Long-Range Supramolecular Synthon Isomerism: Insight from a Case Study of Vinylic Tellurium Trihalides Cl(Ph)C=C(Ph)TeX3 (X = Cl, I) by Yury V. Torubaev & Aida S. Samigullina

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


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