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dc.contributor.authorSchumer, Benjamin N.
dc.contributor.authorAndrade, Marcelo B.
dc.contributor.authorEvans, Stanley H.
dc.contributor.authorDowns, Robert T.
dc.date.accessioned2017-04-07T21:22:47Z
dc.date.available2017-04-07T21:22:47Z
dc.date.issued2017-01-03
dc.identifier.citationA new formula and crystal structure for nickelskutterudite, (Ni,Co,Fe)As 3 , and occupancy of the icosahedral cation site in the skutterudite group 2017, 102 (1):205 American Mineralogisten
dc.identifier.issn0003-004X
dc.identifier.doi10.2138/am-2017-5615
dc.identifier.urihttp://hdl.handle.net/10150/623060
dc.description.abstractWe 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) As-3, cubic, Im (3) over bar, Z = 8: a = 8.2653(6) angstrom, V = 564.65(7) angstrom, has been refined to R-1 = 1.4% for 225 unique reflections I > 2 sigma(1) collected on a Bruker X8 four-circle diffractometer equipped with fine-focus, sealed tube MoKa 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 angstrom. The extreme tilting of BAs6 octahedra is likely a consequence of the As-As bonding. The nickelskutterudite structure differs from the ideal perovskite structure (A(4)B(4)X(12)) 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 (AB(4)X(12)). Electron microprobe analyses of nickelskutterudite gave an empirical chemical formula of (Ni0.62Co0.28Fe0.12)(Sigma 1.02)(AS(2.95)S(0.05))(Sigma 3.00) 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)As-3.
dc.description.sponsorshipFreeport McMoRan; Mineralogical Society of America Krauss Crystallographic Research Grant; Brazilian government [FAPESP 2013/03487-8]en
dc.language.isoenen
dc.publisherMINERALOGICAL SOC AMERen
dc.relation.urlhttp://ammin.geoscienceworld.org/lookup/doi/10.2138/am-2017-5615en
dc.rights© 2017 Mineralogical Society of Americaen
dc.subjectSkutteruditeen
dc.subjecticosahedral metal siteen
dc.subjectcobalten
dc.subjectnickelen
dc.subjectoctahedral tilten
dc.titleA new formula and crystal structure for nickelskutterudite, (Ni,Co,Fe)As-3, and occupancy of the icosahedral cation site in the skutterudite groupen
dc.typeArticleen
dc.contributor.departmentDepartment of Geosciences, University of Arizonaen
dc.identifier.journalAmerican Mineralogisten
dc.description.note12 month embargo; First Published on January 03, 2017en
dc.description.collectioninformationThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at repository@u.library.arizona.edu.en
dc.eprint.versionFinal accepted manuscripten
refterms.dateFOA2018-01-04T00:00:00Z
html.description.abstractWe 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) As-3, cubic, Im (3) over bar, Z = 8: a = 8.2653(6) angstrom, V = 564.65(7) angstrom, has been refined to R-1 = 1.4% for 225 unique reflections I > 2 sigma(1) collected on a Bruker X8 four-circle diffractometer equipped with fine-focus, sealed tube MoKa 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 angstrom. The extreme tilting of BAs6 octahedra is likely a consequence of the As-As bonding. The nickelskutterudite structure differs from the ideal perovskite structure (A(4)B(4)X(12)) 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 (AB(4)X(12)). Electron microprobe analyses of nickelskutterudite gave an empirical chemical formula of (Ni0.62Co0.28Fe0.12)(Sigma 1.02)(AS(2.95)S(0.05))(Sigma 3.00) 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)As-3.


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