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A new formula and crystal structure for nickelskutterudite, (Ni,Co,Fe)As3, and occupancy of the icosahedral cation site in the skutterudite group

  • Benjamin N. Schumer EMAIL logo , Marcelo B. Andrade , Stanley H. Evans and Robert T. Downs
Published/Copyright: January 3, 2017
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American Mineralogist
From the journal American Mineralogist Volume 102 Issue 1

Abstract

We propose a new formula for the mineral nickelskutterudite, based on our observation that either (or both) Co or Fe3+ are essential structure constituents. The crystal structure of nickelskutterudite, (Ni,Co,Fe)As3, cubic, Im3¯,Z = 8: a = 8.2653(6) Å, V = 564.65(7) Å3, has been refined to R1 = 1.4% for 225 unique reflections I > 2σ(I) collected on a Bruker X8 four-circle diffractometer equipped with fine-focus, sealed tube MoKα radiation and an APEX-II CCD detector. This is the first report of the crystal structure of nickelskutterudite. Nickelskutterudite, a member of the skutterudite group of isostructural minerals, adopts a distorted perovskite structure with notably tilted octahedra and an unoccupied to partially occupied icosahedral metal site. In the structure of nickelskutterudite, there is one metal (B) site occupied by Ni, Co, or Fe in octahedral coordination with six As atoms. Procrystal electron density analysis shows each As anion is bonded to two cations and two As anions, resulting in a four-membered ring of bonded As with edges 2.547 and 2.475 Å. The extreme tilting of BAs6 octahedra is likely a consequence of the As-As bonding. The nickelskutterudite structure differs from the ideal perovskite structure (A4B4X12) in that As4 anion rings occupy three of the four icosahedral cages centered on the A sites. There are reported synthetic phases isomorphous with skutterudite with the other A site completely occupied by a cation (AB4X12).

Electron microprobe analyses of nickelskutterudite gave an empirical chemical formula of (Ni0.62Co0.28Fe0.12)Σ1.02(As2.95S0.05)Σ3.00 normalized to three anions. Pure NiAs3 nickelskutterudite, natural or synthesized, has not been reported. In nature, nickelskutterudite is always observed with significant Co and Fe, reportedly because all non-bonded valence electrons must be spin-paired. This suggests that nickelskutterudite must contain Co3+ and Fe2+, consistent with previous models since Ni4+ cannot spin-pair its seven non-bonded electrons, Co3+ and Fe2+, which can spin-pair all non-bonded electrons, are required to stabilize the structure. No anion deficiencies were found in the course of this study so, including the structurally necessary Co and Fe, the chemical formula of nickelskutterudite (currently given as NiAs3–x by the IMA) should be considered (Ni,Co,Fe)As3.

Keywords: Skutterudite; icosahedral metal site; cobalt; nickel; octahedral tilt

Acknowledgements

The authors gratefully acknowledge Ron Gibbs for kindly providing the nickelskutterudite sample to the RRUFF Project. Funding support for this study was given by Freeport McMoRan, the Mineralogical Society of America Krauss Crystallographic Research Grant, and M.B.A. acknowledges support by the Brazilian government (FAPESP 2013/03487-8).

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Received: 2015-11-27
Accepted: 2016-8-23
Published Online: 2017-1-3
Published in Print: 2017-1-1

© 2017 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2017-5615
Keywords for this article
Skutterudite; icosahedral metal site; cobalt; nickel; octahedral tilt

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Periodic activity in continental magmatic arcs
  3. Highlights and Breakthroughs
  4. Early warning signs for mining accidents: Detecting crackling noise
  5. Review
  6. Fluids and trace element transport in subduction zones
  7. Solved: The enigma of labradorite feldspar with incommensurately modulated structure
  8. Solved: The enigma of labradorite feldspar with incommensurately modulated structure
  9. Special Collection: Earth Analogs for Martian Geological Materials and Processes
  10. Formation of the ferruginous smectite SWa-1 by alteration of soil clays
  11. Special Collection: Advances in Ultrahigh-Pressure Metamorphism
  12. Dissolving dolomite in a stable UHP mineral assemblage: Evidence from Cal-Dol marbles of the Dora-Maira Massif (Italian Western Alps)
  13. Special collection: Apatite: a common mineral, uncommonly versatile
  14. Hydroxyl, Cl, and F partitioning between high-silica rhyolitic melts-apatite-fluid(s) at 50–200 MPa and 700–1000 °C
  15. Special collection: Apatite: a common mineral, uncommonly versatile
  16. Apatite trace element and isotope applications to petrogenesis and provenance
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  36. XAFS spectroscopic study of Ti coordination in garnet
  38. Effect of composition on compressibility of skiagite-Fe-majorite garnet
  40. An integrated EPMA-EBSD study of metamorphic histories recorded in garnet
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