Structural Variety in the Pseudo-ternary System M/Ge/I: alpha-[NMe(nBu)(3)](GeI4)I, beta-[NMe(nBu)(3)](GeI4)I and [ImMe(nBu)][N(nBu)(4)](GeI4)(3)I-2

By reaction of GeI4, [N(nBU)(4)]1 as iodide donor, and [NMe(nBu)(3)][N(Tf)(2)] as ionic liquid, reddish-black, plate-like shaped crystals are obtained. X-ray diffraction analysis of' single crystals resulted in the compositions alpha-[NMe(nBu)(3)](GeI4)I (Pbca; a = 1495.4(3) pm; b = 1940.6(4) pm; c = 3643.2(7) pm; Z = 16) and beta-[NMe(nBu)(3)](GeI4)I (Pn; a = 1141.5(2) pm; b = 953.6(2) pm; c = 1208.9(2) pm; beta = 100.8(1)degrees; Z = 2). Depending on the reaction temperature, the one or other compound is formed selectively In addition, the reaction of GeI4 and [N(nBu)(4)]I, using [ImMe(nBu)][BF4] (Im = imidazole) as ionic liquid, resulted in the crystallization of [ImMe(nBu)][N(nBu)(4)](GeI4)(3)I-2 (P2(1)/c; a = 1641.2(3) pm; b = 1903.0(4) pm; c = 1867.7(4) pm, beta = 92.0(1)degrees; Z = 4). The anionic network of all three compounds is established by molecular gemanium(IV)iodide, which is bridged by iodide anions. The different connectivity of (GeI4-I-) networks is attributed to the flexibility of I- regarding its coordination and bond length. Here, a [3+1]-, 4- and 5-fold coordination is first observed in the pseudo-ternary system M/Ge/I (M: cation).