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Four‐Center Nodes: Supramolecular Synthons Based on Cyclic Halogen Bonding
Author(s) -
Kryukova Mariya A.,
Ivanov Daniil M.,
Kinzhalov Mikhail A.,
Novikov Alexander S.,
Smirnov Andrey S.,
Bokach Nadezhda A.,
Yu. Kukushkin Vadim
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902264
Subject(s) - synthon , halogen bond , supramolecular chemistry , crystallography , chemistry , halogen , molecule , hydrogen bond , non covalent interactions , stereochemistry , center (category theory) , halide , nitrile , crystal structure , inorganic chemistry , organic chemistry , alkyl
The isocyanide trans ‐[PdBr 2 (CNC 6 H 4 ‐4‐X′) 2 ] (X′=Br, I) and nitrile trans ‐[PtX 2 (NCC 6 H 4 ‐4‐X′) 2 ] (X/X′=Cl/Cl, Cl/Br, Br/Cl, Br/Br) complexes exhibit similar structural motif in the solid state, which is determined by hitherto unreported four‐center nodes formed by cyclic halogen bonding. Each node is built up by four Type II C−X′⋅⋅⋅X−M halogen‐bonding contacts and include one Type I M−X⋅⋅⋅X−M interaction, thus giving the rhombic‐like structure. These nodes serve as supramolecular synthons to form 2D layers or double chains of molecules linked by a halogen bond. Results of DFT calculations indicate that all contacts within the nodes are typical noncovalent interactions with the estimated strengths in the range 0.6–2.9 kcal mol −1 .