The reactions of RSnCl3 [R = 2-(phenylazo)phenyl] with phosphonic acids, RPO3H2 (R = t-Bu, C6H 11) or (ArO)2PO2H (Ar = 4-NO2-C 6H5O) in refluxing THF afforded hexatin cages, [(RSn) 6(μ-OH)6(μ3-O)2(t-BuPO 3)4]·5THF (1), [(RSn)6(μ-OH) 6(μ3-O)2(C6H11PO 3)4]·THF (2) and [(RSn)6(μ-OH) 4(μ3-O)2{(NO2C6H 4O)PO3}4]·THF (3), respectively. On the other hand, the reactions of RSnCl3 with 1,1,2,3,3-pentamethylene phosphinic acid [cycPO2H] or Ph2P(O)OH under similar reaction conditions afforded trinuclear O-capped clusters [(RSn) 3(μ3-O) (μ2-OH)3 (μ-cycPO2)3] [cycPO2]·CH 3CN·H2O (4) and [(RSn) 3(μ3-O) (μ2-OH)3 (μ-Ph 2PO2)3] [Ph2PO2] ·CH3CN·CH2Cl2 (5) respectively. Molecular structures of 1-3 reveal that the intramolecular N→Sn coordination found in RSnCl3 is hemilabile; 1-3 do not contain such a feature and the tin atoms in these compounds are six coordinate, possessing a 1C, 5O coordination environment in a distorted octahedral geometry. The cage structures in 1-3, containing two trinuclear sub-units, are formed as a result of the coordination action of several ligands: 4 μ3- (η1η1η1)[RPO3] 2-, 2 μ3-O2- and 6 μ-OH. The molecular structures of 4-5 reveal them to be cationic trinuclear complexes where 3 tin and 4 oxygen atoms occupy the vertices of a distorted cube while one of the vertices is unoccupied. The molecular structures of 4-5 also reveal that the intramolecular N→Sn coordination present in RSnCl3 is absent in these compounds attesting to the hemilabile nature of this interaction. © 2014 The Royal Society of Chemistry.