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41Author    Wolfgang Jeitschko, Jörg Wallinda, MartinV. Dewalsky, Ulrich WortmannRequires cookie*
 Title    Preparation, Properties, and Structure of the Polyphosphides VM4P16, NbNi4P16, and WNi4P16  
 Abstract    The title compounds were prepared by reacting powders of the binary transition metal alloys with phosphorus in a tin melt. They crystallize with a monoclinic structure of space group C 2/c, which was determined from single-crystal X-ray data; VNi4P16: a = 1956.0(3), b = 565.9(1), c = 1106.6(2) pm, ß = 100.99(1)°, R -0.020 for 1904 structure factors and 97 variable parameters; NbNi4P16: a = 1973.0(3), b = 571.2(3), c = 1117.2(2) pm, ß = 100.74(1)°, R = 0.023 for 2431 F-values and 97 variables; WNi4P16: a = 1964.2(3), b = 568.3(2), c = 1109.3(2) pm,/? = 101.04(2)°, R = 0.031 for 371 F-values and 43 variables. The T atoms (T = V, Nb, W) have eight P neighbors, which form a slightly distorted square antiprism, and the Ni atoms have appro­ ximately octahedral P coordination. The P atoms form novel P8 units, which consist of 6 -mem-bered rings with a P2 side chain. Chemical bonding is discussed on the basis of classical two-electron bonds. A comparison of the interatomic distances suggests that the Fermi level cuts through a band formed by antibonding nickel-phosphorus states. A band structure is propos­ ed, which also rationalizes the metallic conductivity and the Pauli paramagnetism of the com­ pounds. 
  Reference    Z. Naturforsch. 48b, 1774—1780 (1993); received July 291993 
  Published    1993 
  Keywords    Crystal Structure, Magnetic Properties, Electrical Conductivity, Chemical Bonding, Transition Metal Polyphosphides 
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 TEI-XML for    default:Reihe_B/48/ZNB-1993-48b-1774.pdf 
 Identifier    ZNB-1993-48b-1774 
 Volume    48