Diethyltin(methoxy) methanesulfonate reacts readily with equimolar amount of t-butylphosphonic acid (RT, 8-10 h) in moist dichloromethane and methanol to afford [(Et2Sn)(6)(O3PBut)(4)(OSO2Me)(4)center dot CH2Cl2](n) (1) and [(Et2Sn)(6)(O3PBut)(4)center dot(OSO2Me)(4)center dot 2H(2)O](n) (2), respectively. The identity of these compounds has been established by IR, multinuclear (H-1, C-13, P-31 and Sn-119) NMR as well as X-ray crystallographic studies. Despite apparent similarity in the composition, a marked difference in the structural motifs between 1 and 2 is evident in the solid state. For 1, the formation of three-dimensional self-assembly results from mu(3)-phosphonate and mu(2), mu(3)-sulfonate binding modes and exhibits continuous channel of voids which are occupied by disordered CH2Cl2 molecules. In contrast, the sulfonate ligands in 2 act exclusively in mu(2)-fashion and hydrogen bonding interactions (O-H center dot center dot center dot O) between coordinated water molecules and methanesulfonate groups is significant in the construction of 3D supramolecular assembly. (C) 2011 Elsevier B. V. All rights reserved.