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Push−Pull and Conventional Nitriles as Halogen Bond Acceptors in Their Cocrystals with Iodo-Substituted Perfluorobenzenes. / Тойкка, Юлия Николаевна; Gomila, Rosa; Frontera, Antonio; Изотова, Юлия Анверовна; Кукушкин, Вадим Юрьевич; Бокач, Надежда Арсеньевна.

в: Crystal Growth and Design, 09.10.2023.

Результаты исследований: Научные публикации в периодических изданияхстатьяРецензирование

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@article{b6af527656b54b6387be7dae8a2e5373,
title = "Push−Pull and Conventional Nitriles as Halogen Bond Acceptors in Their Cocrystals with Iodo-Substituted Perfluorobenzenes",
abstract = "Co-crystallization of the push-pull nitriles NCNR2 (R2 = Me2 1, C4H8 2, C5H10 3, and C4H8O 4) with iodo-substituted perfluorobenzenes (1,4-diiodotetrafluorobenzene − 1,4-FIB and 1,3,5-triiodotrifluorobenzene − 1,3,5-FIB) gave cocrystals 1·1,3,5-FIB, 2·1,3,5-FIB, 3·1/2(1,4-FIB), 4·1/2(1,4-FIB), and 4·2(1,3,5-FIB), which were studied by single-crystal X-ray diffractometry (XRD). The structure-directing I···sp-Nnitrile halogen bond (HaB) in all cocrystals was identified based on the consideration of the XRD geometrical (bond length and angles) parameters and also by Hirshfeld surface analysis, whereupon the observed HaBs were analyzed theoretically. The HaB-accepting role of the push-pulling dialkylcyanamides NCNR2 and conventional nitriles NCR (R = Alk) was examined and compared in detail using, as model examples, the structures of cocrystals 3·1/2(1,4-FIB) (this work) and AdCN·1/2(1,4-FIB) (CSD refcode: KIHROL). These two cocrystals, which display similar supramolecular organization, were studied by several quantum chemistry methods including molecular electrostatic potential surface analysis, the natural bond orbital analysis, the quantum theory of atoms in molecules combined with the NCIPlot approach, and also by the Kitaura-Morokuma energy decomposition approach. While AdCN is a slightly poorer sp-N electron donor than the push-pull nitrile 3, HaBs in the cocrystals exhibit similar interaction energies. Although in the covalent chemistry the two types of nitriles often exhibit strikingly different reactivity patterns, the σ-hole-based I···sp-Nnitrile noncovalent interaction provided the leveling effect, resulting in significant similarities between the HaB situations for both nitrile species.",
author = "Тойкка, {Юлия Николаевна} and Rosa Gomila and Antonio Frontera and Изотова, {Юлия Анверовна} and Кукушкин, {Вадим Юрьевич} and Бокач, {Надежда Арсеньевна}",
year = "2023",
month = oct,
day = "9",
doi = "10.1021/acs.cgd.3c00978",
language = "English",
journal = "Crystal Growth and Design",
issn = "1528-7483",
publisher = "American Chemical Society",

}

RIS

TY - JOUR

T1 - Push−Pull and Conventional Nitriles as Halogen Bond Acceptors in Their Cocrystals with Iodo-Substituted Perfluorobenzenes

AU - Тойкка, Юлия Николаевна

AU - Gomila, Rosa

AU - Frontera, Antonio

AU - Изотова, Юлия Анверовна

AU - Кукушкин, Вадим Юрьевич

AU - Бокач, Надежда Арсеньевна

PY - 2023/10/9

Y1 - 2023/10/9

N2 - Co-crystallization of the push-pull nitriles NCNR2 (R2 = Me2 1, C4H8 2, C5H10 3, and C4H8O 4) with iodo-substituted perfluorobenzenes (1,4-diiodotetrafluorobenzene − 1,4-FIB and 1,3,5-triiodotrifluorobenzene − 1,3,5-FIB) gave cocrystals 1·1,3,5-FIB, 2·1,3,5-FIB, 3·1/2(1,4-FIB), 4·1/2(1,4-FIB), and 4·2(1,3,5-FIB), which were studied by single-crystal X-ray diffractometry (XRD). The structure-directing I···sp-Nnitrile halogen bond (HaB) in all cocrystals was identified based on the consideration of the XRD geometrical (bond length and angles) parameters and also by Hirshfeld surface analysis, whereupon the observed HaBs were analyzed theoretically. The HaB-accepting role of the push-pulling dialkylcyanamides NCNR2 and conventional nitriles NCR (R = Alk) was examined and compared in detail using, as model examples, the structures of cocrystals 3·1/2(1,4-FIB) (this work) and AdCN·1/2(1,4-FIB) (CSD refcode: KIHROL). These two cocrystals, which display similar supramolecular organization, were studied by several quantum chemistry methods including molecular electrostatic potential surface analysis, the natural bond orbital analysis, the quantum theory of atoms in molecules combined with the NCIPlot approach, and also by the Kitaura-Morokuma energy decomposition approach. While AdCN is a slightly poorer sp-N electron donor than the push-pull nitrile 3, HaBs in the cocrystals exhibit similar interaction energies. Although in the covalent chemistry the two types of nitriles often exhibit strikingly different reactivity patterns, the σ-hole-based I···sp-Nnitrile noncovalent interaction provided the leveling effect, resulting in significant similarities between the HaB situations for both nitrile species.

AB - Co-crystallization of the push-pull nitriles NCNR2 (R2 = Me2 1, C4H8 2, C5H10 3, and C4H8O 4) with iodo-substituted perfluorobenzenes (1,4-diiodotetrafluorobenzene − 1,4-FIB and 1,3,5-triiodotrifluorobenzene − 1,3,5-FIB) gave cocrystals 1·1,3,5-FIB, 2·1,3,5-FIB, 3·1/2(1,4-FIB), 4·1/2(1,4-FIB), and 4·2(1,3,5-FIB), which were studied by single-crystal X-ray diffractometry (XRD). The structure-directing I···sp-Nnitrile halogen bond (HaB) in all cocrystals was identified based on the consideration of the XRD geometrical (bond length and angles) parameters and also by Hirshfeld surface analysis, whereupon the observed HaBs were analyzed theoretically. The HaB-accepting role of the push-pulling dialkylcyanamides NCNR2 and conventional nitriles NCR (R = Alk) was examined and compared in detail using, as model examples, the structures of cocrystals 3·1/2(1,4-FIB) (this work) and AdCN·1/2(1,4-FIB) (CSD refcode: KIHROL). These two cocrystals, which display similar supramolecular organization, were studied by several quantum chemistry methods including molecular electrostatic potential surface analysis, the natural bond orbital analysis, the quantum theory of atoms in molecules combined with the NCIPlot approach, and also by the Kitaura-Morokuma energy decomposition approach. While AdCN is a slightly poorer sp-N electron donor than the push-pull nitrile 3, HaBs in the cocrystals exhibit similar interaction energies. Although in the covalent chemistry the two types of nitriles often exhibit strikingly different reactivity patterns, the σ-hole-based I···sp-Nnitrile noncovalent interaction provided the leveling effect, resulting in significant similarities between the HaB situations for both nitrile species.

UR - https://www.mendeley.com/catalogue/4086bcf7-1d4c-3cc9-a261-958ee5b1e71f/

U2 - 10.1021/acs.cgd.3c00978

DO - 10.1021/acs.cgd.3c00978

M3 - Article

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

ER -

ID: 111819755