Four-Center Nodes: Supramolecular Synthons Based on Cyclic Halogen Bonding

Mariya A Kryukova; Daniil M Ivanov; Mikhail A Kinzhalov; Alexander S Novikov; Andrey S Smirnov; Nadezhda A Bokach; Vadim Yu Kukushkin

doi:10.1002/chem.201902264

Four-Center Nodes: Supramolecular Synthons Based on Cyclic Halogen Bonding

Chemistry. 2019 Oct 28;25(60):13671-13675. doi: 10.1002/chem.201902264. Epub 2019 Aug 28.

Authors

Mariya A Kryukova¹, Daniil M Ivanov¹, Mikhail A Kinzhalov¹, Alexander S Novikov¹, Andrey S Smirnov¹, Nadezhda A Bokach¹, Vadim Yu Kukushkin¹

Affiliation

¹ Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034, Saint Petersburg, Russian Federation.

PMID: 31232494
DOI: 10.1002/chem.201902264

Abstract

The isocyanide trans-[PdBr₂ (CNC₆ H₄ -4-X')₂ ] (X'=Br, I) and nitrile trans-[PtX₂ (NCC₆ H₄ -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 .

Keywords: crystal engineering; four-center nodes; halogen bonding; noncovalent interactions; supramolecular synthons.

Abstract

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