4.7 Article

An Obscured or Nonexistent Binary Intermetallic, Co7Pr17, Its Existent Neighbor Co2Pr5, and Two New Ternaries in the System Co/Sn/Pr, CoSn3Pr1-x, and Co2-xSn7Pr3

Journal

CRYSTAL GROWTH & DESIGN
Volume 18, Issue 10, Pages 6273-6283

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acs.cgd.8b01141

Keywords

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Funding

  1. University of Cologne, Cologne, Germany
  2. Office of the Basic Energy Sciences, Materials Sciences Division, U.S. Department of Energy (DOE)
  3. Department of Chemistry at Iowa State University (ISU)
  4. DOE [DE-AC02-07CH11358]

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Four compounds are reported in this study. Co7Pr17 (10, cP96, P2(1)3, a = 13.4147(8) angstrom, Z = 4), either nonexistent or obscured in the Co/Pr phase diagram, has been obtained from a PrBr3 flux. With 29.2 mol % Co, it is close to Co2Pr5 (28.6 mol % Co, 2, C2Mn5 type of structure, mC28, C2/c, a = 16.5471(7) angstrom, b = 6.5107(3) angstrom, c = 7.1067(3) angstrom, beta = 96.230(3)degrees, Z = 4), existent in the Co/Pr phase diagram, produced by arc-melting of a stoichiometric mixture of the metals. The addition of the reactive metal tin to Co/Pr mixtures yielded two new ternary polar intermetallics, CoSn3Pr1-x (x = 0.04, 11, RuSn3La type, cP40, Pm(3) over barn, a = 9.587(3) angstrom, Z = 8) and Co2-xSn7Pr3 (x = 0.78, 12, Ni2-xSn7-yCe3 type, oC24, Cmmm, a = 4.5043(4) angstrom, b = 27.227(2) angstrom, c = 4.5444(3) angstrom, Z = 2). Electronic structure calculations reveal extensive heteroatomic Co-Pr interactions in the binaries with little homoatomic contributions. With tin as the third component in the ternaries, heteroatomic Co-Sn and Sn-Pr bonding interactions are dominant, following the sequence of coordination spheres around Co.

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