Naslov
Cooperativity of halogen bonds in cocrystals of 4-halogenoanilines and 1, 4- diiodotetrafluorobenzene

Autori
Franov, Silvia-Maria ; Nemec, Vinko ; Cinčić, Dominik

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
The Twenty-Sixth Croatian-Slovenian Crystallographic Meeting : Book of Abstracts and Programme / Matković-Čalogović, Dubravka ; Popović, Stanko ; Skoko, Željko - Zagreb : Hrvatska akademija znanosti i umjetnosti (HAZU) ; Hrvatska Kristalografska Zajednica, 2018, 63-63

Skup
26th Croatian-Slovenian Crystallographic Meeting (CSCM26)

Mjesto i datum
Poreč, Hrvatska, 13.06.2018. - 17.06.2018

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Nije recenziran

Ključne riječi
halogen bond ; cocrystals ; halogenoanilines ; 1, 4- diiodotetrafluorobenzene

Sažetak
One of the most notable features of halogen bonding [1] is that it involves halogen atoms that are electrophilic species, but that can also be nucleophilic due to induced electron density anisotropy [2]. When considering interactions between two halogen species, it is necessary to differentiate between two types: type I, which arise from close packing requirements, and type II, which represent the interaction between the nucleophilic area of one halogen and the electrophilic area of another halogen and are therefore considered halogen bonding motifs [3]. Our goal in this work was to explore the possibilities in halogen bonding involving halogenated anilines, seeing as halogen atoms and ligands are known halogen bond acceptors [1, 3] and as their amine functional group is also a potential halogen bond acceptor [4]. We selected structurally equivalent reactants, 4-chloroaniline (4ClA), 4-bromoaniline (4BrA) and 4-iodoaniline (4IA), so as to study the effects on the supramolecular interactions on crystal packing. First, we performed mechanochemical and solution based synthesis, reacting each 4-halogenoaniline with 1, 4- diiodotetrafluorobenzene (14tfib) in a 2:1 molar ratio. Products were characterized by means of powder X-ray diffraction and by single crystal X-ray diffraction. The three obtained products are isostructural. In all three cases 14tfib forms remarkably similar halogen bonds only with the amine group (d(I···N) = 3.000 - 2.996 Å, (C–I···N) = 178 – 177 °), leaving the halogen atom of the 4-halogenoanilines to participate as both a halogen bond donor and acceptor in a type II contact. The geometry of the observed type II contacts is shown to be only slightly dependent on the donor capabilities of the halogen atom (d(I···I) = 3.892 Å, (C–I···I) = 169 ° ; d(Br···Br) = 3.666 Å, (C–Br···Br) = 165 ° ; d(Cl···Cl) = 3.623 Å, (C–Cl···Cl) = 165 °). The combination of halogen bonding and type II contacts leads to the formation of layers which are then further stacked into 3D.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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