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

Autori
Popović, Zora ; Pavlović, Gordana ; Soldin, Željka ; Popović, Jasminka ; Matković-Čalogović, Dubravka ; Rajić, Maša

Izvornik
Structural Chemistry (1040-0400) 13 (2002), 5/6; 415-424

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Mercury(II) halide complexes; Heterocyclic thione; Crystal structures; 1^H and 13^C NMR; TGA-DTA analysis

Sažetak
The series of compounds of the general formulae HgX_2(tzdtH) and HgX_2(tzdtH)_2 (X = Cl, Br, I ; tzdtH = 1, 3-thiazolidine-2-thione) have been prepared as well as Hg(tzdt)_2. IR, 1^H and 13^C NMR spectral data of the complexes indicate thione donation, which is confirmed by the crystal structure analyses of (HgBr_2(tzdtH))_2, (HgI_2(tzdtH))_2 and HgI_2(tzdtH)_2. The structures of (HgBr_2(tzdtH))_2 and (HgI_2(tzdtH))_2consist of centrosymmetric doubly bridged dimers, but they are not isostructural. The asymmetry in the HgX_2Hg bridge is more pronounced in the bromo than in the iodo derivative (S-Hg-X(terminal) is 138.19(9)^o for X = Br and 123.49(10) ^o 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) &Aring ; ; ; ; ]. 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 (HgI_2(tzdtH))_2, while in (HgBr_2(tzdtH))_2 there is an intramolecular hydrogen bond of N-H...Br type (3.34(1) &Aring ; ; ; ; ). HgI_2(tzdtH)_2 exists as a mononuclear tetrahedral complex with two long Hg-S (2.672(1) &Aring ; ; ; ; ) and two short Hg-I bond distances (2.688(1) &Aring ; ; ; ; ) related by a twofold axis. The molecules of HgI_2(tzdtH)_2 are linked into infinite chains along the c axis by intermolecular N-H...S (3.38(1) &Aring ; ; ; ; ) hydrogen bonds.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

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