Solvent-induced supramolecular isomerism in silver(i) 2-methylimidazolate

Three pseudo-polymorphs of silver(I) 2-methylimidazolates have been prepared via liquid diffusions with variations of the templating solvent molecules. Among them, the solvated isomers [Ag4(mim)4·(C6H6)]∞ (1a, Pnna, a = 19.6228(8) Å, b = 10.4307(4) Å, c = 12.7867(5) Å, Hmim = 2-methylimidazole) and [Ag4(mim)4·(C8H10)]∞ (1b, P21/c, a = 12.6836(16) Å, b = 19.726(2) Å, c = 11.1137(13) Å, β = 101.835(3)°) exhibit peculiar pseudo-81 helical and S-shaped chains, respectively, which are further extended through short interchain AgI⋯AgI contacts (2.9848(4) Å and 3.2451(2) Å for 1a, 3.0224(6) Å and 3.0744(6) Å for 1b) into complex 3-D networks, whereas the unsolvated isomer [Ag(mim)]∞ (1c, P21/n, a = 7.8906(7) Å, b = 5.9706(5) Å, c = 10.8708(9) Å, β = 92.452(1)°) exhibits a simple zigzag chain without obvious intermolecular interactions.