Syntheses of the first bicyclic dianion containing hexacoordinate silicon with several cations, [(C6H4O2)2-Si(NCS)2]2-[B]+2 (B = pyH (1), 3-mepyH (2), 4-mepyH (3), K (4), Na (5), NH4 (6), Et2NH2 (7)), are described. Complexes 1-3 are prepared from the reactions between benzene- 1,2-diol and the appropriate cationic 5-coordinate silicon(IV) compounds 8-10. Complexes 4-6 are obtained in one-step reaction between diethoxydiisothiocyanatosilane and the diol in the presence of 1 equiv amount of NCS- anion, while 7 is formed using chemoselective metathesis of 6 with diethylamine. All the reactions occur at ambient temperature (less-than-or-equal-to 25-degrees-C). The compounds are characterized by multinuclei (H-1, C-13, N-14, Si-29) NMR spectra besides elemental analyses, IR, and molar conductance data. FAB-mass spectra (NBA matrix) have identified the cations in 1-7 and the dianion as clusters in 1-3 and 6.