Crystal Structure and Non-Hydrostatic Stress-Induced Phase Transition of Urotropine Under High Pressure.

Hirshfeld atom refinement IR spectroscopy X-ray diffraction high-pressure chemistry urotropine

Journal

Chemistry (Weinheim an der Bergstrasse, Germany)
ISSN: 1521-3765
Titre abrégé: Chemistry
Pays: Germany
ID NLM: 9513783

Informations de publication

Date de publication:
13 Jan 2021
Historique:
received: 26 08 2020
pubmed: 24 10 2020
medline: 24 10 2020
entrez: 23 10 2020
Statut: ppublish

Résumé

High-pressure behavior of hexamethylenetetramine (urotropine) was studied in situ using angle-dispersive single-crystal synchrotron X-ray diffraction (XRD) and Fourier-transform infrared absorption (FTIR) spectroscopy. Experiments were conducted in various pressure-transmitting media to study the effect of deviatoric stress on phase transformations. Up to 4 GPa significant damping of molecular librations and atomic thermal motion was observed. A first-order phase transition to a tetragonal structure was observed with an onset at approximately 12.5 GPa and characterized by sluggish kinetics and considerable hysteresis upon decompression. However, it occurs only in non-hydrostatic conditions, induced by deviatoric or uniaxial stress in the sample. This behavior finds analogies in similar cubic crystals built of highly symmetric cage-like molecules and may be considered a common feature of such systems. DFT computations were performed to model urotropine equation of state and pressure dependence of vibrational modes. The first successful Hirshfeld atom refinements carried out for high-pressure diffraction data are reported. The refinements yielded more realistic C-H bond lengths than the independent atom model even though the high-pressure diffraction data are incomplete.

Identifiants

pubmed: 33095457
doi: 10.1002/chem.202003928
doi:

Types de publication

Journal Article

Langues

eng

Sous-ensembles de citation

IM

Pagination

1094-1102

Subventions

Organisme : Wroclawskie Centrum Sieciowo-Superkomputerowe, Politechnika Wroclawska (PL)
ID : 260
Organisme : European Synchrotron Radiation Facility
ID : CH4707, CH5087
Organisme : Ministerstwo Nauki i Szkolnictwa Wyższego
ID : DIR/WK/2016/19

Informations de copyright

© 2020 Wiley-VCH GmbH.

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Auteurs

Piotr A Guńka (PA)

Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00664, Warszawa, Poland.

Anna Olejniczak (A)

Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, 61614, Poznań, Poland.

Samuele Fanetti (S)

Instituto di Chimica dei Composti Organo-Metallici, CNR-ICCOM, Via Madonna del Piano 10, 50019, Sesto Fiorentino, Italy.
LENS, European Laboratory for Nonlinear Spectroscopy, Via Nello Carrara 1, 50019, Sesto Fiorentino, Italy.

Roberto Bini (R)

Instituto di Chimica dei Composti Organo-Metallici, CNR-ICCOM, Via Madonna del Piano 10, 50019, Sesto Fiorentino, Italy.
LENS, European Laboratory for Nonlinear Spectroscopy, Via Nello Carrara 1, 50019, Sesto Fiorentino, Italy.
Dipartimento di Chimica, Università degli Studi di Firenze, Via della Lastruccia 13, 50019, Sesto Fiorentino, Italy.

Ines E Collings (IE)

European Synchrotron Radiation Facility 71, avenue des Martyrs, CS 40220, 38043, Grenoble, France.
current address: Center for X-ray Analytics, Empa-Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, 8600, Dübendorf, Switzerland.

Volodymyr Svitlyk (V)

European Synchrotron Radiation Facility 71, avenue des Martyrs, CS 40220, 38043, Grenoble, France.

Kamil F Dziubek (KF)

LENS, European Laboratory for Nonlinear Spectroscopy, Via Nello Carrara 1, 50019, Sesto Fiorentino, Italy.

Classifications MeSH