Short X···N Halogen Bonds With Hexamethylenetetraamine as the Acceptor
Anyfanti, G., Bauzá, A., Gentiluomo, L., Rodrigues, J., Portalone, G., Frontera, A., Rissanen, K., & Puttreddy, R. (2021). Short X···N Halogen Bonds With Hexamethylenetetraamine as the Acceptor. Frontiers in Chemistry, 9, Article 623595. https://doi.org/10.3389/fchem.2021.623595
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2021Copyright
© 2021 the Authors
Hexamethylenetetramine (HMTA) and N-haloimides form two types of short (imide)X···N and X–X···N (X = Br, I) halogen bonds. Nucleophilic substitution or ligand-exchange reaction on the peripheral X of X–X···N with the chloride of N-chlorosuccinimide lead to Cl–X···N halogen-bonded complexes. The 1:1 complexation of HMTA and ICl manifests the shortest I···N halogen bond [2.272(5) Å] yet reported for an HMTA acceptor. Two halogen-bonded organic frameworks are prepared using 1:4 molar ratio of HMTA and N-bromosuccinimide, each with a distinct channel shape, one possessing oval and the other square grid. The variations in channel shapes are due to tridentate and tetradentate (imide)Br···N coordination modes of HMTA. Density Functional Theory (DFT) studies are performed to gain insights into (imide)X···N interaction strengths (ΔEint). The calculated ΔEint values for (imide)Br···N (−11.2 to −12.5 kcal/mol) are smaller than the values for (imide)I···N (−8.4 to −29.0 kcal/mol). The DFT additivity analysis of (imide)Br···N motifs demonstrates Br···N interaction strength gradually decreasing from 1:1 to 1:3 HMTA:N-bromosuccinimide complexes. Exceptionally similar charge density values ρ(r) for N–I covalent bond and I···N non-covalent bond of a (saccharin)N–I···N motif signify the covalent character for I···N halogen bonding.
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The authors gratefully acknowledge financial support from the Academy of Finland (RP: grant no. 298817) and the University of Jyväskylä. AF and AB thank the MICIU/AEI from Spain for financial support (project number CTQ2017-85821-R, FEDER funds). JR acknowledges the support of FCT-Fundação para a Ciência e a Tecnologia (Base Fund UIDB/00674/2020 and Programmatic Fund UIDP/00674/2020, Portuguese Government Funds). ...License
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