The contribution of silaalkylphosphonic acids Me3SiCH2P(O)(OH)(2) (1) and Me3SiC(CH3)(2)P(O)(OH)(2) (2) as ligands was demonstrated for the first time by the isolation of new diorganotin(IV) phosphonates Et2Sn{OP-(O)(OH)CH2SiMe3}(OSO2Me) (3), (Et2Sn)(6){O3PC-(CH3)(2)SiMe3}(4)(OSO2Me)(4) (4), and Et2Sn(O3PCH2SiMe3) (5). X-ray crystallographic studies of 1-4 are presented. The structures of 1 and 2 adopt extended motifs by virtue of P-OH center dot center dot center dot O=P-type hydrogen bonding interactions. The molecular structure of 3 is composed of a dimer formed by bridging hydrogen phosphonate groups, while the sulfonate group appended on each tin atom acts in a mu(2)-bridging mode to afford the formation of one-dimensional coordination polymer featuring alternate eight-membered [-Sn-O-P-O-](2) and [-Sn-O-S-O](2) rings. The asymmetric unit of 4 is composed of two crystallographically unique trinuclear tin phosphonate clusters with a Sn-3(mu(3)-PO3)(2) core linked together by coordinative association of a mu(2)-sulfonate group, while the remaining sulfonates are involved in the construction of a two-dimensional self-assembly. The identity of 1-5 in solution was established by IR and multinuclear (H-1, C-13, P-31, Sn-119) NMR spectroscopy. The presence of silaalkyl group in 5 imparts unusual solubility in hydrocarbon, aromatic, and ether solvents. As a consequence, the formation of colloidal particles of 5 featuring rodlike morphology was achieved by ultrasonication of a solution in ethanol-chloroform mixture.