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  • Title: Synthesis and characterization of transition-metal zintl phases: K(10)NbInAs(6) and K(9)Nb(2)As(6).
    Author: Gascoin F, Sevov SC.
    Journal: Inorg Chem; 2003 Feb 10; 42(3):904-7. PubMed ID: 12562206.
    Abstract:
    The two title compounds were prepared by direct reactions of the corresponding elements at high temperature. The structures were determined by single-crystal X-ray diffraction: K(10)NbInAs(6), monoclinic, P2(1)/n, Z = 2, a = 9.107(1) A, b = 8.2878(8) A, c = 15.139(1) A, beta = 91.112(9) degrees; K(9)Nb(2)As(6), monoclinic, P2(1)/c, Z = 2, a = 9.348(1) A, b = 9.113(1) A, c = 12.798(1) A, beta = 95.98(1) degrees. They contain isolated dimers made of edge-sharing tetrahedra of [NbAs(4)] and [InAs(4)] in the former, NbInAs(6)(10)(-), and only [NbAs(4)] in the latter, Nb(2)As(6)(9)(-). Magnetic measurements show that K(10)NbInAs(6) is diamagnetic, i.e., a d(0) transition-metal Zintl phase, while K(9)Nb(2)As(6) exhibits a Curie-Weiss behavior consistent with the presence of one unpaired electron. The latter defines K(9)Nb(2)As(6) as a mixed-valence (presumably of type III) transition-metal Zintl phase, only the third example of such phases.
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