Magnetic and electrical properties of a series of new inorganic complex based materials [n-Pr4N]2[Pb(ecda)2], [Et4N]4[Hg2(ecda)4] and M[M′(ecda)2] (M=Co(II), Ni(II), Cu(II), Cd(II) or Pb(II); M′=Hg(II) or Pb(II); ecda2−=1-ethoxycarbonyl-1-cyanoethylene-2,2-dithiolate) have been investigated using molecular spectroscopic (IR, Raman, EPR, electronic and mass) and conducting properties. Complete quenching of paramagnetism indicates strong Cu–Cu interaction in the layered polymeric array of Cu[Hg(ecda)2] and Cu[Pb(ecda)2] in the solid state. The 1H NMR spectrum of Ni[Pb(ecda)2] in DMSO-d6 gives narrow unshifted peaks due to diamagnetic, square-planar geometry around Ni(II) and shows absence of some octahedral units (μeff=1.49 BM) present in the solid state of this product. While the peak broadening indicates paramagnetic nature and absence of dominant Cu–Cu interaction in solution for Cu[Hg(ecda)2] and Cu[Pb(ecda)2]. The temperature dependent (305–373 K) compressed pellet conductivity together with activation energy (0.36–1.23 eV), show semiconducting behaviour of some of the bimetallic derivatives.