A new (E, E)-dioxime (H2L) containing a diazadioxadithia macrocyclic moieties has been synthesized by reaction of an aromatic primary amine with cyanogendi-N-dioxide. The BF2+ -capped Ni2+ mononuclear complex of this new oxime has been synthesized using a precursor hydrogen-bridged mononuclear Ni2+ complex. The solvent extraction of transition metal cations by (3) and (6) with picrate anion into chloroform has been studied at 25degreesC and UV-visible spectroscopy. The extractability and selectivity of transition metal picrates, (Pb2+, Ni2+, Co2+, Cd2+, Zn2+, Cu2+, Ag+) has been evaluated. The structures of new compounds are identified by using elemental analysis, H-1 and C-13-NMR, IR and MS spectral data.