Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure

Autores
Flores Antognini, Andrea; Robles, Norma Lis; Cutin, Edgardo Hugo; Bernhardt, Eduard; Hirschberg, Markus; Zeng, Xiaoqing; Willner, Helge; Oberhammer, Heinz
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Analysis of the vibrational spectra and quantum chemical calculations for morpholine sulfur trifluoride,SF3N(CH2CH2)2O, demonstrate that the morpholine ring possesses chair conformation and occupies an equatorial position of the trigonal bipyramidal SF3 group. The compound exists in the gas phase as a mixture of two conformers. The conformer with the SF3 group in equatorial orientation relative to the sixmembered morpholine ring is slightly more stable than the axial conformer and the equilibrium is surprisingly temperature independent. MP2 and B3LYP calculations with cc-pVTZ basis sets predict free energy differences DG° = G°ax _ G°eq of +0.18 and +0.40 kcal/mol, respectively. At temperatures below 12 °C the title compound crystallizes and the structure of the equatorial conformer, which is the only form present in the crystal, was determined by X-ray diffraction. At 131(1) K a phase transition occurs and the low and high temperature forms were studied at 100 and 150 K, respectively.
Fil: Flores Antognini, Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Bernhardt, Eduard. Universität Wuppertal; Alemania
Fil: Hirschberg, Markus. Universität Wuppertal; Alemania
Fil: Zeng, Xiaoqing. Universität Wuppertal; Alemania
Fil: Willner, Helge. Universität Wuppertal; Alemania
Fil: Oberhammer, Heinz. Universität Tübingen; Alemania
Materia
Morph-Sf3
Matrix Ir Spectra
Low Temperature Raman Spectra
X-Ray Crystallography
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/51931
Acceder
id CONICETDig_85eb723167e2fc33743864675f5e45cb
oai_identifier_str oai:ri.conicet.gov.ar:11336/51931
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structureFlores Antognini, AndreaRobles, Norma LisCutin, Edgardo HugoBernhardt, EduardHirschberg, MarkusZeng, XiaoqingWillner, HelgeOberhammer, HeinzMorph-Sf3Matrix Ir SpectraLow Temperature Raman SpectraX-Ray Crystallographyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Analysis of the vibrational spectra and quantum chemical calculations for morpholine sulfur trifluoride,SF3N(CH2CH2)2O, demonstrate that the morpholine ring possesses chair conformation and occupies an equatorial position of the trigonal bipyramidal SF3 group. The compound exists in the gas phase as a mixture of two conformers. The conformer with the SF3 group in equatorial orientation relative to the sixmembered morpholine ring is slightly more stable than the axial conformer and the equilibrium is surprisingly temperature independent. MP2 and B3LYP calculations with cc-pVTZ basis sets predict free energy differences DG° = G°ax _ G°eq of +0.18 and +0.40 kcal/mol, respectively. At temperatures below 12 °C the title compound crystallizes and the structure of the equatorial conformer, which is the only form present in the crystal, was determined by X-ray diffraction. At 131(1) K a phase transition occurs and the low and high temperature forms were studied at 100 and 150 K, respectively.Fil: Flores Antognini, Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; ArgentinaFil: Bernhardt, Eduard. Universität Wuppertal; AlemaniaFil: Hirschberg, Markus. Universität Wuppertal; AlemaniaFil: Zeng, Xiaoqing. Universität Wuppertal; AlemaniaFil: Willner, Helge. Universität Wuppertal; AlemaniaFil: Oberhammer, Heinz. Universität Tübingen; AlemaniaElsevier Science Sa2012-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/51931Flores Antognini, Andrea; Robles, Norma Lis; Cutin, Edgardo Hugo; Bernhardt, Eduard; Hirschberg, Markus; et al.; Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure; Elsevier Science Sa; Journal of Fluorine Chemistry; 144; 12-2012; 59-640022-1139CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jfluchem.2012.07.003info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022113912002424info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-04-15T10:51:54Zoai:ri.conicet.gov.ar:11336/51931instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982026-04-15 10:51:54.545CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
title Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
spellingShingle Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
Flores Antognini, Andrea
Morph-Sf3
Matrix Ir Spectra
Low Temperature Raman Spectra
X-Ray Crystallography
