Abstract
Crystallization of silver(I) sulfate with the ligand 1-methylimidazole-2-thione ('Hmimt') from aqueous solution, instead of yielding the expected 1:6 Ag(2)SO(4):Hmimt complex analogous to numerous other Ag(2)SO(4):thiourea-based ligand (1:6) complexes, has resulted in novel polymeric forms, one of unusual stoichiometry. Ag(2)SO(4):Hmimt (1:4) (x H(2)O) is of the form [...(mu-Hmimt)(2)Ag(mu-Hmimt)(2)Ag...](infinity|infinity)(SO(4)), with a one-dimensional polymeric cation. Ag(2)SO(4):Hmimt (3:8) (x 9 1/2 H(2)O) is a polymeric sheet structure containing Ag(12)(SO(4))(6)(Hmimt)(15) kernels linked by Hmimt ligands. The IR spectra of these compounds show unusually large shifts of the nu(NH) band due to the presence of N-H...O hydrogen bonding involving the N-H group of the ligand and the sulfate oxygen atoms. The complexes were also readily prepared by the solvent-assisted mechanochemical method, and the utility of this method for the preparation of deuterium-exchanged products for assistance in the assignment of the IR spectra is illustrated.
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