By judicious selection of crystallization conditions, it has been possible to obtain the salts of a common building block, [(RNC)(4)Rh-1)(+), in single-crystal form suitable for X-ray diffraction. Salts that contain a single type of cation include deep green [(C6H11NC)(12)Rh-3(I)](SbF6)(3), deep green [(C6H11NC)(12)Rh-3(I)](AsF6)(3), and straw yellow [(C6H11NC)(8)(Rh2Cl2)-Cl-II](BF4)(2) (in addition to the previously isolated trimeric deep green [(i-PrNC)(12)Rh-3(I)]Cl(3 center dot)4.5H(2)O, monomeric, [(C6H11NC)(4) Rh-I](BPh4), and [(i-PrNC)(4)Rh-I](BPh4) (both yellow), and red, dimeric [(C6H11NC)(8)Rh-2(I)]Cl-2 center dot 0.5C(6)H(6)center dot 2H(2)O). Ordered crystals of [(C6H11NC)(12)Rh-3(I)](SbF6)(3) contain linear Rh-3 units, while those of [(C6H11NC)(12)Rh-3(I)](AsF6)(3) show disorder which is consistent with the presence of linear or bent Rh-3 units. The formation of green [(C6H11NC)(12)(Rh3Cl2)-Cl-V/III][(C6H11NC)(12)Rh-3(I)]Cl-6, and brown [(C6H11NC)(12)(Rh3Cl2)-Cl-V/III][(C6H11NC)(8)Rh-2(I)][(C6H11NC)(4)Rh-I]C l-6 center dot 16H(2)O center dot 3C(6)H(6) along with unidentified red-brown cubes from an air-exposed solution of [(C6H11NC)(4)Rh-I]Cl is reported. As their formulas indicate, green [(C6H11NC)(12)(Rh3Cl2)-Cl-V/III][(C6H11NC)(12)Rh-3(I)]Cl-6, and brown [(C6H11NC)(12)(Rh3Cl2)-Cl-V/III][(C6H11NC)(8)Rh-2(I)][(C6H11NC)(8)Rh-I]C l-6 center dot 16H(2)O center dot 3C(6)H(6) contain two or three chemically distinct cations, respectively, but again are built from a common precursor, [(C6H11NC)(4)Rh-I](+).