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Synthesis, Spectral and Thermal Characterization of Bis(pyridine-3-carboxy-2-thiolato-S)mercury(II). Crystal Structure of Dibromobis(3-metoxycarbonylpyridine-2-thiolato-S)mercury(II)

Solidin, Željka; Vikić-Topić, Dražen; Pavlović, Gordana; Vinković, Marijana; Matković-Čalogović, Dubravka; Popović, Zora (2012) Synthesis, Spectral and Thermal Characterization of Bis(pyridine-3-carboxy-2-thiolato-S)mercury(II). Crystal Structure of Dibromobis(3-metoxycarbonylpyridine-2-thiolato-S)mercury(II). Croatica Chemica Acta, 85 (4). pp. 515-524. ISSN 0011-1643

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Abstract

2-mercaptonicotinic acid (H(2)mna = 2-HS(C5H3N)COOH) gave a thiolato compound of the formula Hg(Hmna)(2) by a reaction with various mercury(II) salts, HgX2 (X = Cl-, Br-, I-, SCN-) in an ethanol or methanol solution irrespectively of the molar ratio of the reactants (1:1 or 1:2). The same compound was obtained from the reaction of mercury(II) acetate in an aqueous-ethanol solution. Hg(Hmna)(2) was characterized by vibrational spectroscopy and thermal analysis. H-1 and C-13 NMR measurements provided additional information on the thiol-thione tautomerism in H(2)mna and Hg(Hmna)(2) and also on the binding mode to mercury in the DMSO-d(6) solution. HgBr2(CH3-Hmna)(2) was obtained from the reaction of H(2)mna with HgBr2 in methanol after filtering off the main product Hg(Hmna)(2) (CH3-Hmna = 2-HS(C5H3N)COOCH3). The crystal structures of H(2)mna and HgBr2(CH3-Hmna)(2) were determined by the X-ray structure analysis. 2-mercaptonicotinic acid exists in the crystalline state in the thione tautomeric form. Two bromine atoms and two S-bound CH3-Hmna ligands form a tetrahedral coordination sphere around the mercury atom in HgBr2(CH3-Hmna)(2).

Item Type: Article
Uncontrolled Keywords: 2-mercaptonicotinic acid; mercury complex; thione-thiol tautomerism; X-ray single crystal structure analysis; intra- and intermolecular hydrogen bonds; H-1; C-13 NMR; HEXANUCLEAR SILVER(I) CLUSTER; 2-MERCAPTONICOTINIC ACID; MERCURY(II) COMPLEXES; MOLYBDENUM(VI) COMPLEXES; HETEROCYCLIC THIONES; MOLECULAR-STRUCTURE; SOFT ACIDS; X-RAY; HALIDES
Subjects: NATURAL SCIENCES > Chemistry
Divisions: NMR Center
Projects:
Project titleProject leaderProject codeProject type
Spektroskopija NMR i modeliranje bioaktivnih molekula[76010] Dejan Plavšić098-0982929-2917MZOS
Strukturno istraživanje bioloških makromolekula metodom rentgenske difrakcije[108862] Dubravka Matković-Čalogović119-1193079-1084MZOS
Kemija metalnih kompleksa u reakcijama od biološkog značaja i novim materijalima[74906] Zora Popović119-1193079-1332MZOS
Depositing User: Dražen Vikić-Topić
Date Deposited: 11 Oct 2013 08:44
Last Modified: 06 Feb 2014 15:36
URI: http://fulir.irb.hr/id/eprint/768
DOI: 10.5562/cca2169

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