Mixed-ligand diorganotin esters, [R2Sn(OP(O)(OH)Ph)(OS(O)(2)R-1)](n) [R = n-Bu, R-1 = Me (1), n-Pr (2); R = Et, R-1 = Me (3)], have been synthesized by reacting the tin precursors, R2Sn(OR1)OS(O)(2)R-1 with an equimolar amount of phenylphosphonic acid under mild conditions (room temperature, 6-8 h, CH2Cl2). These have been characterized by IR, multinuclear (H-1, C-13{H-1}, P-31, and Sn-119) NMR, and single crystal X-ray diffraction studies. The asymmetric unit of 1 is comprised of a tetramer with four crystallographically unique tin atoms. The structure reveals a central eight-membered (Sn-O-S-O)(2) cyclic ring with two exocyclic tin atoms, which results from mu(3)-binding of the two methanesulfonate groups. The remaining two sulfonates are monodentate and contribute in O center dot center dot center dot HO(P) hydrogen bonding. The molecular structure is extended into a 3D coordination polymer with the aid of hydrogenphenylphosphonate group on each tin atom, acting in a mu(2)-O2P mode and forms a series of eight-membered (Sn-O-P-O)(2) rings in the structural framework. 2 and 3 are isostructural and represent linear 1D coordination polymers via, mu(2)-binding mode of both alkanesulfonate and hydrogenphenylphosphonate groups.