A novel tetraoxime containing a substituted twofold macrocycle, 6,6'-spirobi[1,12-di(hydroxyimino)-2,3:9,10-dibenzo-1,11-diaza-4,8-dithiacyclotridecane] (5), has been synthesized from 6,6'-bis(5'-amino-3',4'-benzo-2'-thiapentyl)-1, 11-diamino-2, 3:9, 10-dibenzo-4,8-dithiaundecane (3), which was itself prepared from the potassium salt of 2-aminothiophenol (2), pentaerythrityltetrabromide (1) and cyanogendi-N-oxide (4). A polymeric Co-III complex of (5) containing a 1:1 metal:ligand ratio has been isolated. The template synthesis of a new Co-III complex containing bridging BF2 groups was achieved using the hydrogen-bridged Co-III complex. The hetero-polynuclear complex of (5) was prepared by reacting the BF2+-capped polymeric Co-III complex with bis(benzonitrile)Pd(II)chloride. The structure of the ligand and its complexes are in accord to elemental analyses, H-1- and C-13-n.m.r., i.r. and mass spectral data.