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Reverse Sandwich Structures from Interplay between Lone Pair−π-Hole Atom-Directed C···dz2[M] and Halogen Bond Interactions

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journal contribution
posted on 02.01.2020, 20:16 by Sergey V. Baykov, Sergey I. Filimonov, Anton V. Rozhkov, Alexander S. Novikov, Ivan V. Ananyev, Daniil M. Ivanov, Vadim Yu. Kukushkin
4-Bromo- and 4-iodo-5-nitrophthalonitriles (BNPN and INPN, respectively) were cocrystallized with the metal acetylacetonates [M­(acac)2] (M = Pd (1), Pt (2)) to give the three adducts 1·2BNPN, 2·2BNPN, and 1·2INPN, exhibiting reverse arene sandwich solid-state structures. The inspection of the XRD data for the adducts revealed new types of (lone pair)­[M]···π-hole noncovalent interactions, namely atom-directed C···dz2[M] noncovalent contacts. In addition, C–X···(O,O) (X = I, Br) bifurcated halogen bonds (XBs) along with some other types of short contacts were recognized. The XRD experiments were supported by Hirshfeld surface analysis and DFT calculations: i.e., topological analysis of the electron density distribution within the framework of the QTAIM method at the ωB97XD/DZP-DKH level of theory. Estimated energies of all studied noncovalent contacts vary from 0.6 to 3.8 kcal/mol.