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

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Abstract

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.

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Authors and Affiliations

  1. Laboratory of General and Inorganic Chemistry, Faculty of Science, University of Zagreb, Ul. kralja Zvonimira 8, HR-10000, Zagreb, Croatia

    Zora Popović, Željka Soldin, Jasminka Popović & Dubravka Matković-Čalogović

  2. Polytechnic of Karlovac, I. Meštrovića 10, HR-47000, Karlovac, Croatia

    Gordana Pavlović

  3. Laboratory for Thermal Analysis, Brodarski Institute, Marine Research and Special Technology, Av. V. Holjevca 20, HR-10000, Zagreb, Croatia

    Maša Rajić

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  1. Zora Popović
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  2. Gordana Pavlović
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  3. Željka Soldin
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  4. Jasminka Popović
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  5. Dubravka Matković-Čalogović
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  6. Maša Rajić
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Popović, Z., Pavlović, G., Soldin, Ž. et al. 1:1 and 1:2 Complexes of Mercury(II) Halides with 1,3-Thiazolidine-2-thione. Spectral, Thermal, and Crystal Structure Studies. Structural Chemistry 13, 415–424 (2002). https://doi.org/10.1023/A:1020541602675

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