Dinuclear silver(I) complexes of 24-membered bibracchial tetraimine Schiff base macrocycles derived from 2,5-diformylthiophene

The cyclocondensation of 2,5-diformylthiophene and the amines N,N-bis-(2-aminoethyl)-2-phenylethylamine, N,N-bis-(2-aminoethyl)-n-butylamine and N,N-bis-(2-aminoethyl)-t-butyl-amine in the presence of silver(I) salts yields homodinuclear bibracchial tetraimine Schiff base macrocyclic complexes. The structures of two such complexes are also reported. The complex Ag(2)L(4)(NO3)(PF6) (2) crystallises in the triclinic space group P (1) over bar (C-i(l),No.2) and has unit-cell dimensions a = 12.834(6), b = 13.183(6), c = 14.588(7) Angstrom, alpha = 64.86(4), beta = 79.77(4), gamma = 69.44(3)degrees with Z = 2; there is a monodentate and singly bridging nitrate anion present and the Ag-Ag separation is 4.161 Angstrom. The complex Ag(2)L(4)(CH3CN)(2)(BF4)(2) . CH3CN (9) crystallises in the triclinic space group (1) over bar (C-i(l), No.2) and has unit-cell dimensions a = 9.297(4), b = 12.985(3), c = 21.770(5) Angstrom, alpha = 91.570(10), beta = 92.33(3), gamma = 97.92(3)degrees with Z = 2; there is a strongly bonded acetonitrile molecule coordinated to each silver atom and the Ag-Ag separation is 4.920 Angstrom.