Naslov
The sulfur atom as a halogen bond acceptor in cocrystals containing Werner coordination compounds

Autori
Posavec, Lidija ; Cinčić, Dominik

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

Skup
7th European Crystallographic School

Mjesto i datum
Lisabon, Portugal, 10.07.2022. - 15.07.2022

Vrsta sudjelovanja
Poster

Vrsta recenzije
Podatak o recenziji nije dostupan

Ključne riječi
Wernerovi koordinacijski spojevi ; halogenska veza ; kokristali
(Werner coordination compounds ; halogen bond ; cocrystals)

Sažetak
Werner coordination compounds are metal complexes of MX2L4 general formula, where M is a divalent metal cation, typically Ni(II), Co(II), Fe(II), Cu(II) or Mn(II), X is an anionic ligand (NCS―, CN―, NO3―, NCO―) and L is a substituted pyridine or -arylalkylamine.1, 2 The usage of this type of coordination compounds as halogen bond acceptors has been poorly studied.3 A search of the Cambridge Structural Database (CSD) for I∙∙∙S halogen bonds in cocrystals containing isothiocyanate Werner coordination compounds resulted in only four data sets.4 These are cocrystals containing Co(C5H5N)4(NCS)2 or Ni(C7H7N)4(NCS)2 complexes where isothiocyanate sulfur acts as a halogen bond acceptor moiety. The aim of our research was to study isothiocyanate proclivity for halogen bonding with these compounds as there is no systematic research of this type of interaction. The research was based on Werner coordination compounds containing a nickel metal center with different type of pyridine ligands. To study the steric influence of ligands in halogen bond formation, two coordination compounds were synthesized: Ni(C5H5N)4(NCS)2 (1) and Ni(CH3C5H5N)4(NCS)2 (2). These compounds were cocrystallized with different halogen bond donor molecules. As coformers, we selected perhalogenated donor molecules with different geometric properties: 1, 2- diiodotetrafluorobenzene (12tfib), 1, 3- diiodotetrafluorobenzene (13tfib), 1, 4- diiodotetrafluorobenzene (14tfib) and 1, 3, 5- trifluoro-2, 4, 6-triiodobenzene (135tfib). Cocrystallization experiments were performed both mechanochemically and from the solution. Using Werner coordination compounds as acceptor moieties, a series of 9 cocrystals was obtained, of which 7 were structurally characterized by single-crystal X-ray diffraction. Dominant interactions in the obtained cocrystals are I∙∙∙S halogen bonds, while the ligand in the coordination compound significantly affects the supramolecular architecture. 1 M. M. Wicht, N. B. Báthori, L. R. Nassimbeni, Dalton Trans. 2015, 44, 6863–6870. 2 D. V. Soldatov, G. D. Enright, J. A. Ripmeester, Cryst. Growth Des. 2004, 4, 1185–1194. 3 V. Nemec, K. Lisac, N. Bedeković, L. Fotović, V. Stilinović, D. Cinčić, CrystEngComm. 2021, 23, 3063–3083. 4 C. R. Groom, I. J. Bruno, M. P. Lightfoot, S. C. Ward, Acta Cryst. 2016, B72, 171–179.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA