Complexes formed between 0·034 m dimethyltin dichloride solutions and Na-montmorillonite at pH 2·4 and 4·0 have been characterized using 119Sn Mössbauer spectroscopy, X-ray diffraction, infrared spectroscopy, thermogravimetric analysis and water sorption isotherms. The dominant exchange cation at pH 2·4 is Me2Sn2+ characterized by an isomer shift, δ, and quadrupole splitting, Δ values of 1·25 and 3·80 mm s−1, respectively. The major exchange cation at pH 4·0 is the dimer, [Me2SnOH]2
2+, (δ = 1·38, Δ = 3·34 mm s−1) although the monomer, Me2Sn(OH)+, (δ = 0·95, Δ = 3·29 mm s−1) is also present. These complexes have basal spacings of 15·0 and 16·0 Å, respectively, which are stable up to 200°C. Mössbauer spectroscopy has shown that these ions are converted to SnO2 via Me2SnO upon thermal degradation. The temperature at which these oxides appear coincides with the collapse of the basal spacing. Both complexes display BET Type IV isotherms for the adsorption of water, following thermal pretreatment at 150°C, but the complex prepared at pH 4·0 has a lower sorption capacity. Both complexes, contrary to the normal behaviour of layer-silicates, have a definite pore volume and no further uptake occurs when this is filled.