Five new thiosulfate based inorganic-organic hybrid open-framework compounds have been synthesized employing mild reaction conditions. Of the five compounds, [Na2(H2O)8][Cd(C10H 8N2)(S2O3)2] ·2H2O, I and [Cd2(C10H8N 2)2(HS2O3)2(S 2O3)2][(C10H9N 2)2(C10H8N2) 2]·8H2O, II have one-dimensional (1D) structures and [Cd(C10H8N2)(H2O) 2(S2O3)]·2H2O, III, [Cd 2(C10H8N2)3(S 2O3)2], IV and [Cd2(C 10H8N2)2.5(S2O 3)2], V have three-dimensional (3D) structures. The 1D structures are somewhat related, formed by the bonding between tetrahedral Cd centers (CdN2S2) and 4,4′-bipyridine (bpy) units. The inter-chain spaces are occupied by the hanging thiosulfate units in both the cases along with Na(H2O)6 chains in I and free bpy units in II. The three 3D structures have one-dimensional cadmium thiosulfate chains linked by bpy units. Interpenetration has been observed in all the 3D structures. The 3D structures appear to be related and can be derived from fgs net. Transformation studies on the 1D compound, [Na2(H 2O)8][Cd(C10H8N2)(S 2O3)2]·2H2O, I, indicated a facile formation of [Cd(C10H8N2)(H 2O)2(S2O3)]·2H2O, III. Prolonged heating of I gave rise to a 3D cadmium sulfate phase, [Cd 2(C10H8N2)2(H 2O)3(SO4)2]·2H2O, VI. Compound VI has one-dimensional cadmium sulfate chains formed by six-membered rings connected by bpy units to form a 3D structure, which appears to resemble the topological arrangement of III. Transformation studies of III indicates the formation of IV and V, and at a higher temperature a new 3D cadmium sulfate, [Cd(C10H8N2)(SO4)], VII. Compound VII has a 4 × 4 grid cadmium sulfate layers pillared by bpy units. All the compounds were characterized by PXRD, TGA, IR and UV-visible studies. Preliminary studies on the possible use of the 3D compounds (III-VII) in heterogeneous cyanosilylation of imines appear to be promising. © The Royal Society of Chemistry 2010.