TY - JOUR

T1 - Halogen Bonding Involving Isomeric Isocyanide/Nitrile Groups

AU - Смирнов, Андрей Сергеевич

AU - Катленок, Евгений Анатольевич

AU - Михердов, Александр Сергеевич

AU - Крюкова, Мария Александровна

AU - Бокач, Надежда Арсеньевна

AU - Кукушкин, Вадим Юрьевич

PY - 2023/8/28

Y1 - 2023/8/28

N2 - 2,3,5,6-Tetramethyl-1,4-diisocyanobenzene ( 1), 1,4-diisocyanobenzene ( 2), and 1,4-dicyanobenzene ( 3) were co-crystallized with 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) to give three cocrystals, 1·1,3,5-FIB, 2·2(1,3,5-FIB), and 3·2(1,3,5-FIB), which were studied by X-ray diffraction. A common feature of the three structures is the presence of I···C isocyanide or I···N nitrile halogen bonds (HaBs), which occurs between an iodine σ-hole and the isocyanide C-(or the nitrile N-) atom. The diisocyanide and dinitrile cocrystals 2·2(1,3,5-FIB) and 3·2(1,3,5-FIB) are isostructural, thus providing a basis for accurate comparison of the two types of noncovalent linkages of C≡N/N≡C groups in the composition of structurally similar entities and in one crystal environment. The bonding situation was studied by a set of theoretical methods. Diisocyanides are more nucleophilic than the dinitrile and they exhibit stronger binding to 1,3,5-FIB. In all structures, the HaBs are mostly determined by the electrostatic interactions, but the dispersion and induction components also provide a noticeable contribution and make the HaBs attractive. Charge transfer has a small contribution (<5%) to the HaB and it is higher for the diisocyanide than for the dinitrile systems. At the same time, diisocyanide and dinitrile structures exhibit typical electron-donor and π-acceptor properties in relation to the HaB donor.

AB - 2,3,5,6-Tetramethyl-1,4-diisocyanobenzene ( 1), 1,4-diisocyanobenzene ( 2), and 1,4-dicyanobenzene ( 3) were co-crystallized with 1,3,5-triiodotrifluorobenzene (1,3,5-FIB) to give three cocrystals, 1·1,3,5-FIB, 2·2(1,3,5-FIB), and 3·2(1,3,5-FIB), which were studied by X-ray diffraction. A common feature of the three structures is the presence of I···C isocyanide or I···N nitrile halogen bonds (HaBs), which occurs between an iodine σ-hole and the isocyanide C-(or the nitrile N-) atom. The diisocyanide and dinitrile cocrystals 2·2(1,3,5-FIB) and 3·2(1,3,5-FIB) are isostructural, thus providing a basis for accurate comparison of the two types of noncovalent linkages of C≡N/N≡C groups in the composition of structurally similar entities and in one crystal environment. The bonding situation was studied by a set of theoretical methods. Diisocyanides are more nucleophilic than the dinitrile and they exhibit stronger binding to 1,3,5-FIB. In all structures, the HaBs are mostly determined by the electrostatic interactions, but the dispersion and induction components also provide a noticeable contribution and make the HaBs attractive. Charge transfer has a small contribution (<5%) to the HaB and it is higher for the diisocyanide than for the dinitrile systems. At the same time, diisocyanide and dinitrile structures exhibit typical electron-donor and π-acceptor properties in relation to the HaB donor.

KW - галогенные связи

KW - ИЗОЦИАНИДЫ

KW - нитрилы

KW - QTAIM

KW - SAPT

KW - NBO analysis

UR - https://www.mendeley.com/catalogue/8e1d1aff-f20e-385e-8a6d-714e7ec51328/

U2 - 10.3390/ijms241713324

DO - 10.3390/ijms241713324

M3 - Article

C2 - 37686131

VL - 24

JO - International Journal of Molecular Sciences

JF - International Journal of Molecular Sciences

SN - 1422-0067

IS - 17

M1 - 13324

ER -