An X-ray, spectroscopic and semiempirical quantum-mechanical study on complexes of thiones and selones with molecular diiodine

Cristiani, Franco; Demartin, Francesco; Devillanova, Francesco A.; Isaia, Francesco; Saba, Giuseppe; Verani, Gaetano

doi:10.1039/dt9920003553

Cited by 46 publications

(26 citation statements)

References 18 publications

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“…Morpholine (1), thiomorpholine (2), N-methylmorpholine (3), diiodine, and spectroscopic solvents (benzene, chloroform, and dichloromethane) (Aldrich) were used without further purification.…”

Section: Methodsmentioning

confidence: 99%

“…The structure was solved by Patterson and difference Fourier syntheses and refined in fullmatrix least squares, the function minimized being Rw(|F 0 | ‫מ‬ |F c |) 2 . Anisotropic displacement parameters were refined for all the nonhydrogen atoms.…”

Section: General Proceduresmentioning

confidence: 99%

“…A comparison between the results obtained in solution and in the solid state has shown that very often the stoichiometries of the solids are different from those in solution, where normally 1:1 adducts are formed. In fact, besides neutral charge-transfer complexes, D • I 2 , where diiodine binds linearly with the donor atom [2], it is possible to prepare D • nI 2 compounds [3], in which other diiodine molecules interact with the coordinated I 2 . Depending on several factors (nature of the donor, solvent, reagent ratio, etc.…”

Section: Introductionmentioning

confidence: 99%

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Interaction of morpholine and thiomorpholine with molecular diiodine:X-ray crystal structure of morpholinium triiodide

et al. 1997

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Section: Methodsmentioning

confidence: 99%

Section: General Proceduresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Interaction of morpholine and thiomorpholine with molecular diiodine:X-ray crystal structure of morpholinium triiodide

et al. 1997

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“…Ϫ ] [16] (etu ϭ ethylenethiouria), 7 [{(tu) 2 I ϩ }·I Ϫ ] [29] (tu ϭ thiourea), 8 [(mbzttH) 2 I ϩ ·I Ϫ ·3I 2 ] [12] (mbzttH ϭ N-methylbenzothiazole-2-thione), 9 [ptc·I 2 ] [5] (ptc ϭ 1,3-dithiacyclohexane-2-thione), 10 [ttb·I 2 ], [5] (ttb ϭ 4,5-ethylenedithio-1,3-dithiole-2-thione), 11 [mdtt·I 2 ] [7] [mdtt ϭ 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione], 12 [mbit·I 2 ] [10] [mbit ϭ 1,1-methylenebis(3-methyl-4-imidazoline-2-thione)], 13 [bzoxtH·I 2 ] [11] (bzoxtH ϭ benzoxazole-2-thione), 14 [dmimdtH·I 2 ] [13] (dmimdtH ϭ 5,5-dimethylimidazoline-2,4-dithione), including our compounds 1Ϫ4 Figure 7. Correlation between ν(IϪI) Raman bands of the adducts 9 [ptc·I 2 ] [5] (ptc ϭ 1,3-dithiacyclohexane-2-thione) [ν(IϪI) ϭ 164 cm Ϫ1 ], 10 [ttb·I 2 ] [5] (ttb ϭ 4,5-ethylenedithio-1,3-dithiole-2-thione) [ν(IϪI) ϭ 162 cm Ϫ1 ], 11 [mdtt·I 2 ] [7] [mdtt ϭ 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione] [ν(IϪI) ϭ 136 cm Ϫ1 ], 12 [mbit·I 2 ] [10] [mbit ϭ 1,1-methylenebis(3-methyl-4-imidazoline-2-thione] [ν(IϪI) ϭ 152 cm Ϫ1 ], 13 [bzoxtH·I 2 ] [11] (bzoxtH ϭ benzoxazole-2-thione) [ν(IϪI) ϭ 176 cm Ϫ1 ], 14 [dmimdtH·I 2 ] [13] (dmimdtH ϭ 5,5-dimethylimidazoline-2,4-dithione) [ν(IϪI) ϭ 152 cm Ϫ1 ], including compounds 2Ϫ4 spectively.…”

