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

Published online by Cambridge University Press:  02 January 2018

Fernando Colombo ,
Enrico Mugnaioli ,
Oriol Vallcorba ,
Alberto García ,
Alejandro R. Goñi  and
Jordi Rius
Fernando Colombo*
Affiliation:
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, E-08193 Bellaterra, Catalonia, Spain
Enrico Mugnaioli
Affiliation:
Dipartimento di Scienze Fisiche, della Terra e dell’Ambiente. Università degli Studi di Siena. Via Laterino 8, 53100, Siena, Italy Centre for Nanotechnology Innovation@NEST, Istituto Italiano di Tecnologia, Piazza San Silvestro 12, 56127, Pisa, Italy
Oriol Vallcorba
Affiliation:
Experiments Division - MSPD Beamline (BL04. ALBA Synchrotron Light Source – CELLS. Crta BP 1413 Km 3.3, 08290 Cerdanyola del Vallès, Barcelona, Spain
Alberto García
Affiliation:
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, E-08193 Bellaterra, Catalonia, Spain
Alejandro R. Goñi
Affiliation:
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, E-08193 Bellaterra, Catalonia, Spain ICREA, Passeig Lluís Companys 23, 08010 Barcelona, Spain
Jordi Rius
Affiliation:
Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), Campus UAB, E-08193 Bellaterra, Catalonia, Spain
*
*E-mail: [email protected]
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Abstract

The crystal structure of karibibite, Fe33+(As3+O2)4(As23+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-n stoichiometry. Each ribbon of (Fe3+O6) octahedra is flanked on both edges by the (As3+O2)n-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.

Keywords

karibibitestructurearseniteelectron diffraction tomographylone electron pairdensity functional theory calculationsUrucum mine
Type
Research Article
Information
Mineralogical Magazine , Volume 81 , Issue 5 , October 2017 , pp. 1191 - 1202
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2017

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Footnotes

§

Permanent address: CICTERRA-CONICET. FCEFyN – Universidad Nacional de Córdoba. Av. Vélez Sarsfield 1611 (X5016GCA) Córdoba, Argentina

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