Elucidating the natural–synthetic mismatch of Pb2+Te4+O3: The redefinition of fairbankite to    P b   12   2 +        T e   4 +     O   3      11      S O   4

Owen P. Missen; Michael S. Rumsey; Stuart J. Mills; Matthias Weil; Jens Najorka; John Spratt; Uwe Kolitsch

doi:10.2138/am-2020-7536

Published by De Gruyter January 29, 2021

Elucidating the natural–synthetic mismatch of Pb²⁺Te⁴⁺O₃: The redefinition of fairbankite to P b 12 2 + T e 4 + O 3 11 S O 4

Owen P. Missen , Michael S. Rumsey , Stuart J. Mills , Matthias Weil , Jens Najorka , John Spratt and Uwe Kolitsch

From the journal American Mineralogist

https://doi.org/10.2138/am-2020-7536

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Abstract

For four decades fairbankite was reported to have the formula Pb²⁺(Te⁴⁺O₃), but repeated attempts to isolate fairbankite crystals for structural determination found only the visually similar cerussite and, more rarely, anglesite. The crystal-structure determination of fairbankite using single-crystal X‑ray diffraction, supported by electron microprobe analysis and X‑ray powder diffraction on the type specimen, has shown that fairbankite contains essential S, along with Pb, Te, and O. The chemical formula of fairbankite has been revised to P b 12 2 + T e 4 + O 3 11 S O 4 . This change has been accepted by the IMA–CNMNC, Proposal 19-I. The crystal structure of fairbankite [space group P1 (no. 1); revised cell: a = 7.0205(3) Å, b = 10.6828(6) Å, c = 14.4916(8) Å, a = 75.161(5)°, b = 81.571(4)°, g = 83.744(4)°, V = 1036.35(9) Å³, and Z = 1] is the first atomic arrangement known to contain a T e 3 4 + O 9 6 − non-cyclic, finite building unit. Fairbankite has an average structure, formed from a 3D framework of Pb²⁺O_n polyhedra, Te⁴⁺O_n polyhedra, and SO₄ tetrahedra in a 12:11:1 ratio. The stereoactive lone pairs of the Pb²⁺ and Te⁴⁺ cations are oriented into void space within the structure. Fairbankite contains two mixed sites statistically occupied by Te⁴⁺ and S⁶⁺ in approximately 4:1 and 1:4 ratios. These two sites possess Te⁴⁺ in trigonal-pyramidal environment and S⁶⁺ in tetrahedral environment (with an additional O site to create tetrahedral SO₄ shape for the S-dominant site). Six of the 10 fully occupied Te⁴⁺ sites have Te⁴⁺ in trigonal-pyramidal environment, while four have Te⁴⁺ at the center of highly distorted Te⁴⁺O₄ disphenoids. The disphenoids allow for the creation of two dimeric T e 2 4 + O 6 4 − units in addition to the T e 3 4 + O 9 6 − trimeric unit, which contains two disphenoids. All linkage between disphenoids and trigonal pyramids is via corner-linking. Secondary connectivity is via long Te–O and Pb–O bonds.

Keywords: Lead tellurite; fairbankite; redefinition; crystal structure; tellurium oxysalt; average structure; Tombstone; Arizona; U.S.A

Acknowledgments and Funding

We thank two anonymous reviewers and the technical editor for their insightful comments, which improved the manuscript. This study has been partly funded by The Ian Potter Foundation grant “tracking tellurium” to S.J.M. Microprobe work was funded through Natural Environment Research Council grant NE/M010848/1 “Tellurium and Selenium Cycling and Supply” to Chris J. Stanley (Natural History Museum, London). Support funding has also been provided to OPM by an Australian Government Research Training Program (RTP) Scholarship, a Monash Graduate Excellence Scholarship (MGES) and a Robert Blackwood Monash–Museums Victoria scholarship. Mark D. Welch (Natural History Museum, London) is thanked for his assistance with the absorption correction processes. We acknowledge Joël Brugger (Monash University) for his insightful comments. Paul W. Pohwat (Smithsonian Institution) and Cristiano Ferraris (MNHN Paris) are thanked for their help with providing cataloged fairbankite specimens.

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Received: 2020-04-01

Accepted: 2020-07-03

Published Online: 2021-01-29

Published in Print: 2021-02-23

Elucidating the natural–synthetic mismatch of Pb²⁺Te⁴⁺O₃: The redefinition of fairbankite to P b 12 2 + T e 4 + O 3 11 S O 4

Abstract

Acknowledgments and Funding

References cited

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