Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?

The structure of the metastable form II of 2-bromobenzophenone, obtained by crystallization from the melt, has been determined by powder X-ray diffraction. Form II has been solved in the centrosymmetric monoclinic space group P21/c with a = 8.4896(19) Å, b = 6.5438(8) Å, c = 20.253(1) Å; ß = 104.452...

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Authors: Romanini, Michela|||0000-0002-1685-855X, Rietveld, Ivo B., Barrio Casado, María del|||0000-0003-3467-7581, Negrier, Philippe, Mondieig, Denise, Macovez, Roberto|||0000-0001-5026-9372, Céolin, René, Tamarit Mur, José Luis|||0000-0002-7965-0000
Format: article
Publication Date:2021
Country:España
Institution:Universitat Politècnica de Catalunya (UPC)
Repository:UPCommons. Portal del coneixement obert de la UPC
Language:English
OAI Identifier:oai:upcommons.upc.edu:2117/355603
Online Access:https://hdl.handle.net/2117/355603
https://dx.doi.org/10.1021/acs.cgd.0c01603
Access Level:Open access
Keyword:Crystals
Cristalls
Àrees temàtiques de la UPC::Física::Física de l'estat sòlid::Cristalls
id ES_2e1c5d96f3e2aa10dd36c205e2c01ec9
oai_identifier_str oai:upcommons.upc.edu:2117/355603
network_acronym_str ES
network_name_str España
repository_id_str
spelling Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?Romanini, Michela|||0000-0002-1685-855XRietveld, Ivo B.Barrio Casado, María del|||0000-0003-3467-7581Negrier, PhilippeMondieig, DeniseMacovez, Roberto|||0000-0001-5026-9372Céolin, RenéTamarit Mur, José Luis|||0000-0002-7965-0000CrystalsCristallsÀrees temàtiques de la UPC::Física::Física de l'estat sòlid::CristallsThe structure of the metastable form II of 2-bromobenzophenone, obtained by crystallization from the melt, has been determined by powder X-ray diffraction. Form II has been solved in the centrosymmetric monoclinic space group P21/c with a = 8.4896(19) Å, b = 6.5438(8) Å, c = 20.253(1) Å; ß = 104.452(6)°, and Z = 4 (Z' = 1) at 200 K. Both form I and form II contain a multitude of aromatic interactions, and the strength and direction of these interactions could only be interpreted with the support of the thermal-expansion tensors. Both forms exhibit, unexpectedly, uniaxial negative thermal expansion, while hydrogen bonding does not play a significant role in either of these two structures. It appears to be the first time in the literature that uniaxial negative thermal expansion may be caused by aromatic interactions. Thermodynamic properties at normal and high pressure have been determined for the stable and metastable phases, and a pressure–temperature phase diagram has been constructed. While the metastable form behaves monotropically with respect to the stable form under ambient conditions, the phase relationship becomes enantiotropic at high pressure, providing a clear example of phase behavior in which the densest form is not the most stable form under ambient conditions.Peer ReviewedAmerican Chemical Society20212021-04-0720212021-11-04journal articlehttp://purl.org/coar/resource_type/c_6501AMhttp://purl.org/coar/version/c_ab4af688f83e57aainfo:eu-repo/semantics/articleapplication/pdfapplication/pdfhttps://hdl.handle.net/2117/355603https://dx.doi.org/10.1021/acs.cgd.0c01603reponame:UPCommons. Portal del coneixement obert de la UPCinstname:Universitat Politècnica de Catalunya (UPC)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivs 3.0 Spainhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/info:eu-repo/semantics/openAccessoai:upcommons.upc.edu:2117/3556032026-05-27T15:37:01Z
dc.title.none.fl_str_mv Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
title Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
spellingShingle Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
Romanini, Michela|||0000-0002-1685-855X
Crystals
Cristalls
Àrees temàtiques de la UPC::Física::Física de l'estat sòlid::Cristalls
title_short Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
title_full Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
title_fullStr Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
title_full_unstemmed Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
title_sort Uniaxial negative thermal expansion in polymorphic 2-bromobenzophenone, due to aromatic interactions?
dc.creator.none.fl_str_mv Romanini, Michela|||0000-0002-1685-855X
Rietveld, Ivo B.
Barrio Casado, María del|||0000-0003-3467-7581
Negrier, Philippe
Mondieig, Denise
Macovez, Roberto|||0000-0001-5026-9372
Céolin, René
Tamarit Mur, José Luis|||0000-0002-7965-0000
author Romanini, Michela|||0000-0002-1685-855X
author_facet Romanini, Michela|||0000-0002-1685-855X
Rietveld, Ivo B.
Barrio Casado, María del|||0000-0003-3467-7581
Negrier, Philippe
Mondieig, Denise
Macovez, Roberto|||0000-0001-5026-9372
Céolin, René
Tamarit Mur, José Luis|||0000-0002-7965-0000
author_role author
author2 Rietveld, Ivo B.
Barrio Casado, María del|||0000-0003-3467-7581
Negrier, Philippe
Mondieig, Denise
Macovez, Roberto|||0000-0001-5026-9372
Céolin, René
Tamarit Mur, José Luis|||0000-0002-7965-0000
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Crystals
Cristalls
Àrees temàtiques de la UPC::Física::Física de l'estat sòlid::Cristalls
topic Crystals
Cristalls
Àrees temàtiques de la UPC::Física::Física de l'estat sòlid::Cristalls
description The structure of the metastable form II of 2-bromobenzophenone, obtained by crystallization from the melt, has been determined by powder X-ray diffraction. Form II has been solved in the centrosymmetric monoclinic space group P21/c with a = 8.4896(19) Å, b = 6.5438(8) Å, c = 20.253(1) Å; ß = 104.452(6)°, and Z = 4 (Z' = 1) at 200 K. Both form I and form II contain a multitude of aromatic interactions, and the strength and direction of these interactions could only be interpreted with the support of the thermal-expansion tensors. Both forms exhibit, unexpectedly, uniaxial negative thermal expansion, while hydrogen bonding does not play a significant role in either of these two structures. It appears to be the first time in the literature that uniaxial negative thermal expansion may be caused by aromatic interactions. Thermodynamic properties at normal and high pressure have been determined for the stable and metastable phases, and a pressure–temperature phase diagram has been constructed. While the metastable form behaves monotropically with respect to the stable form under ambient conditions, the phase relationship becomes enantiotropic at high pressure, providing a clear example of phase behavior in which the densest form is not the most stable form under ambient conditions.
publishDate 2021
dc.date.none.fl_str_mv 2021
2021-04-07
2021
2021-11-04
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
AM
http://purl.org/coar/version/c_ab4af688f83e57aa
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/2117/355603
https://dx.doi.org/10.1021/acs.cgd.0c01603
url https://hdl.handle.net/2117/355603
https://dx.doi.org/10.1021/acs.cgd.0c01603
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivs 3.0 Spain
http://creativecommons.org/licenses/by-nc-nd/3.0/es/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:UPCommons. Portal del coneixement obert de la UPC
instname:Universitat Politècnica de Catalunya (UPC)
instname_str Universitat Politècnica de Catalunya (UPC)
reponame_str UPCommons. Portal del coneixement obert de la UPC
collection UPCommons. Portal del coneixement obert de la UPC
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,301603

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