SYNTHESIS, CHARACTERIZATION AND CRYSTAL-STRUCTURES OF 1,7-DIOXA-4-THIA-10-AZACYCLODODECANE ([12]ANENO2S) AND [HG([12]ANENO2S)(NO3)2]

Reaction of 6-(4-methylphenylsulfonyl)-1,11-bis(4-methylphenylsulfonyloxy)-3,9-dioxa-6-azaundecane and ethane-1,2-dithiol in the presence of NaH, results, after removal of the protecting group, in the unexpected isolation of the twelve-membered macrocycle 1,7-dioxa-4-thia-10-azacyclododecane, [12]aneNO2S. The product, suggested to arise from the intramolecular displacement of a tosyl group by a thioether instead of the terminal thiol as in the expected ring closing procedure, was characterised by C-13 NMR spectroscopy, mass spectrometry, microanalysis and a single-crystal X-ray structure determination. The macrocycle crystallizes in the monoclinic space group P2(1), with a = 7.448(5), b = 5.1740(10), c = 12.769(9) angstrom, beta = 93.28(2)-degrees, Z = 2 with R = 0.046. All the donors in the macrocyclic ring are in the endodentate conformation with close contacts between the N-H and atoms 0(1) and 0(7). Reaction of mercury nitrate with 1 molar equivalent of [12]aneNO2S in methanol, and subsequent crystallization of the product, resulted in colourless prisms of [Hg([12]aneNO2S)(NO3)2] which crystallize in the monoclinic space group P2(1)/c, with a = 9.165(17), b = 10.657(15), c = 14.80(2) angstrom, beta = 92.57(8)-degrees, Z = 4 with R = 0.055. In this molecule the mercury(II) cation is co-ordinated by the macrocyclic donors and the nitrate anions, one in a bidentate manner, the other in a monodentate mode.