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

The reaction of {[n-Bu2Sn(OH2)4]2+[2,5-Me2C6H3SO3-]2} (2) with 1,10-phenanthroline affords {[n-Bu2Sn(OH2)(Phen)(O3SC6H3-2,5-Me2)]+[2,5-Me2C6H3SO3]-} (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-Bu2Sn(μ-OH)(O3SC6H3-2,5-Me2)]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-Bu2SnO]n with 2,5-Me2C6H3SO3H·2H2O. 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.