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Crystal engineering with novel antipyrine derivatives: Insights from X-ray diffraction, Hirshfeld surface analysis, and DFT calculations on intermolecular interactions
Article
Authorship:
ROCHA, MARIANA ; Saeed, Aamer ; Gil, Diego M. ; Echeverría, Gustavo A. ; Piro, Oscar E. ; Khurshid, Asma ; Arshad, Muhammad ; Shah, Syed Adnan Ali ; Erben, Mauricio FedericoDate:
2025Publishing House and Editing Place:
ELSEVIER SCIENCE BVMagazine:
JOURNAL OF MOLECULAR STRUCTURE, vol. 1319 ELSEVIER SCIENCE BVSummary *
In this study, we report the synthesis, structural characterization by X-ray diffraction, vibrational (Infrared and Raman) investigation, Hirshfeld surface analysis, and DFT calculations of three new antipyrine derivatives (1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl) bearing amide groups (1–3). The compounds were syn-thesized in good yields and characterized spectroscopically. X-ray diffraction revealed that compound 1 crystallizes as a monohydrate in the monoclinic space group P21/c, while compound 3 also crystallizes as a monohydrate in the orthorhombic space group Pccn, exhibiting quasi-isomorphism with 1. Compound 2 crys-tallizes in the P21/c space group, forming H-bonded centrosymmetric dimers. The crystal packing is stabilized by N–H⋅⋅⋅O and C–H⋅⋅⋅O hydrogen bonds, along with C–H⋅⋅⋅π interactions. FTIR and Raman spectroscopic analysis, supported by DFT calculations, identified key vibrational modes in the amide and pyrazole moieties.Hirshfeld surface analysis indicated that the molecular sheets are primarily formed by hydrogen bonds, with stabilization dominated by electrostatic energy contributions. DFT calculations (PBE0-D3/def2-TZVP) and QTAIM/NCIplot analyses revealed that the H-bonding interactions are energetically significant. Information provided by the agent in SIGEVAKey Words
Hirshfeld surface analysisPyrazoleSingle crystal XRDAminophenazone