X-ray crystallographic structures of enamine and amine Schiff bases of pyridoxal and its 1: 1 hydrogen-bonded complexes with benzoic acid derivatives: Evidence for coupled inter- and intramolecular proton transfer

Shasad Sharif, Douglas R. Powell, David Schagen, Thomas Steiner, Michael D. Toney, Emily Fogle, Hans Heinrich Limbach

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

Crystal structures of Schiff bases containing pyridoxal (PL), N-(pyridoxylidene)-tolylamine, C15H16N2O 2 (I), N-(pyridoxylidene)-methylamine, C9H 12N2O2 (III), and their 1:1 adduct with 2-nitrobenzoic acid, (I)+ C7H4NO (II), and 4-nitrobenzoic acid, (III)+ C7H4NO (IV), serve as models for the coenzyme pyridoxal-5′-phosphate (PLP) in its PLP-dependent enzymes. These models allow the study of the intramolecular OHN hydrogen bond of PL/PLP Schiff bases and the H-acceptor properties of their pyridine rings. The free base (I) forms hydrogen-bonded chains involving the hydroxyl side groups and the rings of adjacent molecules, whereas (III) forms related hydrogen-bonded cyclic dimers. The adducts (II)/(IV) consist of 1:1 hydrogen-bonded complexes, exhibiting strong intermolecular bonds between the carboxylic groups of the acids and the pyridine rings of (I)/(III). In conclusion, the proton in the intramolecular O - H⋯N hydrogen bond of (I)/(III) is located close to oxygen (enolamine form). The added acids protonate the pyridine ring in (II)/(IV), but only in the latter case does this protonation lead to a shift of the intramolecular proton towards the nitrogen (ketoimine form). All crystallographic structures were observed in the open form. In contrast, the formation of the pyridinium salt by dissolving (IV) leads to the cyclic aminal form.

Original languageEnglish (US)
Pages (from-to)480-487
Number of pages8
JournalActa Crystallographica Section B: Structural Science
Volume62
Issue number3
DOIs
StatePublished - Jun 2006

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Pyridoxal
Pyridoxal Phosphate
Proton transfer
Benzoic Acid
Schiff Bases
benzoic acid
imines
Amines
Protons
Hydrogen
amines
4-nitrobenzoic acid
X-Rays
Derivatives
X rays
pyridines
phosphates
acids
protons
rings

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Structural Biology

Cite this

X-ray crystallographic structures of enamine and amine Schiff bases of pyridoxal and its 1 : 1 hydrogen-bonded complexes with benzoic acid derivatives: Evidence for coupled inter- and intramolecular proton transfer. / Sharif, Shasad; Powell, Douglas R.; Schagen, David; Steiner, Thomas; Toney, Michael D.; Fogle, Emily; Limbach, Hans Heinrich.

In: Acta Crystallographica Section B: Structural Science, Vol. 62, No. 3, 06.2006, p. 480-487.

Research output: Contribution to journalArticle

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abstract = "Crystal structures of Schiff bases containing pyridoxal (PL), N-(pyridoxylidene)-tolylamine, C15H16N2O 2 (I), N-(pyridoxylidene)-methylamine, C9H 12N2O2 (III), and their 1:1 adduct with 2-nitrobenzoic acid, (I)+ C7H4NO (II), and 4-nitrobenzoic acid, (III)+ C7H4NO (IV), serve as models for the coenzyme pyridoxal-5′-phosphate (PLP) in its PLP-dependent enzymes. These models allow the study of the intramolecular OHN hydrogen bond of PL/PLP Schiff bases and the H-acceptor properties of their pyridine rings. The free base (I) forms hydrogen-bonded chains involving the hydroxyl side groups and the rings of adjacent molecules, whereas (III) forms related hydrogen-bonded cyclic dimers. The adducts (II)/(IV) consist of 1:1 hydrogen-bonded complexes, exhibiting strong intermolecular bonds between the carboxylic groups of the acids and the pyridine rings of (I)/(III). In conclusion, the proton in the intramolecular O - H⋯N hydrogen bond of (I)/(III) is located close to oxygen (enolamine form). The added acids protonate the pyridine ring in (II)/(IV), but only in the latter case does this protonation lead to a shift of the intramolecular proton towards the nitrogen (ketoimine form). All crystallographic structures were observed in the open form. In contrast, the formation of the pyridinium salt by dissolving (IV) leads to the cyclic aminal form.",
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T1 - X-ray crystallographic structures of enamine and amine Schiff bases of pyridoxal and its 1

