Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo
Autor(a) principal: | |
---|---|
Data de Publicação: | 2020 |
Tipo de documento: | Dissertação |
Idioma: | por |
Título da fonte: | Repositório Institucional Manancial UFSM |
Texto Completo: | http://repositorio.ufsm.br/handle/1/23003 |
Resumo: | This work presents the study of intermolecular interactions and the molecular association process of bis (alkylaryl, aryl) pyridine-2,6-dicarboxamides, where the alkylaryl substitutes are (1) 2,2-diphenylethyl, (2) phenylethyl and (3) benzyl, and the aryl substitutes are (4) 4-fluorophenyl, (5) 4-chlorophenyl and (6) 4-bromophenyl, as well as the compound bis(2-2,diphenylethyl)isophthalamide (7). The supramolecular cluster, consisting of a central molecule and the molecules that make up the first sphere of molecular coordination, was used as a study demarcation. The pyridine-2,6-dicarboxamides 1-6 adopted a curved conformation, with the N-H groups facing inwards, while compound 7 presented a linear conformation. Bis(2,2-diphenylethyl)pyridine-2,6-dicarboxamide (1) crystallized as three conformational polymorphs. X-ray diffraction data showed that compound 2 is also a hydrate. The molecular overlays of the central part (CH – CH2 – NH – C (O) –2 – py – 6 – C (O) –NH – CH2 – CH) between the polymorphs of compound 1 indicated a greater molecular similarity between 1II and 1III. Calculations of the molecular stabilization energy carried out for polymorphs 1I-III indicated that polymorph 1II has a conformation of almost 22 Kcal mol-1 less stable than polymorph 1I, while polymorph 1III is 6 Kcal mol-1 less stable than polymorph 1I. Analyzing supramolecular stabilization energy data for the polymorphs, the highest total stabilization energy value was presented for compound 1II. Regarding the polymorphs, a crystalline packaging efficiency of 0.864 was observed for compound 1I and 0.874 for compound 1II. Compound 1III has the lowest packaging efficiency (0.811). According to the crystallization mechanisms proposed for compounds 1I-II and 3-6, there is a preference for stacking through amides, which form hydrogen bonds. Compounds 1III and 7 form blocks with preferential growth in two directions. Compound 2 forms dimers in the first crystallization stage, presenting the sum of the normalized energy contributions and contact area (NCG%) equal to 19 in this stage. Compound 7 stands out for presenting NCG% = 78 in the first stage. For compounds 1I-III and 3-6, the first crystallization stage has NCG% around 50. The alkylaryl and aryl substitutes are relevant at the end of the crystallization process, where the geometric parameter usually dominates. The ¹H NMR experiments in solution with concentration variation performed for compounds 1 and 7 detected intermolecular interactions N-H ∙∙∙ O = C and C-H ∙∙∙ π, which can be correlated with the respective crystallization mechanisms. From the analysis of the topological and energetic data, the formation of hydrates 1I-III and 2 was attributed to the presence of the amide groups together with the pyridinic nitrogen, interacting with the solvent molecule through hydrogen bonds. The occurrence of polymorphs for compound 1 was attributed to the possibility of different conformations for the molecule, enabling the formation of different intermolecular interactions. For compounds 1I-III and 2, it was observed that the water is positioned in the cavity formed by the other molecules and, therefore, they should not be evaluated in isolation. |
id |
UFSM-20_be10c653aa984664b2c7b5842c5f484d |
---|---|
oai_identifier_str |
oai:repositorio.ufsm.br:1/23003 |
network_acronym_str |
UFSM-20 |
network_name_str |
Repositório Institucional Manancial UFSM |
repository_id_str |
3913 |
spelling |
