of the close contacts are associated with relatively weak HÁ Á ÁH, CÁ Á ÁH and HÁ Á ÁC interactions. The use of Hirshfeld surfaces in combination with fingerprint plots demonstrates that these weak interactions are important for both local packing and crystal packing. The complexes highlight the way in which electrostatic complementarity to a large extent governs the hydrogen bonding pattern in molecular crystals.Scheme 1

The charge density of Co2(CO)6(HC[triple bond]CC6H10OH) (1) in the crystalline state has been determined using multipolar refinement of single-crystal X-ray diffraction data collected (i) with a synchrotron source at very low temperatures (15 K) and (ii) using a conventional source with the crystal at intermediate temperature (100 K). The X-ray charge density model is augmented by complete active space and density functional theory calculations. Topological analyses of the different charge distributions show that the two Co atoms are not bonded to each other in the quantum theory of atoms in molecules (QTAIM) sense of the word. However, the behavior of the source function and the total energy density indicate that there is some bond-like character in the Co-Co interaction. The bridging alkyne fragment provides an unusual bonding situation, with extremely small electron density differences between the two Co-C bond critical points and the "CoC2" ring critical point. Thus, the structure is close to a topological catastrophe point. Comparison of the results obtained from the two diffraction data sets and ab initio theory suggests that the topology of the experimental electron density in this special atomic environment is highly sensitive to subtle effects of measurement errors and potential shortcomings of the multipole model, or to effects of the crystal field. Thus, even the two identical molecules in the asymmetric unit show altered bonding patterns.

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