T2 - 1 hydrogen-bonded complexes with benzoic acid derivatives: Evidence for coupled inter- and intramolecular proton transfer

AU - Sharif, Shasad

AU - Powell, Douglas R.

AU - Schagen, David

AU - Steiner, Thomas

AU - Toney, Michael D.

AU - Fogle, Emily

AU - Limbach, Hans Heinrich

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N2 - Crystal structures of Schiff bases containing pyridoxal (PL), N-(pyridoxylidene)-tolylamine, C15H16N2O 2 (I), N-(pyridoxylidene)-methylamine, C9H 12N2O2 (III), and their 1:1 adduct with 2-nitrobenzoic acid, (I)+ C7H4NO (II), and 4-nitrobenzoic acid, (III)+ C7H4NO (IV), serve as models for the coenzyme pyridoxal-5′-phosphate (PLP) in its PLP-dependent enzymes. These models allow the study of the intramolecular OHN hydrogen bond of PL/PLP Schiff bases and the H-acceptor properties of their pyridine rings. The free base (I) forms hydrogen-bonded chains involving the hydroxyl side groups and the rings of adjacent molecules, whereas (III) forms related hydrogen-bonded cyclic dimers. The adducts (II)/(IV) consist of 1:1 hydrogen-bonded complexes, exhibiting strong intermolecular bonds between the carboxylic groups of the acids and the pyridine rings of (I)/(III). In conclusion, the proton in the intramolecular O - H⋯N hydrogen bond of (I)/(III) is located close to oxygen (enolamine form). The added acids protonate the pyridine ring in (II)/(IV), but only in the latter case does this protonation lead to a shift of the intramolecular proton towards the nitrogen (ketoimine form). All crystallographic structures were observed in the open form. In contrast, the formation of the pyridinium salt by dissolving (IV) leads to the cyclic aminal form.

AB - Crystal structures of Schiff bases containing pyridoxal (PL), N-(pyridoxylidene)-tolylamine, C15H16N2O 2 (I), N-(pyridoxylidene)-methylamine, C9H 12N2O2 (III), and their 1:1 adduct with 2-nitrobenzoic acid, (I)+ C7H4NO (II), and 4-nitrobenzoic acid, (III)+ C7H4NO (IV), serve as models for the coenzyme pyridoxal-5′-phosphate (PLP) in its PLP-dependent enzymes. These models allow the study of the intramolecular OHN hydrogen bond of PL/PLP Schiff bases and the H-acceptor properties of their pyridine rings. The free base (I) forms hydrogen-bonded chains involving the hydroxyl side groups and the rings of adjacent molecules, whereas (III) forms related hydrogen-bonded cyclic dimers. The adducts (II)/(IV) consist of 1:1 hydrogen-bonded complexes, exhibiting strong intermolecular bonds between the carboxylic groups of the acids and the pyridine rings of (I)/(III). In conclusion, the proton in the intramolecular O - H⋯N hydrogen bond of (I)/(III) is located close to oxygen (enolamine form). The added acids protonate the pyridine ring in (II)/(IV), but only in the latter case does this protonation lead to a shift of the intramolecular proton towards the nitrogen (ketoimine form). All crystallographic structures were observed in the open form. In contrast, the formation of the pyridinium salt by dissolving (IV) leads to the cyclic aminal form.

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