Proton sharing and transfer in some zwitterionic compounds based on 4-oxo-4-((1-phenethylpiperidin-4-yl)(phenyl)amino)alcanoic acids

Gary S. Nichol, Vlad K. Kumirov, Ruben S Vardanyan, Victor J Hruby

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Three compounds, each derived from Fentanyl and differing essentially only in the length of a carboxylic acid chain, were synthesized and yielded four crystal structures three of which share several structural similarities, including the length of the chain, while the fourth, with a shorter chain, is quite different. The chain length has a significant influence on the crystal structures formed. The 'three atom' chain compounds are all solvated zwitterions which feature a hydrogen-bonded 'dimer' between adjacent zwitterions. The formation of this large dimer leaves available a second carboxylate O atom to take part in hydrogen bonding interactions with solvent molecules. The shorter 'two atom' chain compound was difficult to crystallize and required the use of synchrotron radiation to measure X-ray diffraction data. It does not form the same dimer motif observed in the 'three atom' chain compounds and has not formally formed a zwitterion; although there is evidence of proton sharing or disorder X-ray data are insufficient to create a disordered model, and the compound was modeled as formally neutral based on O-H and N-H distances. Room temperature analyses showed the proton transfer behavior to be independent of crystal temperature, and nuclear magnetic resonance studies show proton transfer behavior in solution. The formation of a zwitterionic hydrogen-bonded dimer is implicated in providing some stability during crystal growth of the easily crystallized 'three atom' chain compounds.

Original languageEnglish (US)
Pages (from-to)3651-3657
Number of pages7
JournalCrystEngComm
Volume12
Issue number11
DOIs
StatePublished - Nov 2010

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zwitterions
amino acids
Protons
Amino acids
Dimers
Amino Acids
Atoms
protons
Proton transfer
Hydrogen
dimers
Crystal structure
atoms
Fentanyl
Carboxylic Acids
Crystallization
Synchrotron radiation
hydrogen
Carboxylic acids
Chain length

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

Proton sharing and transfer in some zwitterionic compounds based on 4-oxo-4-((1-phenethylpiperidin-4-yl)(phenyl)amino)alcanoic acids. / Nichol, Gary S.; Kumirov, Vlad K.; Vardanyan, Ruben S; Hruby, Victor J.

In: CrystEngComm, Vol. 12, No. 11, 11.2010, p. 3651-3657.

Research output: Contribution to journalArticle

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