The first charge-neutral Lewis base adducts of tin(IV) tetraazide, [Sn(N3)4(bpy)], [Sn(N3)4(phen)] and [Sn(N3)4(py)2], and the salt bis{bis(triphenylphosphine)iminium} hexa(azido)stannate [(PPN)2Sn(N3)6] (bpy = 2,2'-bipyridine; phen = 1,10-phenanthroline; py = pyridine; PPN = N(PPh3)2) have been prepared using covalent or ionic azide-transfer reagents and ligand-exchange reactions. The azides were isolated on the 0.3 to 1 g scale and characterized by IR and NMR spectroscopies, microanalytical and thermal methods and their molecular structures determined by single-crystal XRD. All complexes have a distorted octahedral Sn[N]6 coordination geometry and possess greater thermal stability than their Si and Ge homologues. The nitrogen content of the adducts of up to 44% exceed any Sn(IV) compound known hitherto.