Dioximes related to 2,2'-bis[4-(2,3-bis(hydroxyimino)quinoxaline] phenylpropane (H4L1) and 4,4'-oxy-bis[2,3bis(hydroxyimino)quinoxaline] (H4L2) precursor tetraamine compounds have been prepared. Some polymeric cobalt(III) complexes have been isolated. In addition, polymeric Cu-II complex with the ligand (H4L2) has been prepared. The polymeric complex [Cu(H2L2)](n) Obtained gets coordinated through the deprotonated oximate oxygens to afford a new kind of structure bridged by the oximate groups in the cis arrangement with 1,10-phenanthroline as an end-cap ligand. These complexes have been characterized by elemental analyses, mass, IR and H-1 NMR spectra and electrical conductivity measurements.