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6951452 
Journal Article 
Unprecedented pi center dot center dot center dot pi interaction between an aromatic ring and a pseudo-aromatic ring formed through intramolecular H-bonding in a bidentate Schiff base ligand: crystal structure and DFT calculations 
Dutta, A; Jana, AD; Gangopadhyay, S; Das, KK; Marek, J; Marek, R; Brus, J; Ali, M; , 
2011 
1 
Physical Chemistry Chemical Physics
ISSN: 1463-9076
EISSN: 1463-9084 
ROYAL SOC CHEMISTRY 
CAMBRIDGE 
15845-15853 
21818495 
WOS:000294167700015 
A combination of a single crystal X-ray diffraction study and density functional theory calculations has been applied to a bidentate Schiff base compound to elucidate different cooperative non-covalent interactions involved in the stabilization of the keto form over the enol one in the solid state. The single crystal X-ray structure reveals a remarkable supramolecular assembly of the keto form through a cyclic hydrogen bonded dimeric motif. The most interesting feature in the supramolecular assembly is the formation of a 'dimer of dimer' motif by pi center dot center dot center dot pi, CH center dot center dot center dot pi and N center dot center dot center dot O/O center dot center dot center dot O interactions in which the pi center dot center dot center dot pi interaction involving the aromatic phenyl ring and the intramolecularly hydrogen bonded pseudo-aromatic ring of the keto form lying just above or below the phenyl ring of the other dimer seems to be unprecidented. The optimized geometry of the hydrogen bonded dimeric motif of the keto form of the organic molecule has been obtained by DFT calculations and agrees very well with that found within the crystalline state. The X-ray crystallographic geometry of the 'dimer of dimer' has also been computed, which shows that in the HOMO, the pi electrons are localized in the phenyl rings away from each other, while in the LUMO, there is a strong pi-pi interaction between the phenyl ring of one dimer with the pseudo-aromatic ring of another dimer with an energy estimated to be 7.95 kJ mol(-1). Therefore, on HOMO -> LUMO excitation there is localization of pi electrons in the central part of the complex moiety which plays a stabilizing role of the dimer of dimer motif in the solid state.