Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography

Autores
Colombo, Fernando; Mugnaioli, Enrico; Vallcorba, Oriol; García, Alberto; Goñi, Alejandro; Rius, Jordi
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The crystal structure of karibibite, Fe3+3 (As3+O2)4(As3+2 O5)(OH), from the Urucum mine (Minas Gerais, Brazil), was solved and refined from electron diffraction tomography data [R1 = 18.8% for F > 4σ(F)] and further confirmed by synchrotron X-ray diffraction and density functional theory (DFT) calculations. The mineral is orthorhombic, space group Pnma and unit-cell parameters (synchrotron X-ray diffraction) are a = 7.2558(3), b = 27.992(1), c = 6.5243 (3) Å, V = 1325.10(8) Å3 , Z = 4. The crystal structure of karibibbite consists of bands of Fe3+O6 octahedra running along a framed by two chains of AsO3 trigonal pyramids at each side, and along c by As2O5 dimers above and below. Each band is composed of ribbons of three edge- sharing Fe3+O6 octahedra, apex-connected with other ribbons in order to form a kinked band running along a. The atoms As(2) and As(3), each showing trigonal pyramidal coordination by O, share the O(4) atom to form a dimer. In turn, dimers are connected by the O(3) atoms, defining a zig-zag chain of overall (As3+O2) n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2) n chains. The simultaneous presence of arsenite chains and dimers is previously unknown in compounds with As3+. The lone-electron pairs (4s2 ) of the As(2) and As(3) atoms project into the interlayer located at y = 0 and y = ½, yielding probable weak interactions with the O atoms of the facing (AsO2) chain. The DFT calculations show that the Fe atoms have maximum spin polarization, consistent with the Fe3+ state.
Fil: Colombo, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina
Fil: Mugnaioli, Enrico. Universita Degli Studi Di Siena; Italia
Fil: Vallcorba, Oriol. Experiments Division - Alba Synchrotron; España
Fil: García, Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España
Fil: Goñi, Alejandro. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España
Fil: Rius, Jordi. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España
Materia
ARSENITE
ELECTRON DIFFRACTION TOMOGRAPHY
LONE ELECTRON PAIR
DENSITY FUNCTIONAL THEORY CALCULATIONS
Nivel de accesibilidad
acceso embargado
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:11336/45892
Acceder
id CONICETDig_2ea1052105bf47c640e830666d0370b4
oai_identifier_str oai:ri.conicet.gov.ar:11336/45892
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomographyColombo, FernandoMugnaioli, EnricoVallcorba, OriolGarcía, AlbertoGoñi, AlejandroRius, JordiARSENITEELECTRON DIFFRACTION TOMOGRAPHYLONE ELECTRON PAIRDENSITY FUNCTIONAL THEORY CALCULATIONShttps://purl.org/becyt/ford/1.5https://purl.org/becyt/ford/1The crystal structure of karibibite, Fe3+3 (As3+O2)4(As3+2 O5)(OH), from the Urucum mine (Minas Gerais, Brazil), was solved and refined from electron diffraction tomography data [R1 = 18.8% for F > 4σ(F)] and further confirmed by synchrotron X-ray diffraction and density functional theory (DFT) calculations. The mineral is orthorhombic, space group Pnma and unit-cell parameters (synchrotron X-ray diffraction) are a = 7.2558(3), b = 27.992(1), c = 6.5243 (3) Å, V = 1325.10(8) Å3 , Z = 4. The crystal structure of karibibbite consists of bands of Fe3+O6 octahedra running along a framed by two chains of AsO3 trigonal pyramids at each side, and along c by As2O5 dimers above and below. Each band is composed of ribbons of three edge- sharing Fe3+O6 octahedra, apex-connected with other ribbons in order to form a kinked band running along a. The atoms As(2) and As(3), each showing trigonal pyramidal coordination by O, share the O(4) atom to form a dimer. In turn, dimers are connected by the O(3) atoms, defining a zig-zag chain of overall (As3+O2) n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2) n chains. The simultaneous presence of arsenite chains and dimers is previously unknown in compounds with As3+. The lone-electron pairs (4s2 ) of the As(2) and As(3) atoms project into the interlayer located at y = 0 and y = ½, yielding probable weak interactions with the O atoms of the facing (AsO2) chain. The DFT calculations show that the Fe atoms have maximum spin polarization, consistent with the Fe3+ state.Fil: Colombo, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; ArgentinaFil: Mugnaioli, Enrico. Universita Degli Studi Di Siena; ItaliaFil: Vallcorba, Oriol. Experiments Division - Alba Synchrotron; EspañaFil: García, Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; EspañaFil: Goñi, Alejandro. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; EspañaFil: Rius, Jordi. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; EspañaMineralogical Soc2017-10info:eu-repo/date/embargoEnd/2018-11-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/45892Colombo, Fernando; Mugnaioli, Enrico; Vallcorba, Oriol; García, Alberto; Goñi, Alejandro; et al.; Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography; Mineralogical Soc; Mineralogical Magazine; 81; 5; 10-2017; 1191-12020026-461X1471-8022CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1180/minmag.2016.080.159info:eu-repo/semantics/altIdentifier/url/https://bit.ly/2IITlWlinfo:eu-repo/semantics/embargoedAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:45:25Zoai:ri.conicet.gov.ar:11336/45892instacron: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:34982025-10-15 15:45:25.94CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
title Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
spellingShingle Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
Colombo, Fernando
ARSENITE
ELECTRON DIFFRACTION TOMOGRAPHY
LONE ELECTRON PAIR
DENSITY FUNCTIONAL THEORY CALCULATIONS
title_short Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
