TETRANUCLEAR AG(I) COMPLEXES WITH AN OCTAGONAL AG4S4 CORE - BUILDING LARGE STRUCTURES FROM SMALL MACROCYCLES

Reaction of the thioether macrocycles TT[9]OC and Me(2)[9]OC with Agsalts in a 1:1 ratio produces unique tetrameric cations containing an octagonal [Ag4S4](4+) cavity. The X-ray crystal structures of three of these aggregates {[AgL][X]}(4) (X = BF4-, L = TT[9]OC; X = CF3SO3-, L = TT[9]OC; X = BF4-, L = Me(2)TT[9]OC) were determined. In each case, the thiacyclophane ligand bonds in a facial coordination mode to one Ag(I) ion with the central S-donor bridging to the next Ag(I) ion. Thi s completes a pseudotetrahedral geometry and results in cyclic tetrame rs with a [AgS](4+)(4) octagonal core. Each structure has two symmetry related anions (BF4- or CF3SO3-) included over the opposing faces of the large tetracationic cavity. {[Ag(TT[9]OC)][BF4]}(4) . 2(MeCN): C52 H70Ag4B4F16N2S12 P2(1)/c, a = 14.525(7), b = 16.703(11), c = 16.250(6) Angstrom, beta = 115.54(3)degrees, V = 3557(6) Angstrom(3) and Z = 2. {[Ag(TT[9]OC)][CF3SO3]}(4): C52H64Ag4F12O12S16 P2(1)/c, a = 12.308(2) , b = 23.381(4), c = 14.018(2) Angstrom, beta = 113.30(1)degrees, V = 3705(5) Angstrom(3) and Z = 2. {[Ag(Me(2)TT[9]OC)][BF4]}(4) . 2(MeCN): C60H86Ag4B4F16N2S12, P2(1)/c, a = 14.878(8), b = 17.356(7), c = 16.80 4(11) Angstrom, beta = 114.95(4)degrees, V = 3934(4) Angstrom(3) and Z = 2.