Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations

Autores
Granifo, Juan; Suarez, Sebastian; Boubeta, Fernando Martín; Baggio, Ricardo Fortunato
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We report herein the synthesis, crystallographic analysis and a study of the noncovalent interactions observed in the new 4′-substituted terpyridine-based derivative bis[4′-(isoquinolin-2-ium-4-yl)-2,2′:6′,2′′-terpyridine-1,1′′-diium] tris[tetrachloridozincate(II)] monohydrate, (C24H19N4)2[ZnCl4]3·H2O or (ITPH3)2[ZnCl4]3·H2O, where (ITPH3)3+ is the triply protonated cation derived from 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine (ITP) [Granifo et al. (2016). Acta Cryst. C72, 932-938]. The (ITPH3)3+ cation presents a number of interesting similarities and differences compared with its neutral ITP relative, mainly in the role fulfilled in the packing arrangement by the profuse set of D - H...A [D (donor) = C, N or O; A (acceptor) = O or Cl], π-π and anion...π noncovalent interactions present. We discuss these interactions in two different complementary ways, viz. using a point-to-point approach in the light of Bader's theory of Atoms In Molecules (AIM), analyzing the individual significance of each interaction, and in a more 'global' analysis, making use of the Hirshfeld surfaces and the associated enrichment ratio (ER) approach, evaluating the surprisingly large co-operative effect of the superabundant weaker contacts.The structural analysis of the terpyridine-based compound (ITPH3)2[ZnCl4]3·H2O [(ITPH3)3+ is the triply protonated cation of 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine] demonstrates the concerted way in which a variety of noncovalent interactions, viz. hydrogen bonding, π-π and anion...π, participate in the crystal packing. An unexpected large enrichment ratio between the cationic C...N contacts can be understood in the light of their correlation with the atomic and ring NBO (natural bond order) charges.
Fil: Granifo, Juan. Universidad de La Frontera; Chile
Fil: Suarez, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Boubeta, Fernando Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
Materia
AIM ANALYSIS
ANION...Π INTERACTIONS
COMPUTATIONAL CHEMISTRY
CRYSTAL STRUCTURE
ENRICHMENT RATIO
HIRSHFELD SURFACES
TERPYRIDINE
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:11336/64966

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network_name_str CONICET Digital (CONICET)
spelling Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cationsGranifo, JuanSuarez, SebastianBoubeta, Fernando MartínBaggio, Ricardo FortunatoAIM ANALYSISANION...Π INTERACTIONSCOMPUTATIONAL CHEMISTRYCRYSTAL STRUCTUREENRICHMENT RATIOHIRSHFELD SURFACESTERPYRIDINEhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1We report herein the synthesis, crystallographic analysis and a study of the noncovalent interactions observed in the new 4′-substituted terpyridine-based derivative bis[4′-(isoquinolin-2-ium-4-yl)-2,2′:6′,2′′-terpyridine-1,1′′-diium] tris[tetrachloridozincate(II)] monohydrate, (C24H19N4)2[ZnCl4]3·H2O or (ITPH3)2[ZnCl4]3·H2O, where (ITPH3)3+ is the triply protonated cation derived from 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine (ITP) [Granifo et al. (2016). Acta Cryst. C72, 932-938]. The (ITPH3)3+ cation presents a number of interesting similarities and differences compared with its neutral ITP relative, mainly in the role fulfilled in the packing arrangement by the profuse set of D - H...A [D (donor) = C, N or O; A (acceptor) = O or Cl], π-π and anion...π noncovalent interactions present. We discuss these interactions in two different complementary ways, viz. using a point-to-point approach in the light of Bader's theory of Atoms In Molecules (AIM), analyzing the individual significance of each interaction, and in a more 'global' analysis, making use of the Hirshfeld surfaces and the associated enrichment ratio (ER) approach, evaluating the surprisingly large co-operative effect of the superabundant weaker contacts.The structural analysis of the terpyridine-based compound (ITPH3)2[ZnCl4]3·H2O [(ITPH3)3+ is the triply protonated cation of 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine] demonstrates the concerted way in which a variety of noncovalent interactions, viz. hydrogen bonding, π-π and anion...π, participate in the crystal packing. An unexpected large enrichment ratio between the cationic C...N contacts can be understood in the light of their correlation with the atomic and ring NBO (natural bond order) charges.Fil: Granifo, Juan. Universidad de La Frontera; ChileFil: Suarez, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Boubeta, Fernando Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; ArgentinaInternational Union of Crystallography2017-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/64966Granifo, Juan; Suarez, Sebastian; Boubeta, Fernando Martín; Baggio, Ricardo Fortunato; Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations; International Union of Crystallography; Acta Crystallographica Section C: Structural Chemistry; 73; 12; 12-2017; 1121-11302053-2296CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1107/S2053229617016308info:eu-repo/semantics/altIdentifier/url/http://scripts.iucr.org/cgi-bin/paper?S2053229617016308info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:53:58Zoai:ri.conicet.gov.ar:11336/64966instacron: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:34982025-09-29 09:53:58.938CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
title Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
spellingShingle Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
Granifo, Juan
AIM ANALYSIS
ANION...Π INTERACTIONS
COMPUTATIONAL CHEMISTRY
CRYSTAL STRUCTURE
ENRICHMENT RATIO
HIRSHFELD SURFACES
TERPYRIDINE
title_short Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
title_full Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
title_fullStr Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
