Bond orders for intermolecular interactions in crystals: charge transfer, ionicity and the effect on intramolecular bonds

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Bond orders for intermolecular interactions in crystals : charge transfer, ionicity and the effect on intramolecular bonds. / Alhameedi, Khidhir; Karton, Amir; Jayatilaka, Dylan; Thomas, Sajesh P.

In: IUCrJ, Vol. 5, No. 5, 09.2018, p. 635-646.

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Alhameedi, Khidhir ; Karton, Amir ; Jayatilaka, Dylan ; Thomas, Sajesh P. / Bond orders for intermolecular interactions in crystals : charge transfer, ionicity and the effect on intramolecular bonds. In: IUCrJ. 2018 ; Vol. 5, No. 5. pp. 635-646.

Bibtex

@article{b6d27aba3ff7426e96b78f15f5461b04,
title = "Bond orders for intermolecular interactions in crystals: charge transfer, ionicity and the effect on intramolecular bonds",
abstract = "The question of whether intermolecular interactions in crystals originate from localized atom center dot center dot center dot atom interactions or as a result of holistic molecule center dot center dot center dot molecule close packing is a matter of continuing debate. In this context, the newly introduced Roby-Gould bond indices are reported for intermolecular 'sigma-hole' interactions, such as halogen bonding and chalcogen bonding, and compared with those for hydrogen bonds. A series of 97 crystal systems exhibiting these interaction motifs obtained from the Cambridge Structural Database (CSD) has been analysed. In contrast with conventional bond-order estimations, the new method separately estimates the ionic and covalent bond indices for atom center dot center dot center dot atom and molecule center dot center dot center dot molecule bond orders, which shed light on the nature of these interactions. A consistent trend in charge transfer from halogen/chalcogen bond-acceptor to bond-donor groups has been found in these intermolecular interaction regions via Hirshfeld atomic partitioning of the electron populations. These results, along with the 'conservation of bond orders' tested in the interaction regions, establish the significant role of localized atom center dot center dot center dot atom interactions in the formation of these intermolecular binding motifs.",
keywords = "intermolecular interactions, bond order, ionicity, hydrogen bonding, halogen bonding, crystal engineering, computational modelling, molecular crystals, CAMBRIDGE STRUCTURAL DATABASE, ATOM-ATOM BONDS, DENSITY ANALYSIS, HALOGEN BOND, CHALCOGEN, HYDROGEN, PERSPECTIVE, DEFINITION, MOLECULES, ENERGIES",
author = "Khidhir Alhameedi and Amir Karton and Dylan Jayatilaka and Thomas, {Sajesh P.}",
year = "2018",
month = "9",
doi = "10.1107/S2052252518010758",
language = "English",
volume = "5",
pages = "635--646",
journal = "IUCrJ",
issn = "2052-2525",
publisher = "INT UNION CRYSTALLOGRAPHY",
number = "5",

}

RIS

TY - JOUR

T1 - Bond orders for intermolecular interactions in crystals

T2 - charge transfer, ionicity and the effect on intramolecular bonds

AU - Alhameedi, Khidhir

AU - Karton, Amir

AU - Jayatilaka, Dylan

AU - Thomas, Sajesh P.

PY - 2018/9

Y1 - 2018/9

N2 - The question of whether intermolecular interactions in crystals originate from localized atom center dot center dot center dot atom interactions or as a result of holistic molecule center dot center dot center dot molecule close packing is a matter of continuing debate. In this context, the newly introduced Roby-Gould bond indices are reported for intermolecular 'sigma-hole' interactions, such as halogen bonding and chalcogen bonding, and compared with those for hydrogen bonds. A series of 97 crystal systems exhibiting these interaction motifs obtained from the Cambridge Structural Database (CSD) has been analysed. In contrast with conventional bond-order estimations, the new method separately estimates the ionic and covalent bond indices for atom center dot center dot center dot atom and molecule center dot center dot center dot molecule bond orders, which shed light on the nature of these interactions. A consistent trend in charge transfer from halogen/chalcogen bond-acceptor to bond-donor groups has been found in these intermolecular interaction regions via Hirshfeld atomic partitioning of the electron populations. These results, along with the 'conservation of bond orders' tested in the interaction regions, establish the significant role of localized atom center dot center dot center dot atom interactions in the formation of these intermolecular binding motifs.

AB - The question of whether intermolecular interactions in crystals originate from localized atom center dot center dot center dot atom interactions or as a result of holistic molecule center dot center dot center dot molecule close packing is a matter of continuing debate. In this context, the newly introduced Roby-Gould bond indices are reported for intermolecular 'sigma-hole' interactions, such as halogen bonding and chalcogen bonding, and compared with those for hydrogen bonds. A series of 97 crystal systems exhibiting these interaction motifs obtained from the Cambridge Structural Database (CSD) has been analysed. In contrast with conventional bond-order estimations, the new method separately estimates the ionic and covalent bond indices for atom center dot center dot center dot atom and molecule center dot center dot center dot molecule bond orders, which shed light on the nature of these interactions. A consistent trend in charge transfer from halogen/chalcogen bond-acceptor to bond-donor groups has been found in these intermolecular interaction regions via Hirshfeld atomic partitioning of the electron populations. These results, along with the 'conservation of bond orders' tested in the interaction regions, establish the significant role of localized atom center dot center dot center dot atom interactions in the formation of these intermolecular binding motifs.

KW - intermolecular interactions

KW - bond order

KW - ionicity

KW - hydrogen bonding

KW - halogen bonding

KW - crystal engineering

KW - computational modelling

KW - molecular crystals

KW - CAMBRIDGE STRUCTURAL DATABASE

KW - ATOM-ATOM BONDS

KW - DENSITY ANALYSIS

KW - HALOGEN BOND

KW - CHALCOGEN

KW - HYDROGEN

KW - PERSPECTIVE

KW - DEFINITION

KW - MOLECULES

KW - ENERGIES

U2 - 10.1107/S2052252518010758

DO - 10.1107/S2052252518010758

M3 - Journal article

C2 - 30224966

VL - 5

SP - 635

EP - 646

JO - IUCrJ

JF - IUCrJ

SN - 2052-2525

IS - 5

ER -