2021-11-26T12:49:50Z2021-11-26T12:49:50Z2020-03-02http://repositorio.ufsm.br/handle/1/23003This work presents the study of intermolecular interactions and the molecular association process of bis (alkylaryl, aryl) pyridine-2,6-dicarboxamides, where the alkylaryl substitutes are (1) 2,2-diphenylethyl, (2) phenylethyl and (3) benzyl, and the aryl substitutes are (4) 4-fluorophenyl, (5) 4-chlorophenyl and (6) 4-bromophenyl, as well as the compound bis(2-2,diphenylethyl)isophthalamide (7). The supramolecular cluster, consisting of a central molecule and the molecules that make up the first sphere of molecular coordination, was used as a study demarcation. The pyridine-2,6-dicarboxamides 1-6 adopted a curved conformation, with the N-H groups facing inwards, while compound 7 presented a linear conformation. Bis(2,2-diphenylethyl)pyridine-2,6-dicarboxamide (1) crystallized as three conformational polymorphs. X-ray diffraction data showed that compound 2 is also a hydrate. The molecular overlays of the central part (CH – CH2 – NH – C (O) –2 – py – 6 – C (O) –NH – CH2 – CH) between the polymorphs of compound 1 indicated a greater molecular similarity between 1II and 1III. Calculations of the molecular stabilization energy carried out for polymorphs 1I-III indicated that polymorph 1II has a conformation of almost 22 Kcal mol-1 less stable than polymorph 1I, while polymorph 1III is 6 Kcal mol-1 less stable than polymorph 1I. Analyzing supramolecular stabilization energy data for the polymorphs, the highest total stabilization energy value was presented for compound 1II. Regarding the polymorphs, a crystalline packaging efficiency of 0.864 was observed for compound 1I and 0.874 for compound 1II. Compound 1III has the lowest packaging efficiency (0.811). According to the crystallization mechanisms proposed for compounds 1I-II and 3-6, there is a preference for stacking through amides, which form hydrogen bonds. Compounds 1III and 7 form blocks with preferential growth in two directions. Compound 2 forms dimers in the first crystallization stage, presenting the sum of the normalized energy contributions and contact area (NCG%) equal to 19 in this stage. Compound 7 stands out for presenting NCG% = 78 in the first stage. For compounds 1I-III and 3-6, the first crystallization stage has NCG% around 50. The alkylaryl and aryl substitutes are relevant at the end of the crystallization process, where the geometric parameter usually dominates. The ¹H NMR experiments in solution with concentration variation performed for compounds 1 and 7 detected intermolecular interactions N-H ∙∙∙ O = C and C-H ∙∙∙ π, which can be correlated with the respective crystallization mechanisms. From the analysis of the topological and energetic data, the formation of hydrates 1I-III and 2 was attributed to the presence of the amide groups together with the pyridinic nitrogen, interacting with the solvent molecule through hydrogen bonds. The occurrence of polymorphs for compound 1 was attributed to the possibility of different conformations for the molecule, enabling the formation of different intermolecular interactions. For compounds 1I-III and 2, it was observed that the water is positioned in the cavity formed by the other molecules and, therefore, they should not be evaluated in isolation.Este trabalho apresenta o estudo das interações intermoleculares e o processo de associação molecular das bis(alquilaril, aril)piridina-2,6-dicarboxamidas, onde os substituíntes alquilaril são (1) 2,2-difeniletil, (2) feniletil e (3) benzil, e os substituíntes aril são (4) 4-fluorofenil, (5) 4-clorofenil e (6) 4-bromofenil, assim como o composto bis(2-2,difeniletil)isoftalamida (7). O cluster supramolecular, constituído por uma molécula central e as moléculas que compõem a primeira esfera de coordenação molecular, foi utilizado como demarcação de estudo. As piridina-2,6-dicarboxamidas 1-6 adotaram uma conformação curva, com os grupos NH voltados para a parte interna, enquanto que o composto (7) apresentou uma conformação linear. A bis(2,2-difeniletil)piridina-2,6-dicarboxamida (1) cristalizou na forma de três polimorfos conformacionais. Dados de difração de raios X mostraram que o composto 2 também é um hidrato. As sobreposições moleculares da parte central (CH–CH2–NH–C(O)–2–py–6–C(O)–NH–CH2–CH) entre os polimorfos do composto 1 indicaram maior semelhança molecular entre 1II e 1III. Cálculos da energia de estabilização molecular realizados para os polimorfos 1I-III indicaram que o polimorfo 1II tem uma conformação de quase 22 Kcal mol-1 menos estável que o polimorfo 1I, enquanto o polimorfo 1III é 6 