The energy frameworks of aufbau synthon modules in 4-cyanopyridine co-crystals

The supramolecular arrangement of 4-cyanopyridine (4CNpy) in its native crystal form and its co-crystals with halogen bond (XB) donors is discussed in terms of long-range synthon aufbau modules (LSAMs) and energy frameworks. Dissociations of 2D zigzag chains of parent 4CNpy into 1D dimers observed in its co-crystals are in good agreement with the aufbau model. Its co-formers, XB donors 1,4-I₂(CF₂)₄, C₂I₂, 1,3-and 1,4-I₂C₆F₄ (m-and p-DITFB), provide equal energy of I⋯N XBs, but perfluorinated iodo-Alkane 1,4-I₂(CF₂)₄ and diiodoacetylene C₂I₂ cannot achieve the same strength of homomolecular aggregation as π-π stacking in columnar DITFB modules. As a result, DITFBs form I⋯N XBs with both N_py and N_CN nitrogen atoms of 4CNpy, while 1,4-I₂(CF₂)₄ and C₂I₂ only with the N_py atom. This is not a particular case of 4CNpy co-crystals, but in general, DITFB appears to be a more effective XB donor co-former than C₂I₂, 1,4-I₂(CF₂)_n and other iodo-XB donors, which has similar potential to an iodine atom but lacks homomolecular aggregation. In supramolecular reactions of p-DITFB with (η⁶-Ar)RuX₂(4CNpy) (Ar = p-cymene, X = Cl, I) bearing N_py-coordinated 4CNpy, the former gives definite preference to the XBs with the halogen atoms, but not to the CN group of the 4CNpy ligand.