A new method of syntheses of 18-membered macrocyclic diphenyltin(IV) compounds and crystal structures of {Ph2Sn[S(C6H3NO)O]}3·Y (Y = 2H2O or 4C6H6) and {Ph3Sn[S(C6H3NO)O]SnPh3(EtOH)}·[EtOH]
Two diphenyltin(IV) compounds: {Ph2Sn[S(C6H3NO)O]}3·Y (Y = 2H2O, 1; 4C6H6, 2) have been unexpectedly obtained by the reactions of triphenyltin chloride with 2-mercaptonicotinic acid in the presence of Et3N. However, by the reaction of the same reactants in the presence of EtONa, only a new triphenyltin(IV) compound ({Ph3Sn[S(C6H3NO)O]SnPh3(EtOH)}·[EtOH], 3) was obtained. The X-ray analyses reveal that compounds 1 and 2 are trinuclear, 18-membered macrocyclic compounds while 3 is a dinuclear compound. Specially, π-π stacking interaction was recognized in crystals of compound 1, which makes it a dimer. Co-crystallization was found in the crystals of all the three compounds 1, 2, and 3, the co-crystallized solvent molecules are water, benzene, and ethanol molecules, respectively. A possible dephenylation mechanism of 1 and 2 was illustrated in detail.Key words: triphenyltin, 2-mercaptonicotinic acid, dephenylation, macrocyclic, π-π stacking interaction, co-crystallization, crystal structure.