Kcal mol-1 menos estável que o polimorfo 1I. Analisando dados de energia de estabilização supramolecular para os polimorfos, o composto 1II apresentou o maior valor total de energia de estabilização. Em relação aos polimorfos, foi observada uma eficiência do empacotamento cristalino de 0,864 para o composto 1I e 0,874 para o composto 1II. O composto 1III tem a menor eficiência de empacotamento (0,811). De acordo com os mecanismos de cristalização propostos para os compostos 1I-II e 3-6, há uma preferência pelo empilhamento através das amidas, que formam ligações de hidrogênio. Os compostos 1III e 7 formam blocos com crescimento preferencial em duas direções. O composto 2 forma dímeros no primeiro estágio de cristalização, apresentando a soma das contribuições de energia e área de contato normalizadas (NCG%) igual a 19 neste estágio. O composto 7 se destaca por apresentar NCG% = 78 no primeiro estágio. Para os compostos 1I-III e 3-6, o primeiro estágio de cristalização possui NCG% em torno de 50. Os substituíntes alquilaril e aril são relevantes ao final do processo de cristalização, onde o parâmetro geométrico geralmente domina. Os experimentos de RMN de ¹H em solução com variação de concentração realizados para os compostos 1 e 7 detectaram interações intermoleculares N-H∙∙∙O=C e C-H∙∙∙π, podendo ser correlacionadas com os respectivos mecanismos de cristalização. A partir da análise dos dados topológicos e energéticos, a formação dos hidratos 1I-III e 2 foi atribuída à presença dos grupos amida juntamente com o nitrogênio piridínico, interagindo com a molécula do solvente através de ligações de hidrogênio. A ocorrência dos polimorfos para o composto 1 foi atribuída à possibilidade de diferentes conformações para a molécula, possibilitanto a formação de diferentes interações intermoleculares. Para os compostos 1I-III e 2, foi observado que a água está localizada na cavidade formada pelas outras moléculas e, portanto, estas não devem ser avaliadas isoladamente.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPESConselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPqporUniversidade Federal de Santa MariaCentro de Ciências Naturais e ExatasPrograma de Pós-Graduação em QuímicaUFSMBrasilQuímicaAttribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessEngenharia de cristaisCluster supramolecularPolimorfosHidratosCristalizaçãoCrystal engineeringSupramolecular clusterPolymorphsHydratesCrystallizationCNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICABis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismoBis(alkylaryl, aryl)pyridine-2,6-dicarboxyamides: molecular, supramolecular structure and polymorphisminfo:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/masterThesisMartins, Marcos Antonio Pintohttp://lattes.cnpq.br/6457412713967642Hörner, ManfredoFiss, Gabriela Fehnhttp://lattes.cnpq.br/7576749712683442Rosa, Jéssica Maria Luis100600000000600600600600600c28419d9-6027-4f9c-acd2-76e8067a85d17b659cb1-da15-48cd-abf4-bb4fd9931f1734252cc3-b6c0-4876-9bb6-6020475d2214dea8c68c-cf04-46ff-bbf0-a9d1fe9003b8reponame:Repositório Institucional Manancial UFSMinstname:Universidade Federal de Santa Maria (UFSM)instacron:UFSMORIGINALDIS_PPGQUIMICA_2020_ROSA_JESSICA.pdfDIS_PPGQUIMICA_2020_ROSA_JESSICA.pdfDissertaçãoapplication/pdf7195710http://repositorio.ufsm.br/bitstream/1/23003/1/DIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf63fa50edaf72a323c63aa4d7038fd09dMD51CC-LICENSElicense_rdflicense_rdfapplication/rdf+xml; charset=utf-8805http://repositorio.ufsm.br/bitstream/1/23003/2/license_rdf4460e5956bc1d1639be9ae6146a50347MD52LICENSElicense.txtlicense.txttext/plain; charset=utf-81956http://repositorio.ufsm.br/bitstream/1/23003/3/license.txt2f0571ecee68693bd5cd3f17c1e075dfMD53TEXTDIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.txtDIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.txtExtracted texttext/plain143624http://repositorio.ufsm.br/bitstream/1/23003/4/DIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.txtca68c6833c79032f2f690683d102953aMD54THUMBNAILDIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.jpgDIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.jpgIM Thumbnailimage/jpeg4360http://repositorio.ufsm.br/bitstream/1/23003/5/DIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.jpg56b21961d189149831e71225027b13b6MD551/230032021-11-27 03:03:19.818oai:repositorio.ufsm.br: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ório Institucionalhttp://repositorio.ufsm.br/PUBhttp://repositorio.ufsm.br/oai/requestouvidoria@ufsm.bropendoar:39132021-11-27T06:03:19Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM)false |