title_full Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
title_fullStr Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
title_full_unstemmed Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
title_sort Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography
dc.creator.none.fl_str_mv Colombo, Fernando
Mugnaioli, Enrico
Vallcorba, Oriol
García, Alberto
Goñi, Alejandro
Rius, Jordi
author Colombo, Fernando
author_facet Colombo, Fernando
Mugnaioli, Enrico
Vallcorba, Oriol
García, Alberto
Goñi, Alejandro
Rius, Jordi
author_role author
author2 Mugnaioli, Enrico
Vallcorba, Oriol
García, Alberto
Goñi, Alejandro
Rius, Jordi
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv ARSENITE
ELECTRON DIFFRACTION TOMOGRAPHY
LONE ELECTRON PAIR
DENSITY FUNCTIONAL THEORY CALCULATIONS
topic ARSENITE
ELECTRON DIFFRACTION TOMOGRAPHY
LONE ELECTRON PAIR
DENSITY FUNCTIONAL THEORY CALCULATIONS
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.5
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The crystal structure of karibibite, Fe3+3 (As3+O2)4(As3+2 O5)(OH), from the Urucum mine (Minas Gerais, Brazil), was solved and refined from electron diffraction tomography data [R1 = 18.8% for F > 4σ(F)] and further confirmed by synchrotron X-ray diffraction and density functional theory (DFT) calculations. The mineral is orthorhombic, space group Pnma and unit-cell parameters (synchrotron X-ray diffraction) are a = 7.2558(3), b = 27.992(1), c = 6.5243 (3) Å, V = 1325.10(8) Å3 , Z = 4. The crystal structure of karibibbite consists of bands of Fe3+O6 octahedra running along a framed by two chains of AsO3 trigonal pyramids at each side, and along c by As2O5 dimers above and below. Each band is composed of ribbons of three edge- sharing Fe3+O6 octahedra, apex-connected with other ribbons in order to form a kinked band running along a. The atoms As(2) and As(3), each showing trigonal pyramidal coordination by O, share the O(4) atom to form a dimer. In turn, dimers are connected by the O(3) atoms, defining a zig-zag chain of overall (As3+O2) n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2) n chains. The simultaneous presence of arsenite chains and dimers is previously unknown in compounds with As3+. The lone-electron pairs (4s2 ) of the As(2) and As(3) atoms project into the interlayer located at y = 0 and y = ½, yielding probable weak interactions with the O atoms of the facing (AsO2) chain. The DFT calculations show that the Fe atoms have maximum spin polarization, consistent with the Fe3+ state.
Fil: Colombo, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina
Fil: Mugnaioli, Enrico. Universita Degli Studi Di Siena; Italia
Fil: Vallcorba, Oriol. Experiments Division - Alba Synchrotron; España
Fil: García, Alberto. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España
Fil: Goñi, Alejandro. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España
Fil: Rius, Jordi. Consejo Superior de Investigaciones Científicas. Instituto de Ciencia de los Materiales de Barcelona; España
description The crystal structure of karibibite, Fe3+3 (As3+O2)4(As3+2 O5)(OH), from the Urucum mine (Minas Gerais, Brazil), was solved and refined from electron diffraction tomography data [R1 = 18.8% for F > 4σ(F)] and further confirmed by synchrotron X-ray diffraction and density functional theory (DFT) calculations. The mineral is orthorhombic, space group Pnma and unit-cell parameters (synchrotron X-ray diffraction) are a = 7.2558(3), b = 27.992(1), c = 6.5243 (3) Å, V = 1325.10(8) Å3 , Z = 4. The crystal structure of karibibbite consists of bands of Fe3+O6 octahedra running along a framed by two chains of AsO3 trigonal pyramids at each side, and along c by As2O5 dimers above and below. Each band is composed of ribbons of three edge- sharing Fe3+O6 octahedra, apex-connected with other ribbons in order to form a kinked band running along a. The atoms As(2) and As(3), each showing trigonal pyramidal coordination by O, share the O(4) atom to form a dimer. In turn, dimers are connected by the O(3) atoms, defining a zig-zag chain of overall (As3+O2) n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2) n chains. The simultaneous presence of arsenite chains and dimers is previously unknown in compounds with As3+. The lone-electron pairs (4s2 ) of the As(2) and As(3) atoms project into the interlayer located at y = 0 and y = ½, yielding probable weak interactions with the O atoms of the facing (AsO2) chain. The DFT calculations show that the Fe atoms have maximum spin polarization, consistent with the Fe3+ state.
publishDate 2017
dc.date.none.fl_str_mv 2017-10
info:eu-repo/date/embargoEnd/2018-11-01
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/11336/45892
Colombo, Fernando; Mugnaioli, Enrico; Vallcorba, Oriol; García, Alberto; Goñi, Alejandro; et al.; Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography; Mineralogical Soc; Mineralogical Magazine; 81; 5; 10-2017; 1191-1202
0026-461X
1471-8022
CONICET Digital
CONICET
url http://hdl.handle.net/11336/45892
identifier_str_mv Colombo, Fernando; Mugnaioli, Enrico; Vallcorba, Oriol; García, Alberto; Goñi, Alejandro; et al.; Crystal structure determination of karibibite, an Fe3+ arsenite, using electron diffraction tomography; Mineralogical Soc; Mineralogical Magazine; 81; 5; 10-2017; 1191-1202
0026-461X
1471-8022
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1180/minmag.2016.080.159
info:eu-repo/semantics/altIdentifier/url/https://bit.ly/2IITlWl
dc.rights.none.fl_str_mv info:eu-repo/semantics/embargoedAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv embargoedAccess
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 Mineralogical Soc
publisher.none.fl_str_mv Mineralogical Soc
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 13.22299

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