In contrast to the reactions of Sn(NMe2)(2) with unfunctionalized primary amines (RNH2), which yield the simple imido Sn-II cubanes [SnNR](4), the reactions of 2-pyridyl or 2-pyrimidinyl amines give the mixed-oxidation-state Sn-II/ Sn-IV double cubanes [Sn-7(NR)(8)]. In addition to [Sn-7{2-N(5-Mepy}(8)](.)2thf (1(.)2thf) (py = pyridine) and [Sn-7{2N(pm)}(8)](.)0.33thf (2(.)0.33thf) (pm = pyrimidine), which were communicated previously, the syntheses and structures of the new complexes [Sn-7{2-N(4-Mepm)}(8)](.)2thf (3(.)2thf), [Sn-7{2-N(4,6-Me2Pm)}(8)](.)4thf (4(.)4thf), [Sn-7{2-N(4-Me-6-MeO-pm) }(8)] (5), and [Sn-7{2-N(4-MeO-6-MeO-pm)}(8)] (6) are reported. Model DFT calculations on the reactions of Sn(NMe2)(2) with 2-pmNH(2) or PhNH2, producing the cubanes [Sn{2-1N(pm)}](4) and [SnNPh](4) (respectively), and the corresponding double cubanes [Sn-7{2-N(pm)}(8)] and [Sn-7(NPh)(8)], show that the presence of intramolecular (SnN)-N-... bonding which spans the cubane halves of the complexes is crucial to the formation of the double-cubane structure.