A Supramolecular Assembly of Organotin Complexes: Syntheses, Characterization and Crystal Structures of Organotin Complexes with meso ‐2,3‐Dimercaptosuccinic Acid

A series of two types of organotin complexes, namely [(R 3 Sn) 4 (dmsa)] (R = Ph 1 , PhCH 2 2 , CH 3 3 , n Bu 4 ; H 4 dmsa = meso ‐2,3‐dimercaptosuccinic acid) and [(R 2 Sn) 2 (dmsa)(Y)] · L (R = Ph, Y = 2H 2 O, L = H 2 O, Et 2 O 5 ; R = PhCH 2 6 ; R = CH 3 7 ; R = n Bu 8 ; R = n Bu, Y = 0.5MeOH 9 ) have been synthesized. All complexes were characterized by elemental analysis and FT‐IR and NMR ( 1 H, 13 C and 119 Sn) spectroscopy. Among them, the strucrtures of complexes 1 , 3 , 5 , and 9 were also determined by X‐ray crystallography. The structural analyses show that complexes 1 and 3 are tetranuclear triorganotin monomers, complex 5 is a dinuclear diphenyltin monomer, and complex 9 is a 3D di‐ n ‐butyltin coordination polymer with a metal‐organic framework structure. The supramolecular structure analyses reveal that the type of organic substituent attached to the tin atoms can apparently affect the supramolecular assembly: when the substituents attached to the tin atom are aromatic groups ( 1 and 5 ) the supramolecular structures are dominated by intermolecular π–π (C–H ··· π) weak interactions, whereas when the substituents attached to the tin atom are alkyl groups ( 3 and 9 ) the supramolecular structures are dominated by intermolecular Sn←X (X = S, O) coordination interactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)