The C–I･･･⁻O–N⁺ Halogen Bonds with Tetraiodoethylene and Aromatic N-oxides
Truong, K.-N., Rautiainen, J. M., Rissanen, K., & Puttreddy, R. (2020). The C–I･･･⁻O–N⁺ Halogen Bonds with Tetraiodoethylene and Aromatic N-oxides. Crystal Growth and Design, 20(8), 5330-5337. https://doi.org/10.1021/acs.cgd.0c00560
Published inCrystal Growth and Design
DisciplineOrgaaninen kemiaEpäorgaaninen ja analyyttinen kemiaOrganic ChemistryInorganic and Analytical Chemistry
© 2020 American Chemical society
The nature of C–I⋯⁻O–N⁺ interactions, first of its kind, between non-fluorinated tetraiodoethylene XB-donor and pyridine N-oxides (PyNO) are studied by single-crystal X-ray diffraction (SCXRD) and Density Functional Theory (DFT) calculations. Despite the non-fluorinated nature of the C2I4, the I⋯O halogen bond distances are similar to well-known perfluorohaloalkane/-arene donor-PyNO analogues. With C2I4, oxygens of the N-oxides adopt exclusively 2-XB-coordination in contrast to the versatile bonding modes observed with perfluorinated XB-donors. The C2I4 as the XB donor forms with PyNO’s one-dimensional chain polymer structures in which the C2I4⋯(μ-PyNO)2⋯C2I4 segments manifesting two bonding motifs, namely, side-by-side (vicinal di-iodo) and head-to-head (geminal di-iodo), due to the nearly symmetric square planar structure of the C2I4. While the attractive nature between I- and O-atoms is mainly electrostatic, the narrow range of C⋯O bond parameters demonstrate that the -bond between four iodine atoms also plays an important role in enhancing the -hole strength. DFT-based monodentate XB interaction energies, ΔEint, in thirteen 1:1 XB complexes vary between 31.9 – 46.5 kJ mol–1, the strongest remarkably exceeding the value reported for I–I⋯⁻O–N⁺ = 42.0 kJ mol–1. In case of C2I4･(pyridine N-oxide) [31.9 kJ mol–1], the monodentate XB energy is on a par with perfluorinated donor complexes, namely, CF3I･(pyridine N-oxide) [31.1 kJ mol–1] and C6F5I･(pyridine N-oxide) [32.3 kJ mol–1]. ...
PublisherAmerican Chemical Society
Publication in research information system
MetadataShow full item record
Related funder(s)Academy of Finland
Funding program(s)Postdoctoral Researcher, AoF
Additional information about fundingThe research work is funded by Academy of Finland (RP: grant no. 298817), and Prof. H. M. Tuononen (University of Jyvaskyla) provided the computational resources. The authors gratefully acknowledge University of Jyvaskyla for providing laboratory and SCXRD resources.
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