Structural Variety in the Pseudo‐ternary System M/Ge/I: ;alpha; ‐[NMe( n Bu) 3 ](GeI 4 )I, β ‐[NMe( n Bu) 3 ](GeI 4 )I and [ImMe( n Bu)][N( n Bu) 4 ](GeI 4 ) 3 I 2

By reaction of GeI 4 , [N( n Bu) 4 ]I as iodide donor, and [NMe( n Bu) 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( n Bu) 3 ](GeI 4 )I ( Pbca ; a = 1495.4(3) pm; b = 1940.6(4) pm; c = 3643.2(7) pm; Z = 16) and β ‐[NMe( n Bu) 3 ](GeI 4 )I ( Pn ; a = 1141.5(2) pm; b = 953.6(2) pm; c = 1208.9(2) pm; β = 100.8(1)°; Z = 2 ). Depending on the reaction temperature, the one or other compound is formed selectively. In addition, the reaction of GeI 4 and [N( n Bu) 4 ]I, using [ImMe( n Bu)][BF 4 ] (Im = imidazole) as ionic liquid, resulted in the crystallization of [ImMe( n Bu)][N( n Bu) 4 ](GeI 4 ) 3 I 2 ( P 2 1 / c ; a = 1641.2(3) pm; b = 1903.0(4) pm; c = 1867.7(4) pm; β = 92.0(1)°; Z = 4). The anionic network of all three compounds is established by molecular germanium(IV)iodide, which is bridged by iodide anions. The different connectivity of (GeI 4 –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).