Trigonal-prismatische Nb6-Einheiten in Verbindungen des Typs A3[Nb6SBr17] (A = Tl,K, Cs)

Trigonal-prismatic Nb₆-Units in Compounds of the Type A₃[Nb₆SBr₁₇] (A = Tl, K, Cs) The new compounds A₃[Nb₆SBr₁₇] (A = Tl, K, Cs) were synthesized and their lattice parameters were calculated from indexed X-ray powder patterns. An intensity measurement based on a single-crystal of Tl₃[Nb₆SBr₁₇] was performed with an automatic four-circle diffractometer (a = 1704.9(1) pm, b = 1862.8(3) pm, c = 932.51(7) pm; β = 90.747(7)°, V_m = 445.9(3) cm³/mol; C2/c, Z = 4). The structure refinement confirmed consistency with the Rb₃[Nb₆SBr₁₇] structure, found previously. The comparison of both structures yielded no significant differences concerning the distances within the sulfur-centered Nb₆S cluster core. Extended Hückel calculations revealed a maximum of the niobium–niobium overlap populations for (the actual present number of) 14 electrons occupying metal–metal bonding states.