1:1 and 1:2 Complexes of Mercury(II) Halides with 1,3-Thiazolidine-2-thione. Spectral, Thermal, and Crystal Structure Studies

The series of compounds of the general formulae HgX2(tzdtH) and HgX2(tzdtH)2 (X = Cl, Br, I; tzdtH = 1,3-thiazolidine-2-thione) have been prepared, as well as Hg(tzdt)2. IR, 1H, and 13C NMR spectral data of the complexes indicate thione donation, which is confirmed by the crystal structure analyses of [HgBr2(tzdtH)]2, [HgI2(tzdtH)]2, and HgI2(tzdtH)2. The structures of [HgBr2(tzdtH)]2 and [HgI2(tzdtH)]2 consist of centrosymmetric doubly bridged dimers, but they are not isostructural. The asymmetry in the HgX2Hg bridge is more pronounced in the bromo than in the iodo derivative [S–Hg–X(terminal) is 138.19(9)° for X = Br and 123.49(10)° for X = I], which is accompanied by the stronger Hg–S covalent bond in the bromo than in the iodo complex [2.435(4) vs. 2.510(3) Å]. The Hg–X(bridging) (X = Br, I) bond distances are shorter than the sum of van der Waals radii for mercury and X. Dimeric centrosymmetric complex units are held together only by van der Waals forces in [HgI2(tzdtH)]2, while in [HgBr2(tzdtH)]2 there is an intramolecular hydrogen bond of N–H⋅ ⋅ ⋅Br type (3.34(1) Å). HgI2(tzdtH)2 exists as a mononuclear tetrahedral complex with two long Hg–S [2.672(1) Å] and two short Hg–I bond distances [2.688(1) Å] related by a twofold axis. The molecules of HgI2(tzdtH)2 are linked into infinite chains along the c axis by intermolecular N–H⋅ ⋅ ⋅S [3.38(1) Å] hydrogen bonds.