The reaction of [(CpFe)-Fe-Bn(eta(5)-P-5)] (1) (Cp-Bn = eta(5)-C-5(CH2Ph)(5)) with CuI selectively yields a novel spherical supramolecule (CH2Cl2)3.4@[((CpFeP5)-Fe-Bn)(12){CuI}(54)(MeCN)(1.46)] (2) showing a linkage of the scaffold atoms which is beyond the Fullerene topology. Its extended CuI framework reveals an outer diameter of 3.7 nm-a size that has not been reached before using five-fold symmetric building blocks. Furthermore, 2 shows a remarkable solubility in CH2Cl2, and NMR spectroscopy reveals that the scaffold of the supramolecule remains intact in solution. In addition, a novel 2D polymer [{(CpFe)-Fe-Bn(eta(5)-P-5)}2{Cu-6(mu-I)2(mu(3)-I)4}](n) (3) with an uncommon structural motif was isolated. Its formation can be avoided by using a large excess of CuI in the reaction with 1.