Synthesis and structure of [K(+)-(2,2)diaza-[18]-crown-6][K3Ge9]-2ethylenediamine: stabilization of the...

Large bright-red, transparent crystalline plates of [K-(2,2)diaza-[18]-crown-6]K3Ge9-2en are obtained, in high-yield, from a reaction of (2,2)diaza-[18]-crown-6 in toluene with a solution of K4Ge9/potassium metal (K) in ethylenediamine (en). The compound crystallizes in the monoclinic space group P2(1)/m (a = 10.740(1) A, b = 15.812(1) A, c = 12.326(1) A, beta = 114.74 degrees; Z = 2). The crystal structure of [K-(2,2)diaza-[18]-crown-6]K3Ge9-2en features two-dimensional [K3Ge9] layers formed by uncomplexed K(+) cations and Ge94(-) anions. The "not-so-bare" cluster compound features a unique Ge94(-) cluster that exhibits a slightly distorted C(2v) geometry that is closer to D(3h) than the expected C(4v). Use of noncryptand sequestering agents in the isolation of Ge cluster anions from en solutions opens new avenues in understanding important cation-anion interactions in the stability and reactivity of Zintl ions, as well as a viable route to isolating Zintl anions with higher charges per atom.