Spectroscopic characterization, crystallographic elucidation and DFT investigation of 5-fluoro-6-(4-methylpiperazin-1-yl)benzo[d]thiazol-2-amine

Thuraya S. Al-Harthy, Musa Shongwe, John Husband, Raphael Stoll, Klaus Merz, Raid Abdel-Jalil

Research output: Contribution to journalArticle

Abstract

The spectroscopic features and molecular structure of 5-fluoro-6-(4-methylpiperazin-1-yl)benzo[d]thiazol-2-amine (2-ABT) have been determined. Single-crystal X-ray analysis and vibrational spectroscopy have revealed the existence of 2-ABT in the amino tautomeric form in the solid state. Properties of 2-ABT in solution have been investigated using 1H and 13C NMR spectroscopy along with electronic absorption spectroscopy. The experimental data are complemented by DFT and TD-DFT calculations at the B3LYP/6–311 + g(2d,p) level. TD-DTF-predicted spectroscopic and structural properties for both amino and imino tautomers of 2-ABT are compared with the measured data; no strong evidence for the presence of the imino tautomer is found within the experimental data. Calculated energy differences between the tautomers strongly favour the amino tautomer over the other. Indeed, X-ray crystallography has unequivocally shown the amino tautomer which co-crystallized with one water molecule in the orthorhombic space group Pnna. Analysis of the crystal packing reveals an interesting structural motif which comprises an assemblage of the 2-ABT molecules through π···π stacking interactions. Furthermore, there exist hydrogen-bonding interactions involving the lattice solvent and the amino group along with the benzothiazole nitrogen atom.

Original languageEnglish
Pages (from-to)614-621
Number of pages8
JournalJournal of Molecular Structure
Volume1176
DOIs
Publication statusPublished - Jan 15 2019

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Discrete Fourier transforms
Vibrational spectroscopy
Molecules
X ray crystallography
X ray analysis
Absorption spectroscopy
Molecular structure
Nuclear magnetic resonance spectroscopy
Structural properties
Hydrogen bonds
Nitrogen
2-(4'-diethylaminophenyl)benzothiazole
benzo(d)thiazol-2-amine
Single crystals
Atoms
Crystals
Water

Keywords

  • 2-aminobenzothiazole
  • Amino-imino tautomer
  • DFT calculations
  • H-bonding interactions
  • Single-crystal X-ray

ASJC Scopus subject areas

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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title = "Spectroscopic characterization, crystallographic elucidation and DFT investigation of 5-fluoro-6-(4-methylpiperazin-1-yl)benzo[d]thiazol-2-amine",
abstract = "The spectroscopic features and molecular structure of 5-fluoro-6-(4-methylpiperazin-1-yl)benzo[d]thiazol-2-amine (2-ABT) have been determined. Single-crystal X-ray analysis and vibrational spectroscopy have revealed the existence of 2-ABT in the amino tautomeric form in the solid state. Properties of 2-ABT in solution have been investigated using 1H and 13C NMR spectroscopy along with electronic absorption spectroscopy. The experimental data are complemented by DFT and TD-DFT calculations at the B3LYP/6–311 + g(2d,p) level. TD-DTF-predicted spectroscopic and structural properties for both amino and imino tautomers of 2-ABT are compared with the measured data; no strong evidence for the presence of the imino tautomer is found within the experimental data. Calculated energy differences between the tautomers strongly favour the amino tautomer over the other. Indeed, X-ray crystallography has unequivocally shown the amino tautomer which co-crystallized with one water molecule in the orthorhombic space group Pnna. Analysis of the crystal packing reveals an interesting structural motif which comprises an assemblage of the 2-ABT molecules through π···π stacking interactions. Furthermore, there exist hydrogen-bonding interactions involving the lattice solvent and the amino group along with the benzothiazole nitrogen atom.",
keywords = "2-aminobenzothiazole, Amino-imino tautomer, DFT calculations, H-bonding interactions, Single-crystal X-ray",
author = "Al-Harthy, {Thuraya S.} and Musa Shongwe and John Husband and Raphael Stoll and Klaus Merz and Raid Abdel-Jalil",
year = "2019",
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T1 - Spectroscopic characterization, crystallographic elucidation and DFT investigation of 5-fluoro-6-(4-methylpiperazin-1-yl)benzo[d]thiazol-2-amine

AU - Al-Harthy, Thuraya S.

AU - Shongwe, Musa

AU - Husband, John

AU - Stoll, Raphael

AU - Merz, Klaus

AU - Abdel-Jalil, Raid

PY - 2019/1/15

Y1 - 2019/1/15

N2 - The spectroscopic features and molecular structure of 5-fluoro-6-(4-methylpiperazin-1-yl)benzo[d]thiazol-2-amine (2-ABT) have been determined. Single-crystal X-ray analysis and vibrational spectroscopy have revealed the existence of 2-ABT in the amino tautomeric form in the solid state. Properties of 2-ABT in solution have been investigated using 1H and 13C NMR spectroscopy along with electronic absorption spectroscopy. The experimental data are complemented by DFT and TD-DFT calculations at the B3LYP/6–311 + g(2d,p) level. TD-DTF-predicted spectroscopic and structural properties for both amino and imino tautomers of 2-ABT are compared with the measured data; no strong evidence for the presence of the imino tautomer is found within the experimental data. Calculated energy differences between the tautomers strongly favour the amino tautomer over the other. Indeed, X-ray crystallography has unequivocally shown the amino tautomer which co-crystallized with one water molecule in the orthorhombic space group Pnna. Analysis of the crystal packing reveals an interesting structural motif which comprises an assemblage of the 2-ABT molecules through π···π stacking interactions. Furthermore, there exist hydrogen-bonding interactions involving the lattice solvent and the amino group along with the benzothiazole nitrogen atom.

AB - The spectroscopic features and molecular structure of 5-fluoro-6-(4-methylpiperazin-1-yl)benzo[d]thiazol-2-amine (2-ABT) have been determined. Single-crystal X-ray analysis and vibrational spectroscopy have revealed the existence of 2-ABT in the amino tautomeric form in the solid state. Properties of 2-ABT in solution have been investigated using 1H and 13C NMR spectroscopy along with electronic absorption spectroscopy. The experimental data are complemented by DFT and TD-DFT calculations at the B3LYP/6–311 + g(2d,p) level. TD-DTF-predicted spectroscopic and structural properties for both amino and imino tautomers of 2-ABT are compared with the measured data; no strong evidence for the presence of the imino tautomer is found within the experimental data. Calculated energy differences between the tautomers strongly favour the amino tautomer over the other. Indeed, X-ray crystallography has unequivocally shown the amino tautomer which co-crystallized with one water molecule in the orthorhombic space group Pnna. Analysis of the crystal packing reveals an interesting structural motif which comprises an assemblage of the 2-ABT molecules through π···π stacking interactions. Furthermore, there exist hydrogen-bonding interactions involving the lattice solvent and the amino group along with the benzothiazole nitrogen atom.

KW - 2-aminobenzothiazole

KW - Amino-imino tautomer

KW - DFT calculations

KW - H-bonding interactions

KW - Single-crystal X-ray

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