ChemInform Abstract: NIOBIUM‐NICKEL‐PHOSPHORUS SYSTEM

Lomnitskaya, Ya. F.; Kuz’ma, Yu. B.

doi:10.1002/chin.198351016

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“…In this structure, P is located in a trigonal Nb 4 Ni 2 prism, capped by one Ni and two Nb atoms. The only phosphide known today in the Nb/Ni/P system with a Nb/(Ni + P) ratio between 3/2 and 1/1 is Nb 3 Ni 2 P, which structure has been reported as of the U 3 Si 2 type with mixed Nb/Ni occupancies on one site and mixed Ni/P occupancies on the interstitial site, coordinated by Nb in a trigonal prism. This shows that it is possible to find Ni and P together on interstitial trigonal prismatic coordinated positions in Nb compounds; however, we have not been able to prepare any new niobium nickel phosphides with structures similar to those of M 2 NiP (M = Zr, Hf), Zr 9 Ni 2 P 4 , or Hf 5 NiP 3 .…”

Section: Resultsmentioning

confidence: 99%

Novel Quaternary Metal-Rich Phosphides: Stabilization by Differential Fractional Site Occupancies and Polar Intermetallic Bonding

Kleinke

Franzen

1997

J. Am. Chem. Soc.

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The new phosphide Hf5Nb5Ni3P5 has been prepared by arc-melting of a pressed stoichiometric mixture of HfP, Nb, and Ni. Single crystals suitable for the structure determination were obtained after annealing in an induction furnace at 1350 °C. Hf5Nb5Ni3P5 crystallizes in the hexagonal space group P6̄2m (No. 189). The early transition metal atoms Hf and Nb are found on three crystallographically different sites, with refined occupancies of 100% Hf for the M1, 59.5(4)% Hf and 40.5(4)% Nb for the M2, and 13.1(6)% Hf and 86.9(6)% Nb for the M3 site. Small variations of the Hf to Nb ratio are possible, occurring with significantly different lattice parameters. The early transition elements form a three-dimensional framework with numerous M−M (M = Hf, Nb) interactions, including Ni and P in its trigonal prismatic voids. The differential fractional site occupancies can be understood on the basis of the different preferences of Hf and Nb to form M−M, M−Ni, and M−P bonds. The metallic character is confirmed by the Pauli paramagnetism experimentally obtained.

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Section: Resultsmentioning

confidence: 99%