Direct Hydrolysis of Hydrated Organotin Cations:  Synthesis and Structural Characterization of {[<i>n</i>-Bu₂Sn(OH₂)(Phen)(O₃SC₆H₃-2,5-Me₂)]⁺[2,5-Me₂C₆H₃SO₃]^-} (Phen = 1,10-phenanthroline) and {[<i>n</i>-Bu₂Sn(μ-OH)(O₃SC₆H₃-2,5-Me₂)]₂}<i>_n</i>

Abstract

The reaction of {[ n -Bu 2 Sn(OH 2 ) 4 ] 2+ [2,5-Me 2 C 6 H 3 SO 3 - ] 2 } ( 2 ) with 1,10-phenanthroline affords {[ n -Bu 2 Sn(OH 2 )(Phen)(O 3 SC 6 H 3 -2,5-Me 2 )] + [2,5-Me 2 C 6 H 3 SO 3 ] - } ( 3 ) by the displacement of two water molecules by the chelating phenanthroline ligand and one water molecule by a sulfonate ligand. In contrast, 2 undergoes hydrolysis on treatment with pyridine, resulting in the formation of {[ n -Bu 2 Sn(μ-OH)(O 3 SC 6 H 3 -2,5-Me 2 )] 2 } n ( 4 ). Formation of 4 also occurs in the reaction of 3 with pyridine as well as in a 1:1 reaction of [ n -Bu 2 SnO] n with 2,5-Me 2 C 6 H 3 SO 3 H·2H 2 O. The molecular structure of 3 contains a six-coordinate tin with a coordination environment comprising the chelating phenanthroline ligands, two butyl substituents, one water molecule, and one sulfonate ligand. Extensive hydrogen-bonding interactions (O−H- - -O, C−H- - -O, and O- - -π) in the crystal structure result in the formation of a three-dimensional supramolecular architecture for 3 . The crystal structure of 4 reveals that it is a two-dimensional coordination polymer. The basic repeat unit of the coordination polymer contains a [Sn(μ-OH)] 2 distannoxane ring. Anisobidentate coordination action of the sulfonate ligand results in the generation of 20-membered macrocycles, which are linked to each other to form the two-dimensional coordination polymer network.