dc.title.por.fl_str_mv |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo |
dc.title.alternative.eng.fl_str_mv |
Bis(alkylaryl, aryl)pyridine-2,6-dicarboxyamides: molecular, supramolecular structure and polymorphism |
title |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo |
spellingShingle |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo Rosa, Jéssica Maria Luis Engenharia de cristais Cluster supramolecular Polimorfos Hidratos Cristalização Crystal engineering Supramolecular cluster Polymorphs Hydrates Crystallization CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
title_short |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo |
title_full |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo |
title_fullStr |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo |
title_full_unstemmed |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo |
title_sort |
Bis(alquilaril, aril)piridina-2,6-dicarboxiamidas: estrutura molecular, supramolecular e polimorfismo |
author |
Rosa, Jéssica Maria Luis |
author_facet |
Rosa, Jéssica Maria Luis |
author_role |
author |
dc.contributor.advisor1.fl_str_mv |
Martins, Marcos Antonio Pinto |
dc.contributor.advisor1Lattes.fl_str_mv |
http://lattes.cnpq.br/6457412713967642 |
dc.contributor.referee1.fl_str_mv |
Hörner, Manfredo |
dc.contributor.referee2.fl_str_mv |
Fiss, Gabriela Fehn |
dc.contributor.authorLattes.fl_str_mv |
http://lattes.cnpq.br/7576749712683442 |
dc.contributor.author.fl_str_mv |
Rosa, Jéssica Maria Luis |
contributor_str_mv |
Martins, Marcos Antonio Pinto Hörner, Manfredo Fiss, Gabriela Fehn |
dc.subject.por.fl_str_mv |
Engenharia de cristais Cluster supramolecular Polimorfos Hidratos Cristalização |
topic |
Engenharia de cristais Cluster supramolecular Polimorfos Hidratos Cristalização Crystal engineering Supramolecular cluster Polymorphs Hydrates Crystallization CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
dc.subject.eng.fl_str_mv |
Crystal engineering Supramolecular cluster Polymorphs Hydrates Crystallization |
dc.subject.cnpq.fl_str_mv |
CNPQ::CIENCIAS EXATAS E DA TERRA::QUIMICA |
description |
This work presents the study of intermolecular interactions and the molecular association process of bis (alkylaryl, aryl) pyridine-2,6-dicarboxamides, where the alkylaryl substitutes are (1) 2,2-diphenylethyl, (2) phenylethyl and (3) benzyl, and the aryl substitutes are (4) 4-fluorophenyl, (5) 4-chlorophenyl and (6) 4-bromophenyl, as well as the compound bis(2-2,diphenylethyl)isophthalamide (7). The supramolecular cluster, consisting of a central molecule and the molecules that make up the first sphere of molecular coordination, was used as a study demarcation. The pyridine-2,6-dicarboxamides 1-6 adopted a curved conformation, with the N-H groups facing inwards, while compound 7 presented a linear conformation. Bis(2,2-diphenylethyl)pyridine-2,6-dicarboxamide (1) crystallized as three conformational polymorphs. X-ray diffraction data showed that compound 2 is also a hydrate. The molecular overlays of the central part (CH – CH2 – NH – C (O) –2 – py – 6 – C (O) –NH – CH2 – CH) between the polymorphs of compound 1 indicated a greater molecular similarity between 1II and 1III. Calculations of the molecular stabilization energy carried out for polymorphs 1I-III indicated that polymorph 1II has a conformation of almost 22 Kcal mol-1 less stable than polymorph 1I, while polymorph 1III is 6 Kcal mol-1 less stable than polymorph 1I. Analyzing supramolecular stabilization energy data for the polymorphs, the highest total stabilization energy value was presented for compound 1II. Regarding the polymorphs, a crystalline packaging efficiency of 0.864 was observed for compound 1I and 0.874 for compound 1II. Compound 