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Complexes of heterocyclic thiones and group 12 metals part 2: The chemical and electrochemical synthesis of mercury(II) complexes of 1-methylimidazoline-2(3H)-thionate. The crystal structure of trans-[bis-{(η1-S-1-methylimidazoline-2(3H)-thione)(η1-S-1-methylimidazo line-2(3 H)-thionate)-(μ2-S,N-1-methylimidazoline-2-thionate)mercury(II)}] at 160K

Lookup NU author(s): Emeritus Professor Bill Clegg

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Abstract

Two complexes of mercury(II) and the anion of 1-methylimidazoline-2(3H)-thione (1-meimz2SH) have been prepared and characterised. The addition of an aqueous Solution of mercury(II) acetate to an aqueous solution of 1-methylimidazoline-2(3H)-thione and triethylamine produced [Hg(1-meimz2S)2], as a colourless and intractable precipitate. The electrochemical oxidation of elemental mercury, in the presence of a saturated acetonitrile solution of 1-methylimidazoline-2(3H)-thione and a supporting electrolyte, produced two crystalline products, a pale-yellow microcrystalline complex, [Hg(1-meimz2S)2] and a colourless crystalline complex, [Hg(1-meimz2S)2(1-meimz2SH)]. An X-ray crystal structure analysis of [Hg(1-meimz2S)2(1-meimz2SH)] showed that the complex consists of discrete, centrosymmetrically constrained, mercury(II) dimers. Each dimer contains a pair of bifunctional, binuclear bridging, μ2-S,N(η1-S;η1-N), 1-methylimidazoline-2(3H)-thionate anionic ligands (Hg-S(bridging) = 2.5196(6), Hg-N = 2.325(2) Å, N-C-S(exo) = 126.0(2)°). The bridging ligands adopt a 'head-to-tail' configuration. This arrangement generates a central eight-membered ring, Hg2S2C2N2, in the complex. The ring adopts a chair conformation. Distorted, pseudo-tetrahedral four-coordination at each metal is completed by a pair of monodentate, sulfur donating, 1-methyl-imidazoline-2(3H)-thione neutral and anionic ligands (Hg-S(thione) = 2.5735(7) and Hg-S(thionate) = 2.4829(7) Å). N-H···N hydrogen bonds (N···N = 2.701 Å) effectively link the terminal ligands into eight-membered chelates. (C) 2000 Elsevier Science S.A.


Publication metadata

Author(s): Bell NA, Clegg W, Creighton JR, Raper ES

Publication type: Article

Publication status: Published

Journal: Inorganica Chimica Acta

Year: 2000

Volume: 303

Issue: 1

Pages: 12-16

ISSN (print): 0020-1693

ISSN (electronic): 1873-3255

Publisher: Elsevier B.V.

URL: http://dx.doi.org/10.1016/S0020-1693(99)00487-9

DOI: 10.1016/S0020-1693(99)00487-9


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