title_full_unstemmed Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
title_sort Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations
dc.creator.none.fl_str_mv Granifo, Juan
Suarez, Sebastian
Boubeta, Fernando Martín
Baggio, Ricardo Fortunato
author Granifo, Juan
author_facet Granifo, Juan
Suarez, Sebastian
Boubeta, Fernando Martín
Baggio, Ricardo Fortunato
author_role author
author2 Suarez, Sebastian
Boubeta, Fernando Martín
Baggio, Ricardo Fortunato
author2_role author
author
author
dc.subject.none.fl_str_mv AIM ANALYSIS
ANION...Π INTERACTIONS
COMPUTATIONAL CHEMISTRY
CRYSTAL STRUCTURE
ENRICHMENT RATIO
HIRSHFELD SURFACES
TERPYRIDINE
topic AIM ANALYSIS
ANION...Π INTERACTIONS
COMPUTATIONAL CHEMISTRY
CRYSTAL STRUCTURE
ENRICHMENT RATIO
HIRSHFELD SURFACES
TERPYRIDINE
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We report herein the synthesis, crystallographic analysis and a study of the noncovalent interactions observed in the new 4′-substituted terpyridine-based derivative bis[4′-(isoquinolin-2-ium-4-yl)-2,2′:6′,2′′-terpyridine-1,1′′-diium] tris[tetrachloridozincate(II)] monohydrate, (C24H19N4)2[ZnCl4]3·H2O or (ITPH3)2[ZnCl4]3·H2O, where (ITPH3)3+ is the triply protonated cation derived from 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine (ITP) [Granifo et al. (2016). Acta Cryst. C72, 932-938]. The (ITPH3)3+ cation presents a number of interesting similarities and differences compared with its neutral ITP relative, mainly in the role fulfilled in the packing arrangement by the profuse set of D - H...A [D (donor) = C, N or O; A (acceptor) = O or Cl], π-π and anion...π noncovalent interactions present. We discuss these interactions in two different complementary ways, viz. using a point-to-point approach in the light of Bader's theory of Atoms In Molecules (AIM), analyzing the individual significance of each interaction, and in a more 'global' analysis, making use of the Hirshfeld surfaces and the associated enrichment ratio (ER) approach, evaluating the surprisingly large co-operative effect of the superabundant weaker contacts.The structural analysis of the terpyridine-based compound (ITPH3)2[ZnCl4]3·H2O [(ITPH3)3+ is the triply protonated cation of 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine] demonstrates the concerted way in which a variety of noncovalent interactions, viz. hydrogen bonding, π-π and anion...π, participate in the crystal packing. An unexpected large enrichment ratio between the cationic C...N contacts can be understood in the light of their correlation with the atomic and ring NBO (natural bond order) charges.
Fil: Granifo, Juan. Universidad de La Frontera; Chile
Fil: Suarez, Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Boubeta, Fernando Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Baggio, Ricardo Fortunato. Comisión Nacional de Energía Atómica. Centro Atómico Constituyentes; Argentina
description We report herein the synthesis, crystallographic analysis and a study of the noncovalent interactions observed in the new 4′-substituted terpyridine-based derivative bis[4′-(isoquinolin-2-ium-4-yl)-2,2′:6′,2′′-terpyridine-1,1′′-diium] tris[tetrachloridozincate(II)] monohydrate, (C24H19N4)2[ZnCl4]3·H2O or (ITPH3)2[ZnCl4]3·H2O, where (ITPH3)3+ is the triply protonated cation derived from 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine (ITP) [Granifo et al. (2016). Acta Cryst. C72, 932-938]. The (ITPH3)3+ cation presents a number of interesting similarities and differences compared with its neutral ITP relative, mainly in the role fulfilled in the packing arrangement by the profuse set of D - H...A [D (donor) = C, N or O; A (acceptor) = O or Cl], π-π and anion...π noncovalent interactions present. We discuss these interactions in two different complementary ways, viz. using a point-to-point approach in the light of Bader's theory of Atoms In Molecules (AIM), analyzing the individual significance of each interaction, and in a more 'global' analysis, making use of the Hirshfeld surfaces and the associated enrichment ratio (ER) approach, evaluating the surprisingly large co-operative effect of the superabundant weaker contacts.The structural analysis of the terpyridine-based compound (ITPH3)2[ZnCl4]3·H2O [(ITPH3)3+ is the triply protonated cation of 4′-(isoquinolin-4-yl)-2,2′:6′,2′′-terpyridine] demonstrates the concerted way in which a variety of noncovalent interactions, viz. hydrogen bonding, π-π and anion...π, participate in the crystal packing. An unexpected large enrichment ratio between the cationic C...N contacts can be understood in the light of their correlation with the atomic and ring NBO (natural bond order) charges.
publishDate 2017
dc.date.none.fl_str_mv 2017-12
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/11336/64966
Granifo, Juan; Suarez, Sebastian; Boubeta, Fernando Martín; Baggio, Ricardo Fortunato; Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations; International Union of Crystallography; Acta Crystallographica Section C: Structural Chemistry; 73; 12; 12-2017; 1121-1130
2053-2296
CONICET Digital
CONICET
url http://hdl.handle.net/11336/64966
identifier_str_mv Granifo, Juan; Suarez, Sebastian; Boubeta, Fernando Martín; Baggio, Ricardo Fortunato; Crystallographic and computational study of a network composed of [ZnCl4]2- anions and triply protonated 4′-functionalized terpyridine cations; International Union of Crystallography; Acta Crystallographica Section C: Structural Chemistry; 73; 12; 12-2017; 1121-1130
2053-2296
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1107/S2053229617016308
info:eu-repo/semantics/altIdentifier/url/http://scripts.iucr.org/cgi-bin/paper?S2053229617016308
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 International Union of Crystallography
publisher.none.fl_str_mv International Union of Crystallography
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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