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The influence of stereochemically active lone-pair electrons on crystal symmetry and twist angles in lead apatite-2H type structures

Published online by Cambridge University Press:  05 July 2018

T. Baikie ,
M. Schreyer ,
F. Wei ,
J. S. Herrin ,
C. Ferraris ,
F. Brink ,
J. Topolska ,
R. O. Piltz ,
J. Price  and
T. J. White
T. Baikie*
Affiliation:
Energy Research Institute @ NTU (ERI@N), Research Technoplaza, Nanyang Technological University, Nanyang Drive, 637553, Singapore
M. Schreyer
Affiliation:
Institute of Chemical & Engineering Sciences, 1 Pesek Road, Jurong Island, Singapore
F. Wei
Affiliation:
School of Materials Science and Engineering, Nanyang Technological University, Nanyang Avenue, 639798, Singapore
J. S. Herrin
Affiliation:
School of Materials Science and Engineering, Nanyang Technological University, Nanyang Avenue, 639798, Singapore Earth Observatory of Singapore, Nanyang Technological University, Nanyang Avenue, 639798, Singapore
C. Ferraris
Affiliation:
Laboratoire de Minéralogie et Cosmochimie du Muséum National d’Histoire Naturelle, UMR CNRS 7202, CP52, 61 Rue Buffon, 75005 Paris, France
F. Brink
Affiliation:
Centre for Advanced Microscopy, Australian National University, Canberra, ACT 0200, Australia
J. Topolska
Affiliation:
Department of Mineralogy, Petrography and Geochemistry, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059, Krakow, Poland
R. O. Piltz
Affiliation:
Bragg Institute, Australian Nuclear Science and Technology Organisation (ANSTO), Lucas Heights, NSW 2234, Australia
J. Price
Affiliation:
Australian Synchrotron Company Ltd, 800 Blackburn Rd, Clayton, VIC 3168, Australia
T. J. White
Affiliation:
School of Materials Science and Engineering, Nanyang Technological University, Nanyang Avenue, 639798, Singapore
*
E-mail: tbaikie@ntu.edu.sg
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Abstract

Lead-containing (Pb-B-X)-2H apatites encompass a number of [AF]4[AT]6[(BO4)6]X2 compounds used for waste stabilization, environmental catalysis and ion conduction, but the influence of the stereochemically active lone-pair electrons of Pb2+ on crystal chemistry and functionality is poorly understood. This article presents a compilation of existing structural data for Pb apatites that demonstrate paired electrons of Pb2+ at both the AF and AT results in substantial adjustments to the PbFO6 metaprism twist angle, φ. New structure refinements are presented for several natural varieties as a function of temperature by single-crystal X-ray diffraction (XRD) of vanadinite-2H (ideally Pb10(VO4)6Cl2), pyromorphite-2H (Pb10(PO4)6Cl2), mimetite-2H/M (Pb10(As5+O4)6Cl2) and finnemanite-2H (Pb10(As3+O3)6Cl2). A supercell for mimetite is confirmed using synchrotron single-crystal XRD. It is suggested the superstructure is necessary to accommodate displacement of the stereochemically active 6s2 lone-pair electrons on the Pb2+ that occupy a volume similar to an O2− anion. We propose that depending on the temperature and concentration of minor substitutional ions, the mimetite superstructure is a structural adaptation common to all Pb-containing apatites and by extension apatite electrolytes, where oxide ion interstitials are found at similar positions to the lonepair electrons. It is also shown that plumbous apatite framework flexes substantially through adjustments of the PbFO6 metaprism twist-angles (φ) as the temperature changes. Finally, crystalchemical [100] zoning observed at submicron scales will probably impact on the treatment of diffraction data and may account for certain inconsistencies in reported structures.

Keywords

Pb apatite structureslone-pair electronscrystal symmetrytwist angles
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 2 , April 2014 , pp. 325 - 345
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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