Publication:
5-Methylhydantoin: from isolated molecules in a low-temperature argon matrix to solid state polymorphs characterization

Date
2017-07-20
Authors
Nogueira, Bernardo A.
Öğrüç Ildız, Gülce
Canotilho, J.
Eusebio, M. E. S.
Henriques, M. S. C.
Paixao, J. A.
Fausto, Rui
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Amer Chemical Soc, 1155 16th St, Nw, Washington, Dc 20036 USA
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Abstract

The molecular structure, vibrational spectra and photochemistry of 5-methylhydantoin (C4H6N2O2; 5-MH) were studied by matrix isolation infrared spectroscopy and theoretical calculations at the DFT(B3LYP)/6-311++G(d,p) theory level. The natural bond orbital (NBO) analysis approach was used to study in detail the electronic structure of the minimum energy structure of 5-MH, namely the specific characteristics of the sigma and pi electronic systems of the molecule and the stabilizing orbital interactions. UV irradiation of 5-MH isolated in argon matrix resulted in its photofragmentation through a single photochemical pathway, yielding isocyanic acid, ethanimine, and carbon monoxide, thus following a pattern already observed before for the parent hydantoin and 1-methylhydantoin molecules. The investigation of the thermal properties of 5-MH was undertaken by differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM) and Raman spectroscopy. Four different polymorphs of 5-MH were identified. The crystal structure of one of the polymorphs, for which it was possible to grow up suitable crystals, was determined by X-ray diffraction (XRD). Two of the additional polymorphs were characterized by powder XRD, which confirmed the molecules pack in different crystallographic arrangements.

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Keywords
Crystal-Structures , Infrared-Spectra , Hydantoins , Photochemistry , Derivatives , Inhibitors , Density
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