title_short Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
title_full Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
title_fullStr Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
title_full_unstemmed Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
title_sort Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure
dc.creator.none.fl_str_mv Flores Antognini, Andrea
Robles, Norma Lis
Cutin, Edgardo Hugo
Bernhardt, Eduard
Hirschberg, Markus
Zeng, Xiaoqing
Willner, Helge
Oberhammer, Heinz
author Flores Antognini, Andrea
author_facet Flores Antognini, Andrea
Robles, Norma Lis
Cutin, Edgardo Hugo
Bernhardt, Eduard
Hirschberg, Markus
Zeng, Xiaoqing
Willner, Helge
Oberhammer, Heinz
author_role author
author2 Robles, Norma Lis
Cutin, Edgardo Hugo
Bernhardt, Eduard
Hirschberg, Markus
Zeng, Xiaoqing
Willner, Helge
Oberhammer, Heinz
author2_role author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Morph-Sf3
Matrix Ir Spectra
Low Temperature Raman Spectra
X-Ray Crystallography
topic Morph-Sf3
Matrix Ir Spectra
Low Temperature Raman Spectra
X-Ray Crystallography
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Analysis of the vibrational spectra and quantum chemical calculations for morpholine sulfur trifluoride,SF3N(CH2CH2)2O, demonstrate that the morpholine ring possesses chair conformation and occupies an equatorial position of the trigonal bipyramidal SF3 group. The compound exists in the gas phase as a mixture of two conformers. The conformer with the SF3 group in equatorial orientation relative to the sixmembered morpholine ring is slightly more stable than the axial conformer and the equilibrium is surprisingly temperature independent. MP2 and B3LYP calculations with cc-pVTZ basis sets predict free energy differences DG° = G°ax _ G°eq of +0.18 and +0.40 kcal/mol, respectively. At temperatures below 12 °C the title compound crystallizes and the structure of the equatorial conformer, which is the only form present in the crystal, was determined by X-ray diffraction. At 131(1) K a phase transition occurs and the low and high temperature forms were studied at 100 and 150 K, respectively.
Fil: Flores Antognini, Andrea. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química Física; Argentina
Fil: Bernhardt, Eduard. Universität Wuppertal; Alemania
Fil: Hirschberg, Markus. Universität Wuppertal; Alemania
Fil: Zeng, Xiaoqing. Universität Wuppertal; Alemania
Fil: Willner, Helge. Universität Wuppertal; Alemania
Fil: Oberhammer, Heinz. Universität Tübingen; Alemania
description Analysis of the vibrational spectra and quantum chemical calculations for morpholine sulfur trifluoride,SF3N(CH2CH2)2O, demonstrate that the morpholine ring possesses chair conformation and occupies an equatorial position of the trigonal bipyramidal SF3 group. The compound exists in the gas phase as a mixture of two conformers. The conformer with the SF3 group in equatorial orientation relative to the sixmembered morpholine ring is slightly more stable than the axial conformer and the equilibrium is surprisingly temperature independent. MP2 and B3LYP calculations with cc-pVTZ basis sets predict free energy differences DG° = G°ax _ G°eq of +0.18 and +0.40 kcal/mol, respectively. At temperatures below 12 °C the title compound crystallizes and the structure of the equatorial conformer, which is the only form present in the crystal, was determined by X-ray diffraction. At 131(1) K a phase transition occurs and the low and high temperature forms were studied at 100 and 150 K, respectively.
publishDate 2012
dc.date.none.fl_str_mv 2012-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/51931
Flores Antognini, Andrea; Robles, Norma Lis; Cutin, Edgardo Hugo; Bernhardt, Eduard; Hirschberg, Markus; et al.; Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure; Elsevier Science Sa; Journal of Fluorine Chemistry; 144; 12-2012; 59-64
0022-1139
CONICET Digital
CONICET
url http://hdl.handle.net/11336/51931
identifier_str_mv Flores Antognini, Andrea; Robles, Norma Lis; Cutin, Edgardo Hugo; Bernhardt, Eduard; Hirschberg, Markus; et al.; Morpholine sulfur trifluoride: Vibrational spectra, conformational properties and crystal structure; Elsevier Science Sa; Journal of Fluorine Chemistry; 144; 12-2012; 59-64
0022-1139
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jfluchem.2012.07.003
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022113912002424
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.203462

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