Insight into the role of pseudo-halides as multiple hydrogen bond acceptors in the formation of supramolecular 1D assembly of di and trinuclear zinc complexes.

The role of thiocyanate/azide moiety as multiple hydrogen bond acceptors (CH•••S,N and NH•••S,N) in the solid state structures of two new zinc(II) complexes with N 2 O 2 donor 'reduced Schiff bases' been analyzed by DFT calculations. [Display omitted] • The synthesis of two new zinc(II) complexes. • Characterization by single crystal X-ray diffraction analysis. • Formation of 1D supramoelcular assemblies utilizing the multiple H-bond acceptor behavior of pseudo halides. • Analysis of supramolecular assemblies theoretically using DFT calculations. • Estimation of the energy associated to each contact using the quantum theory of atoms-in-molecules. • Emphasis on the importance of long-range van der Waals interactions. In this manuscript we report the synthesis of two new zinc(II) complexes, [(DMSO) 2 ZnL1Zn(NCS) 2 ] (1), and [{(N 3)ZnL2} 2 Zn(DMSO) 2 ] (2) that were characterized by elemental and spectral analyses {H 2 L1 is 2,2-dimethyl-1,3-propanediylbis(iminomethylene)bis(phenol), and H 2 L2 is 1,2-propanediylbis(iminomethylene)bis(4-chlorophenol)}. The structures have been confirmed by single crystal X-ray diffraction analysis. Both complexes form 1D supramoelcular assemblies where the pseudohalides act as multiple H-bond acceptors (CH•••S,N and NH•••S,N). These assemblies have been analyzed theoretically using DFT calculations, and the energy associated to each contact has been estimated using the quantum theory of atoms-in-molecules. The importance of long-range van der Waals interactions is emphasized. This manuscript, where two new complexes are synthesized and the H-bonding contacts individually estimated, is expected to attract the attention not only of synthetic inorganic chemists, but also theoreticians and chemists working in crystal engineering and supramolecular chemistry. [ABSTRACT FROM AUTHOR]