X = Cl, Br) as Tectons in Crystal Engineering Involving Halogen Bonds

Authors :: Kashina, Maria V.
Ivanov, Daniil M.
Kinzhalov, Mikhail A.
Source :: Crystals, Volume 11, Issue 7
Publication Year :: 2021
Publisher :: Multidisciplinary Digital Publishing Institute, 2021.
Abstract: The isocyanide complexes cis-[MCl2(CNC6H4-4-X)2] (M = Pd<br />X = Cl, Br<br />M = Pt<br />X = Br) form isomorphous crystal structures exhibiting the Cl/Br and Pd/Pt exchanges featuring 1D chains upon crystallisation. Crystal packing is supported by the C–X···X–C halogen bonds (HaBs), C–H···X–C hydrogen bonds (HB), X···M semicoordination, and C···C contacts between the C atoms of aryl isocyanide ligands. The results of DFT calculations and topological analysis indicate that all the above contact types belong to attractive noncovalent interactions. A projection of the electron localization function (ELF) and an inspection of the electron density (ED) and the electrostatic potential (ESP) reveal the amphiphilic nature of X atoms playing the role of HaB donors, HaB and HB acceptors, and a nucleophilic partner in X···M semicoordination.