Tetranuclear Ag(I) complexes with an octagonal Ag 4S 4 core: building large structures from small macrocycles

Abstract

Reaction of the thioether macrocycles TT[9]OC and Me 2TT[9]OC with Ag + salts in a 1:1 ratio produces unique tetrameric cations containing an octagonal [Ag 4S 4] 4+ cavity. The X-ray crystal structures of three of these aggregates {[AgL][X]}4 (X =BF 4 −, L = TT[9]OC; X = CF 3SO 3 −, L = TT[9]OC; X = BF 4 −, L = Me 2TT[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. This completes a pseudotetrahedral geometry and results in cyclic tetramers with a [AgS] 4 4+ octagonal core. Each structure has two symmetry related anions (BF 4 − or CF 3SO 3 − included over the opposing faces of the large tetracationic cavity. {[Ag(TT[9]OC)][BF 4]} 4·2(MeCN): C 52H 70B 4F 16N 2S 12, P2 1 c , a=14.525(7), b=16.703(11), c = 16.250(6) Å, β = 115.54(3)°, V = 3557(6)Å 3 and Z=2. {[Ag(TT[9]OC)][CF 3SO 3]} 4: C 52H 64Ag 4F 12O 12S 16, P2 1 c , a=12.308(2), b=23.381(4), c=14.018(2) A, β = 113.30(1)°, V = 3705(5)Å 3 and Z=2. {[Ag(Me 2[9]OC)][BF 4]} 4·2(MeCN): C 60H 86Ag 4B 4F 16N 2S 12, P2 1 c , a=14.878(8), b=17.356(7), c = ]6.804([1) Å, P = 114.95(4)°, V = 3934(4) A3 and Z = 2.