1III has the lowest packaging efficiency (0.811). According to the crystallization mechanisms proposed for compounds 1I-II and 3-6, there is a preference for stacking through amides, which form hydrogen bonds. Compounds 1III and 7 form blocks with preferential growth in two directions. Compound 2 forms dimers in the first crystallization stage, presenting the sum of the normalized energy contributions and contact area (NCG%) equal to 19 in this stage. Compound 7 stands out for presenting NCG% = 78 in the first stage. For compounds 1I-III and 3-6, the first crystallization stage has NCG% around 50. The alkylaryl and aryl substitutes are relevant at the end of the crystallization process, where the geometric parameter usually dominates. The ¹H NMR experiments in solution with concentration variation performed for compounds 1 and 7 detected intermolecular interactions N-H ∙∙∙ O = C and C-H ∙∙∙ π, which can be correlated with the respective crystallization mechanisms. From the analysis of the topological and energetic data, the formation of hydrates 1I-III and 2 was attributed to the presence of the amide groups together with the pyridinic nitrogen, interacting with the solvent molecule through hydrogen bonds. The occurrence of polymorphs for compound 1 was attributed to the possibility of different conformations for the molecule, enabling the formation of different intermolecular interactions. For compounds 1I-III and 2, it was observed that the water is positioned in the cavity formed by the other molecules and, therefore, they should not be evaluated in isolation. |
publishDate |
2020 |
dc.date.issued.fl_str_mv |
2020-03-02 |
dc.date.accessioned.fl_str_mv |
2021-11-26T12:49:50Z |
dc.date.available.fl_str_mv |
2021-11-26T12:49:50Z |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/masterThesis |
format |
masterThesis |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://repositorio.ufsm.br/handle/1/23003 |
url |
http://repositorio.ufsm.br/handle/1/23003 |
dc.language.iso.fl_str_mv |
por |
language |
por |
dc.relation.cnpq.fl_str_mv |
100600000000 |
dc.relation.confidence.fl_str_mv |
600 600 600 600 600 |
dc.relation.authority.fl_str_mv |
c28419d9-6027-4f9c-acd2-76e8067a85d1 7b659cb1-da15-48cd-abf4-bb4fd9931f17 34252cc3-b6c0-4876-9bb6-6020475d2214 dea8c68c-cf04-46ff-bbf0-a9d1fe9003b8 |
dc.rights.driver.fl_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ info:eu-repo/semantics/openAccess |
rights_invalid_str_mv |
Attribution-NonCommercial-NoDerivatives 4.0 International http://creativecommons.org/licenses/by-nc-nd/4.0/ |
eu_rights_str_mv |
openAccess |
dc.publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.publisher.program.fl_str_mv |
Programa de Pós-Graduação em Química |
dc.publisher.initials.fl_str_mv |
UFSM |
dc.publisher.country.fl_str_mv |
Brasil |
dc.publisher.department.fl_str_mv |
Química |
publisher.none.fl_str_mv |
Universidade Federal de Santa Maria Centro de Ciências Naturais e Exatas |
dc.source.none.fl_str_mv |
reponame:Repositório Institucional Manancial UFSM instname:Universidade Federal de Santa Maria (UFSM) instacron:UFSM |
instname_str |
Universidade Federal de Santa Maria (UFSM) |
instacron_str |
UFSM |
institution |
UFSM |
reponame_str |
Repositório Institucional Manancial UFSM |
collection |
Repositório Institucional Manancial UFSM |
bitstream.url.fl_str_mv |
http://repositorio.ufsm.br/bitstream/1/23003/1/DIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf http://repositorio.ufsm.br/bitstream/1/23003/2/license_rdf http://repositorio.ufsm.br/bitstream/1/23003/3/license.txt http://repositorio.ufsm.br/bitstream/1/23003/4/DIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.txt http://repositorio.ufsm.br/bitstream/1/23003/5/DIS_PPGQUIMICA_2020_ROSA_JESSICA.pdf.jpg |
bitstream.checksum.fl_str_mv |
63fa50edaf72a323c63aa4d7038fd09d 4460e5956bc1d1639be9ae6146a50347 2f0571ecee68693bd5cd3f17c1e075df ca68c6833c79032f2f690683d102953a 56b21961d189149831e71225027b13b6 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Repositório Institucional Manancial UFSM - Universidade Federal de Santa Maria (UFSM) |
repository.mail.fl_str_mv |
ouvidoria@ufsm.br |
_version_ |
1808854722507964416 |