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Structural characterization of hydrogen bonding for antipyrine derivatives: Single-crystal X-ray diffraction and theoretical studies

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Objectives. The paper is devoted to the crystal structure characterization of 5-methyl-2-phenyl4H-pyrazol-3-one (compound I) and 2-(4-chlorophenyl)-5-methyl-4H-pyrazol-3-one (compound II).

Methods. Single-crystal X-ray diffraction studies and theoretical calculations: Density functional theory and quantum theory of atoms in molecules.

Results. In the solid state, the crystal structure of compound I is characterized by the alternation of OH and NH tautomers connected via O–H---O and N–H---N hydrogen bonds. For compound II, the existence of chains built from the NH monomers via hydrogen bonding can be explained by the peculiarities of cooperative effects. In the framework of quantum theory of atoms in molecules, the following topological characteristics are calculated for all dimers: electron density, Laplacian of electron density, density of kinetic, potential, and total energy in the critical point of the intermolecular hydrogen bond. It is concluded that the hydrogen bond in dimers 1–4, 7 (compound I), and 8–11 (compound II) can be assigned to the intermediate (between covalent and dispersion types) interaction owing to hydrogen bond formation with the participation of electronegative oxygen- (and/or nitrogen-) atoms, whereas H-bond in dimers 5 and 6 (compound I) can be attributed to the dispersion one (no hydrogen bond formation or weak H-bond formation), and it represents the weak interaction, being in agreement with length for intermolecular hydrogen bond in dimers. The electron density and total energy density values demonstrate that the strongest intermolecular H-bonds take place in dimers 1 (OH---O), 4 (OH---O), 7 (OH---N), 8 (OH---O), 9 (NH---N), and 11 (OH---N). The results obtained for compounds I and II are compared with data for antipyrine (1,2-dihydro-1,5-dimethyl-2-phenyl-3H-pyrazol-3-one; compound III)

Conclusions. An important role of intermolecular hydrogen bonding in the crystal packing, molecule association and self-organization via dimer- or more extended species formation has been demonstrated. 

About the Authors

N. S. Rukk
MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
Russian Federation

Cand. Sci. (Chem.), Associate Professor, A.N. Reformatskii Department of Inorganic Chemistry,

86, Vernadskogo pr., Moscow, 119571

R. S. Shamsiev
MIREA – Russian Technological University (M.V. Lomonosov Institute of Fine Chemical Technologies)
Russian Federation

Dr. Sci. (Chem.), Professor, Ya.K. Syrkin Department of Physical Chemistry, 

86, Vernadskogo pr., Moscow, 119571

D. V. Albov
Lomonosov Moscow State University
Russian Federation

Cand. Sci. (Chem.), Senior Scientific Researcher, Faculty of Chemistry, 

1, Leninskie Gory, Moscow, 119992

S. N. Mudretsova
Lomonosov Moscow State University
Russian Federation

Senior Scientific Researcher, Faculty of Chemistry,

1, Leninskie Gory, Moscow, 119992


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Supplementary files

1. Fig. 3. Asymmetric unit of compound III with the crystallographic numbering scheme: crystal structure packing.
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2. Appendix A
Subject Appendix A to the article "Structural characterization of hydrogen bonding for antipyrine derivatives: Single-crystal X-ray diffraction and theoretical studies"
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3. This is to certify that the paper titled Structural characterization of hydrogen bonding for antipyrine derivatives: Single-crystal X-ray diffraction and theoretical studies commissioned to us by Nataliya S. Rukk, Ravshan S. Shamsiev, Dmitry V. Albov, Svetlana N. Mudretsovai has been edited for English language and spelling by Enago, an editing brand of Crimson Interactive Inc.
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  • Structural specific features and packing particularities of antipyrine and its derivatives.
  • Self-organization of molecules in the solid state: single crystal XRD studies and DFT calculations.
  • Hydrogen bonding contribution in the process of dimers formation.


For citations:

Rukk N.S., Shamsiev R.S., Albov D.V., Mudretsova S.N. Structural characterization of hydrogen bonding for antipyrine derivatives: Single-crystal X-ray diffraction and theoretical studies. Fine Chemical Technologies. 2021;16(2):113-137.

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