Benzyl Dihydrazone versus Thiosemicarbazone Schiff Base: Effects on the Supramolecular Arrangement of Cobalt Thiocyanate Complexes and the Generation of CoN6 and CoN4S2 Coordination Spheres

In this study, we examine the coordination chemistry of benzyl dihydrazone and thiosemicarbazone Schiff bases featuring different chelation modes, steric bulk, and reactivities towards cobalt(II) thiocyanate. The tetradentate benzyl dihydrazone ligands coordinate to the Co(SCN)2 fragment to form CoN6 coordination spheres (1–3), whereas the thiosemicarbazone ligands provide CoIII complexes featuring CoN4S2 coordination spheres (4 and 5) and charge-balancing anions {SCN– and [Co(SCN)4]2– for 4 and 5, respectively}. Hirshfeld surface (HS) analysis revealed a substituent effect that results in an increasing number of H···H contacts in the order –H < –CH3 < –Ph (1–3, respectively). The H bonding in 4 and 5 as well as the associated energies were computed by the DFT approach, and these interactions appear to be crucial for the formation of the supramolecular systems. The DFT study also suggested that the H-bonded dimers in 5 are examples of the recently described “antielectrostatic” H bonds. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Mahmoudi G.1 , Zaręba J.K.2 , Gurbanov A.V. 3, 4 , Bauzá A.5 , Zubkov F.I. 4 , Kubicki M.6 , Stilinović V.7 , Kinzhybalo V.8 , Frontera A.5
Wiley-VCH Verlag
Номер выпуска
  • 1 Department of Chemistry, Faculty of Science, University of Maragheh, P. O. Box 55181-83111, Maragheh, Iran
  • 2 Advanced Materials Engineering and Modelling Group, Wroclaw University of Science and Technology, Wyb. Wyspiańskiego 27, Wrocław, 50370, Poland
  • 3 Department of Chemistry, Baku State University, Z. Khalilov str. 23, Baku, AZ 1148, Azerbaijan
  • 4 Organic Chemistry Department, RUDN University, Moscow, 117198, Russian Federation
  • 5 Departament de Química, Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, Palma (Baleares), 07122, Spain
  • 6 Faculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89b, Poznan, 61-614, Poland
  • 7 Department of Chemistry, Faculty of Science, University of Zagreb, Horvatovac 102a, Zagreb, 10000, Croatia
  • 8 Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, Wrocław, 50-422, Poland
Ключевые слова
Hirshfeld surface analysis; Hydrogen bonds; Ligand effects; Noncovalent interactions; Schiff bases
Дата создания
Дата изменения
Постоянная ссылка

Другие записи