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The crystal structure of sarmientite, Fe2 3+ (AsO4)(SO4)(OH)·5H2O, solved ab initio from laboratory powder diffraction data

Published online by Cambridge University Press:  05 July 2018

F. Colombo ,
J. Rius ,
O. Vallcorba  and
E. V. Pannunzio Miner
F. Colombo*
Affiliation:
CONICET−CICTERRA. Cátedra de Mineralogía, Facultad de Ciencias Exactas, Físicas y Naturales, Universidad Nacional de Córdoba, Vélez Sarsfield 1611, (X5016GCA) Córdoba, Argentina
J. Rius
Affiliation:
CONICET−CICTERRA. Cátedra de Mineralogía, Facultad de Ciencias Exactas, Físicas y Naturales, Universidad Nacional de Córdoba, Vélez Sarsfield 1611, (X5016GCA) Córdoba, Argentina
O. Vallcorba
Affiliation:
CONICET−CICTERRA. Cátedra de Mineralogía, Facultad de Ciencias Exactas, Físicas y Naturales, Universidad Nacional de Córdoba, Vélez Sarsfield 1611, (X5016GCA) Córdoba, Argentina
E. V. Pannunzio Miner
Affiliation:
CONICET−CICTERRA. Cátedra de Mineralogía, Facultad de Ciencias Exactas, Físicas y Naturales, Universidad Nacional de Córdoba, Vélez Sarsfield 1611, (X5016GCA) Córdoba, Argentina
*
E-mail: fosfatos@yahoo.com.ar
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Abstract

The crystal structure of sarmientite, Fe2 3+ (AsO4)(SO4)(OH)·5H2O, from the type locality (Santa Elena mine, San Juan Province, Argentina), was solved and refined from in-house powder diffraction data (CuKα1,2 radiation). It is monoclinic, space group P21/n, with unit-cell dimensions a = 6.5298(1), b = 18.5228(4), c = 9.6344(3) Å, β = 97.444(2)º, V = 1155.5(5) Å3, and Z = 4. The structure model was derived from cluster-based Patterson-function direct methods and refined by means of the Rietveld method to R wp = 0.0733 (X2 = 2.20). The structure consists of pairs of octahedral-tetrahedral (Fe−As) chains at (y,z) = (0,0) and (½,½), running along a. There are two symmetry-independent octahedral Fe sites. The Fe1 octahedra share two corners with the neighbouring arsenate groups. Both individual chains are related by a symmetry centre and joined by two symmetry-related Fe2 octahedra. Each Fe2 octahedron shares three corners with double-chain polyhedra (O3, O4 with arsenate groups; the O8 hydroxyl group with the Fe1 octahedron) and one corner (O11) with the monodentate sulfate group. The coordination of the Fe2 octahedron is completed by two H2O molecules (O9 and O10). There is also a complex network of H bonds that connects polyhedra within and among chains. Raman and infrared spectra show that (SO4)2− tetrahedra are strongly distorted.

Keywords

arsenicsulfateRietveld refinementoctahedral-tetrahedral chainshydrogen bondingab initio structure solution
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 2 , April 2014 , pp. 347 - 360
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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