Hydroxido-bridged dinuclear monoorganostannoxane [(RSnIV)2(μ-OH)(μ-OMe)Cl4]·CH3OH (R = 2-phenylazophenyl) (1) was obtained by the reaction of RSnCl3 (R = 2-phenylazophenyl) with sodium hydroxide in a stoichiometric ratio of acetone/methanol (1:1) at room temperature. Compound 1 crystallizes in the monoclinic space group Cc. The partial hydrolysis of RSnCl3 is accompanied by the substitution of two chlorides by one hydroxido and one methoxy ligand. The molecular structure of 1 contains two tin centers in distorted octahedral geometry which are bridged by hydroxido and methoxy ligands. In addition, single-crystal X-ray diffraction analysis of 1 revealed the formation of 1-D and 2-D supramolecular architectures because of the intermolecular hydrogen bonding and CH···πinteractions. Density functional theory studies suggested that the major transitions occurring in 1 involves ligand to ligand transitions. The reduced species calculations on compound 1 results are compatible to show the negative differential resistance (NDR) effect in this molecule. The I-V characteristic studies of a device made using compound 1 revealed that it exhibits very interesting NDR behavior in the region of 1.5-2.5 V. ©