Benzo[c]cinnolinium Trifluoromethanesulfonate Architectures Induced by Organotin(IV) Complexes

Four novel crystalline architectures based on benzo[c]cinnolininium trifluoromethanesulonate salts, [C12H9N2]+[CF3SO3]−, have been isolated as single-crystals, and their structures have been determined by X-ray diffraction analysis. The formation of the new salts results from reactions involving the dimeric hydroxo di-n-butylstannane trifluoromethanesulfonato complex [n-Bu2Sn(OH)(H2O)(CF3SO3)]2 (1) and benzo[c]cinnoline (C12H8N2, BCC). Organic salts I, II, III, and IV were crystallized through slow evaporation at room temperature from a mixture of toluene/dichloromethane. The cystallographic structures of I, II, and IV exhibit the presence of monoprotonated benzo[c]cinnolinium cations in interactions with a free benzo[c]cinnoline molecule through N–H···N hydrogen bonding, while for salt III, the monoprotonated cation directly interacts with the CF3SO3− anion via an N–H···O interaction. For all four salts, aromatic π-π interactions involving rings of various components (free benzo[c]cinnoline molecule, benzo[c]cinnolinium cation, toluene molecule), combined with weak C–H···O and C–H···F interactions implying the trifluoromethanesulfonate anion, promote the solid-state self-assembly of supramolecular stacks. In parallel to the formation of benzo[c]cinnolinium based-salts, organotin(IV) 1 was converted into a distannoxane compound, 2∞{[n-Bu2(μ-OH)SnOSn(μ-η2-O3SCF3)n-Bu2]2[n-Bu2(η1-O3SCF3)SnOSn(μ-OH)n-Bu2]2} (3), which was also isolated as a single crystal and whose crystallographic structure was previously established by us.