Naslov
Evaluation of the morpholinyl oxygen atom as a halogen bond acceptor in imines containing other potential acceptor sites

Autori
Nemec, Vinko ; Lisac, Katarina ; Stanić, Petra ; Cinčić, Dominik

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

Izvornik
Second International Conference on Noncovalent Interactions : Book of Abstracts / Djukic, Jean-Pierre - Strasbourg : University of Strasbourg, 2022, 93-93

Skup
2nd International Conference on Noncovalent Interactions (ICNI)

Mjesto i datum
Strasbourg, Francuska, 18.07.2022. - 22.07.2022

Vrsta sudjelovanja
Predavanje

Vrsta recenzije
Međunarodna recenzija

Ključne riječi
cocrystals ; halogen bonding ; morpholine oxygen

Sažetak
The morpholinyl oxygen atom has previously been established as a halogen bond acceptor[1] in both small molecules[2, 3] and larger building blocks derived from them, i. e. metal complexes with imine ligands[3] and metal complex adducts.[4] However, crystal engineering of more complex halogen-bonded materials is still hindered by a lack of comprehensive data on the reliability of specific acceptor species in larger building blocks which contain multiple halogen bond acceptor sites or competing hydrogen bond donor groups. In order to systematically study the halogen bonding capability of the morpholinyl oxygen atom, we synthesized a series of imines from either N-aminomorpholine or N-(2-aminoethyl)-morpholine, and one aldehyde from a selection of aromatic aldehydes containing a variety of competing or cooperating functional groups and acceptor sites: pyridine-2-, 3- and 4-carbaldehydes, 4-nitrobenzaldehyde, 3, 4-dimethoxybenzaldehyde, 4-dimethylaminobenzaldehyde, salicylaldehyde, 5-bromosalicylaldehyde, 3, 5-dibromosalicylaldehyde and 2-hydroxy-1-naphthaldehyde. As halogen bond donors, we used perhalogenated benzenes: 1, 2-, 1, 3-, and 1, 4-diiodotetrafluorobenzene, 1, 3, 5-triiodotrifluorobenzene and 1, 4-dibromotetrafluorobenzene. As of the time of writing, 55 new cocrystals have been obtained and characterized by powder and single crystal X-ray diffraction. These datasets were then combined with literature data in order to analyze trends. Overall, the morpholinyl oxygen atom is a halogen bond acceptor in 70 % of the cocrystals, and is significantly more represented than both the morpholinyl nitrogen (39 %) and imine nitrogen atoms (29 %). The morpholinyl oxygen atom is expectedly secondary as a halogen bond acceptor to the pyridine nitrogen atom, participating in halogen bonding in 54 % of that cocrystal data subset.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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