Isocyanide and Cyanide Entities Form Isostructural Halogen Bond-Based Supramolecular Networks Featuring Five-Center Tetrafurcated Halogen···C/N Bonding

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Isocyanide and Cyanide Entities Form Isostructural Halogen Bond-Based Supramolecular Networks Featuring Five-Center Tetrafurcated Halogen···C/N Bonding. / Mikherdov, Alexander S.; Popov, Roman A.; Smirnov, Andrey S.; Eliseeva, Anastasiya A.; Novikov, Alexander S.; Boyarskiy, Vadim P.; Gomila, Rosa Maria; Frontera, Antonio ; Kukushkin, Vadm Yu.; Bokach, Nadezhda A.

In: Crystal Growth and Design, Vol. 22, No. 10, 05.10.2022, p. 6079-6087.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{52296226dbff41568056734646f7e9b2,

title = "Isocyanide and Cyanide Entities Form Isostructural Halogen Bond-Based Supramolecular Networks Featuring Five-Center Tetrafurcated Halogen···C/N Bonding",

abstract = "A typical halogen bond (HaB) donor, 1,4-dibromo-2,3,5,6-tetrafluorobenzene (FBB), was cocrystallized with the isocyanide CNMes and the cyanide NCMes to give two isostructural cocrystals, (CNMes)·FBB and (NCMes)·FBB. Their solid-state architecture exhibits a close similarity between the isocyanide and cyanide groups in their HaB-accepting role. This similarity and particular bonding features of the HaBs were additionally verified by theoretical calculations (molecular electrostatic potential analysis, electron density/electrostatic potential profiles, atoms-in-molecules charge analysis, and calculations of pKa values and binding energies). Remarkably, both cocrystals form unusual heterohexamers where one Br atom of FBB simultaneously forms four contacts with two C (or N) and two Br atoms of neighboring molecules. On the basis of the geometric parameters and the theoretical data, these contacts can be defined as five-center tetrafurcated μ4-Br···(C, Br, C, Br) and μ4-Br···(N, Br, N, Br) HaBs; this is the first observation of the tetrafurcated HaB involving four disunited HaB acceptors.",

author = "Mikherdov, {Alexander S.} and Popov, {Roman A.} and Smirnov, {Andrey S.} and Eliseeva, {Anastasiya A.} and Novikov, {Alexander S.} and Boyarskiy, {Vadim P.} and Gomila, {Rosa Maria} and Antonio Frontera and Kukushkin, {Vadm Yu.} and Bokach, {Nadezhda A.}",

note = "Publisher Copyright: {\textcopyright} 2022 American Chemical Society.",

year = "2022",

month = oct,

day = "5",

doi = "10.1021/acs.cgd.2c00686",

language = "English",

volume = "22",

pages = "6079--6087",

journal = "Crystal Growth and Design",

issn = "1528-7483",

publisher = "American Chemical Society",

number = "10",

}

RIS

TY - JOUR

T1 - Isocyanide and Cyanide Entities Form Isostructural Halogen Bond-Based Supramolecular Networks Featuring Five-Center Tetrafurcated Halogen···C/N Bonding

AU - Mikherdov, Alexander S.

AU - Popov, Roman A.

AU - Smirnov, Andrey S.

AU - Eliseeva, Anastasiya A.

AU - Novikov, Alexander S.

AU - Boyarskiy, Vadim P.

AU - Gomila, Rosa Maria

AU - Frontera, Antonio

AU - Kukushkin, Vadm Yu.

AU - Bokach, Nadezhda A.

PY - 2022/10/5

Y1 - 2022/10/5

N2 - A typical halogen bond (HaB) donor, 1,4-dibromo-2,3,5,6-tetrafluorobenzene (FBB), was cocrystallized with the isocyanide CNMes and the cyanide NCMes to give two isostructural cocrystals, (CNMes)·FBB and (NCMes)·FBB. Their solid-state architecture exhibits a close similarity between the isocyanide and cyanide groups in their HaB-accepting role. This similarity and particular bonding features of the HaBs were additionally verified by theoretical calculations (molecular electrostatic potential analysis, electron density/electrostatic potential profiles, atoms-in-molecules charge analysis, and calculations of pKa values and binding energies). Remarkably, both cocrystals form unusual heterohexamers where one Br atom of FBB simultaneously forms four contacts with two C (or N) and two Br atoms of neighboring molecules. On the basis of the geometric parameters and the theoretical data, these contacts can be defined as five-center tetrafurcated μ4-Br···(C, Br, C, Br) and μ4-Br···(N, Br, N, Br) HaBs; this is the first observation of the tetrafurcated HaB involving four disunited HaB acceptors.

AB - A typical halogen bond (HaB) donor, 1,4-dibromo-2,3,5,6-tetrafluorobenzene (FBB), was cocrystallized with the isocyanide CNMes and the cyanide NCMes to give two isostructural cocrystals, (CNMes)·FBB and (NCMes)·FBB. Their solid-state architecture exhibits a close similarity between the isocyanide and cyanide groups in their HaB-accepting role. This similarity and particular bonding features of the HaBs were additionally verified by theoretical calculations (molecular electrostatic potential analysis, electron density/electrostatic potential profiles, atoms-in-molecules charge analysis, and calculations of pKa values and binding energies). Remarkably, both cocrystals form unusual heterohexamers where one Br atom of FBB simultaneously forms four contacts with two C (or N) and two Br atoms of neighboring molecules. On the basis of the geometric parameters and the theoretical data, these contacts can be defined as five-center tetrafurcated μ4-Br···(C, Br, C, Br) and μ4-Br···(N, Br, N, Br) HaBs; this is the first observation of the tetrafurcated HaB involving four disunited HaB acceptors.

UR - https://www.mendeley.com/catalogue/b8d20dc3-421c-3fff-8789-c8b03a248b58/

UR - http://www.scopus.com/inward/record.url?scp=85138048556&partnerID=8YFLogxK

U2 - 10.1021/acs.cgd.2c00686

DO - 10.1021/acs.cgd.2c00686

M3 - Article

VL - 22

SP - 6079

EP - 6087

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 10

ER -

ID: 98270420