The coordination-driven self-assemblies of mixed-ligand dialkyltin derivatives, [(Et2Sn)(4) (O2P(OH)Me)(2)(O3PMe)(2)-OSO2Et)(2)center dot 2H(2)O](n) 1, [(Et2Sn)(3)(O3PMe)(2)(OSO2Me)(2)center dot CHCl3](n) 2, and [(Me2Sn)(3)(O3PBut)(2)(OSO2Me)(2)center dot 2CHCl(3)](n) 3 have been achieved by reacting the tin precursors, [R2Sn(OR1)(OSO2R1)](n) (R = Et, R-1 = Et (1a), Me (2a); R = Me, R-1 = Me (3a)) with an equimolar amount of methylphosphonic/t-butylphosphonic acid under mild conditions (rt, 8 h, CH2Cl2). These have been characterized by IR and multinuclear (H-1, C-13, P-31, and Sn-119) NMR spectroscopy as well as single crystal X-ray diffraction. The asymmetric unit of 1 is composed of a tetranuclear, Sn-4(mu(2)-PO2)(2)(mu(3)-PO3)(2) core bearing an appended ethanesulfonate group on each terminal tin (Sn2) atom and two P(OH)center dot center dot center dot O hydrogen bonded water molecules. The ladder-like structural motif thus formed is extended into one-dimensional polymeric chains by virtue of bridging bidentate mode of the sultonate groups. These chains are linked by O-H center dot center dot center dot O(S) hydrogen bonds involving H2O molecules and oxygen atoms of the sulfonate groups. The asymmetric units of 2 and 3 are composed of trinuclear tin clusters with a Sn-3(mu(3)-PO3)(2) core and two dangling methanesulfonate groups which are covalently bonded to the tin centers. The construction of three-dimensional self-assemblies is effected by variable bonding modes (mu(2), mu(3) in 2; mu(2) in 3) of the methanesulfonate groups. Both the structural motifs possess five- and six-coordinated tin atoms and form rectangular channels which are occupied by CHCl3 molecules.