A coordination polymer, {[Cd(L)(2)(DMF)(2)]center dot(ClO(4))(2)center dot(2DMF)}(n) (1) (L = bis-(4-imidazol-1-yl-phenyl)diazene) has been synthesized at room temperature. The polymer forms a two-dimensional (2D) rhombus-grid sheet structure. These 2D sheets are stacked in ABAB ... mode with an inter-planar spacing of 3.729 angstrom. Each Cd(II) ion is equatorially bonded to four imidazole N atoms belong to four different ligand units while 0 atoms from two DMF molecules occupy the axial sites. Two ClO(4)(-) counter anions as well as two DMF molecules occupy the void space in each rhombus grid. This compound catalyzes cyanosilylation reactions of aromatic aldehydes in dichloromethane under mild conditions in heterogeneous fashion. On heating 1 at 120 degrees C for 4 h. all DMF molecules are lost and the ClO(4)(-) anions move out of the void space to occupy the axial sites on the metal to yield, de-solvated {[Cd(L)(2)(ClO(4))(2)]}(n) (1) without losing crystallinity. De-solvated 1 exhibits heterogeneous catalytic activity in several Knoevenagel condensation reactions at RT. (C) 2011 Elsevier B.V. All rights reserved.