Experimental and theoretical structural study of (3E,5E)-3,5-bis-(benzylidene)-4-oxopiperidinium mono- and (3E,5E)-3,5-bis-(4-N,N-dialkylammonio)benzylidene)-4-oxopiperidini u m trications

• Published in: Journal of molecular structure 2011-08, Vol.1001 (1-3), p.68-77
• Main Authors: Fonari, Alexandr, Leonova, Evgeniya S, Makarov, Michail V, Bushmarinov, Ivan S, Odinets, Irina L, Fonari, Marina S, Antipin, Mikhail Yu, Timofeeva, Tatiana V
• Format: Article
• Language: English
• Subjects: Anions; Cations; Charging; Derivatives; Diffraction; Mathematical analysis; NMR spectroscopy; X-rays
• ISSN: 0022-2860
• DOI: 10.1016/j.molstruc.2011.06.020

(3E,5E)-3,5-Bis(benzylidene)-4-oxopiperidinium tetrafluoroborate [C sub(19H) sub(1)8NO][BF sub(4] ( 1), (3E,5E)-3,5-bis[4-(dimethylammonio)benzylidene]-4-oxopiperidinium bearing mixed tetrafluoroborate and bis(hexafluoro( mu -hydroxo)diborate) anions [C) sub(2)3H sub(30N) sub(3)O][B sub(2F) sub(6)OH] sub(n[BF) sub(4)] sub(m[ sup].xH) sub(2)O ( 2), and (3E,5E)-3,5-bis[4-(diethylammonio)benzylidene]-4-oxopiperidinium tris(tetrafluoroborate) monohydrate [C sub(27H) sub(3)8N sub(3O][BF) sub(4)] sub(3) super(.)H sub(2O ( 3) were obtained via mediated by the boron trifluoride etherate aldol-crotonic condensation of the corresponding aldehyde and piperidin-4-one hydrochloride monohydrate. Their structures were studied by IR and multinuclear NMR spectroscopy, and single crystal X-ray diffraction. The X-ray analysis revealed the presence of monoprotonated piperidinium cation in 1 and triprotonated cations in 2 and 3. The hexafluoro( mu -hydroxo)diborate anion was found in the mixed-anionic salts 2A and 2B which differ by the ratio of the anions. The extended hydrogen-bonded system is registered in all compounds. Static first order hyperpolarizabilities for the neutral (3E,5E)-3,5-bis[4-(dimethylamino)benzylidene]-piperidin-4-one and its positively charged derivatives along with their molecular geometries and binding energy of 1 were calculated using DFT approach.)