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The C-I···-O-N+Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides

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The C-I···-O-N+Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides. / Truong, Khai Nghi; Rautiainen, J. Mikko; Rissanen, Kari; Puttreddy, Rakesh.

In: Crystal Growth and Design, Vol. 20, No. 8, 05.08.2020, p. 5330-5337.

Research output: Contribution to journalArticleScientificpeer-review

Harvard

Truong, KN, Rautiainen, JM, Rissanen, K & Puttreddy, R 2020, 'The C-I···-O-N+Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides', Crystal Growth and Design, vol. 20, no. 8, pp. 5330-5337. https://doi.org/10.1021/acs.cgd.0c00560

APA

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

Vancouver

Truong KN, Rautiainen JM, Rissanen K, Puttreddy R. The C-I···-O-N+Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides. Crystal Growth and Design. 2020 Aug 5;20(8):5330-5337. https://doi.org/10.1021/acs.cgd.0c00560

Author

Truong, Khai Nghi ; Rautiainen, J. Mikko ; Rissanen, Kari ; Puttreddy, Rakesh. / The C-I···-O-N+Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides. In: Crystal Growth and Design. 2020 ; Vol. 20, No. 8. pp. 5330-5337.

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@article{bad2252e8ba2480abb058a09d4128f88,
title = "The C-I···-O-N+Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides",
abstract = "The nature of C-I···-O-N+ interactions, the first of its kind, between nonfluorinated tetraiodoethylene halogen bond (XB) donor and pyridine N-oxides (PyNO) are studied by single-crystal X-ray diffraction and density functional theory (DFT) calculations. Despite the nonfluorinated 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 μ2-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 manifest 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 demonstrates that the ?-bond between four iodine atoms also plays an important role in enhancing the σ-hole strength. DFT-Based monodentate XB interaction energies, ?Eint, in 13 1:1 XB complexes vary between 31.9 and 46.5 kJ mol-1, the strongest remarkably exceeding the value reported for I-I···-O-N+ = 42.0 kJ mol-1. In the 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].",
author = "Truong, {Khai Nghi} and Rautiainen, {J. Mikko} and Kari Rissanen and Rakesh Puttreddy",
year = "2020",
month = "8",
day = "5",
doi = "10.1021/acs.cgd.0c00560",
language = "English",
volume = "20",
pages = "5330--5337",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",
number = "8",

}

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TY - JOUR

T1 - The C-I···-O-N+Halogen Bonds with Tetraiodoethylene and Aromatic N-Oxides

AU - Truong, Khai Nghi

AU - Rautiainen, J. Mikko

AU - Rissanen, Kari

AU - Puttreddy, Rakesh

PY - 2020/8/5

Y1 - 2020/8/5

N2 - The nature of C-I···-O-N+ interactions, the first of its kind, between nonfluorinated tetraiodoethylene halogen bond (XB) donor and pyridine N-oxides (PyNO) are studied by single-crystal X-ray diffraction and density functional theory (DFT) calculations. Despite the nonfluorinated 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 μ2-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 manifest 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 demonstrates that the ?-bond between four iodine atoms also plays an important role in enhancing the σ-hole strength. DFT-Based monodentate XB interaction energies, ?Eint, in 13 1:1 XB complexes vary between 31.9 and 46.5 kJ mol-1, the strongest remarkably exceeding the value reported for I-I···-O-N+ = 42.0 kJ mol-1. In the 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].

AB - The nature of C-I···-O-N+ interactions, the first of its kind, between nonfluorinated tetraiodoethylene halogen bond (XB) donor and pyridine N-oxides (PyNO) are studied by single-crystal X-ray diffraction and density functional theory (DFT) calculations. Despite the nonfluorinated 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 μ2-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 manifest 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 demonstrates that the ?-bond between four iodine atoms also plays an important role in enhancing the σ-hole strength. DFT-Based monodentate XB interaction energies, ?Eint, in 13 1:1 XB complexes vary between 31.9 and 46.5 kJ mol-1, the strongest remarkably exceeding the value reported for I-I···-O-N+ = 42.0 kJ mol-1. In the 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].

U2 - 10.1021/acs.cgd.0c00560

DO - 10.1021/acs.cgd.0c00560

M3 - Article

VL - 20

SP - 5330

EP - 5337

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 8

ER -