Long-Range Supramolecular Synthon Isomerism: Insight from a Case Study of Vinylic Tellurium Trihalides Cl(Ph)C=C(Ph)TeX3 (X = Cl, I)

A slight modification of the synthetic procedure resulted in a new (Cc) polymorph vinylic tellurium-trichloride Z-Cl(Ph)C=C(Ph)TeCl3 (1, β-form) which is stabilized by Te⋯Cl chalcogen bonds, assembling its molecules into zigzag chains. Such packing motive contrast to known (Pca21) α-form, CCDC refcode: BESHOW), built upon Te⋯π(Ph) bonded We noted similar case [Te⋯halogen] vs. [Te⋯π(Ph)] supramolecular synthon polymorphism triiodide congener Z-Cl(Ph)C=CPh(TeI3) (2, α and β-polymorphic forms). Quantum chemical calculations intermolecular interaction lattice energies for 1α–β 2α–β supported assumption that thermodynamic while β kinetic form. Kinetic forms 1β 2β are isostructural (Cc), 1α 2α (P21/c) not feature an unusual example long-range module isomerism. In other words, 1α–2α pairs demonstrate very similarly Te⋯πPh ChB chains, further packed differently relative each other, following different angular geometry type-I Cl⋯Cl type-II I⋯I halogen bonding. These structural considerations backed quantum support proposed hierarchy primary secondary synthons assignment as forms, respectively.