Section: Correlationsmentioning

confidence: 99%

“…Correlation between ν(IϪI) Raman bands of the adducts 9 [ptc·I 2 ] [5] (ptc ϭ 1,3-dithiacyclohexane-2-thione) [ν(IϪI) ϭ 164 cm Ϫ1 ], 10 [ttb·I 2 ] [5] (ttb ϭ 4,5-ethylenedithio-1,3-dithiole-2-thione) [ν(IϪI) ϭ 162 cm Ϫ1 ], 11 [mdtt·I 2 ] [7] [mdtt ϭ 4,5-bis(methylsulfanyl)-1,3-dithiole-2-thione] [ν(IϪI) ϭ 136 cm Ϫ1 ], 12 [mbit·I 2 ] [10] [mbit ϭ 1,1-methylenebis(3-methyl-4-imidazoline-2-thione] [ν(IϪI) ϭ 152 cm Ϫ1 ], 13 [bzoxtH·I 2 ] [11] (bzoxtH ϭ benzoxazole-2-thione) [ν(IϪI) ϭ 176 cm Ϫ1 ], 14 [dmimdtH·I 2 ] [13] (dmimdtH ϭ 5,5-dimethylimidazoline-2,4-dithione) [ν(IϪI) ϭ 152 cm Ϫ1 ], including compounds 2Ϫ4 spectively. Therefore, complex 3 could be classified as a type C adduct, and complexes 2 and 4 as types B.…”

Section: Correlationsmentioning

confidence: 99%

Synthesis, Spectroscopic and Structural Characterization of Novel Diiodine Adducts with the Heterocyclic Thioamides, Thiazolidine-2-thione (tzdtH), Benzothiazole-2-thione (bztzdtH) and Benzimidazole-2-thione (bzimtH)

Daga

Hadjikakou

Hadjiliadis

et al. 2002

Eur. J. Inorg. Chem.

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Direct reaction of thiazolidine‐2‐thione (tzdtH), an anti‐thyroidal agent with diiodine in a molar ratio of 1:2 caused the heterolytic cleavage of diiodine and formation of [{(tzdtH)2I+}·I3−·2I2] (1), whereas the reaction of benzothiazole‐2‐thione (bztzdtH) with diiodine in a molar ratio of 1:2 and 1:1 resulted in the formation of the [{(bztzdtH)I2}·I2] (2) and [(bztzdtH)I2] (3) charge‐transfer (c.t.) complexes. In addition, the reaction between benzimidazole‐2‐thione (bzimtH) with diiodine in a molar ratio 1:2 yielded the c.t. complex [{(bzimtH)I2}2·I2·2H2O] (4). All reactions were carried out in dichloromethane. The molecules have been characterized by m.p., elemental analyses, and FT‐Raman, FT‐IR, UV/Vis and 1H NMR spectroscopy. Crystal structures of the named complexes have been determined by X‐ray diffraction at −103 °C (1), 20 °C (2 and 3) and −168 °C (4). The charge‐transfer nature of the bonds of the adducts (1−4) has been verified by the lengthening of the I−I bond lengths as compared to the S−I bond lengths, by the characteristic c.t. bands observed in the UV spectra and by the shifts of frequencies measured for the I−I bond vibration in the FT‐Raman spectra of the complexes. Compound 1 (C3H5NS2I4) is monoclinic with a space group P21/n and a = 9.145(2) Å, b = 13.259(2) Å, c = 10.615(2) Å, β = 106.30(2)°, Z = 4. The complex is ionic, containing an S−I+−S linkage and an I3− counter anion. Compound 2 [C7H5NS2I4, monoclinic, space group P21/n, a = 8.357(2) Å, b = 17.829(4) Å, c = 9.603(2) Å, Z = 4, β = 94.39(3)°] consists of a benzothiazole‐2‐thione ligand bonded with an iodine atom through a sulfur atom. A neutral diiodine molecule is also co‐crystallized. A benzothiazole‐2‐thione ligand is also bonded through its sulfur atom to an iodine atom in molecule 3 [C7H5NS2I2, orthorhombic, space group P212121, a = 4.189(1) Å, b = 9.770(3) Å, c = 27.704(8) Å, Z = 4]. Extended intramolecular N−H···I contacts link the molecules forming a supramolecular assembly. The crystal structure of 4 (C7H6N2SI3·H2O) reveals a monoclinic space group P21/c and a = 13.4828(14) Å, b = 4.6704(4) Å, c = 21.267(2) Å, β = 101.029(8)°, Z = 4. It consists of a benzimidazole‐2‐thione ligand bonded to an iodine atom through a sulfur atom. An extended intramolecular linkage via I(2)···H(4)[C(4)] leads to the formation of dimers, while an extended hydrogen‐bonding network {H(12w)[O(12)w]···N(3), O(1w)···N(3)} links the alternate parallel dimers forming a supramolecular assembly. Attempts to draw conclusions on the behavior of a thione, when used as an anti‐thyroidal agent, towards diiodine have been made. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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The Thiocarbonyl Group

Molina

Yáñez

Mó

et al. 2009

Patai's Chemistry of Functional Groups

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An X-ray, spectroscopic and semiempirical quantum-mechanical study on complexes of thiones and selones with molecular diiodine

Cited by 46 publications

References 18 publications

Interaction of morpholine and thiomorpholine with molecular diiodine:X-ray crystal structure of morpholinium triiodide

Interaction of morpholine and thiomorpholine with molecular diiodine:X-ray crystal structure of morpholinium triiodide

Synthesis, Spectroscopic and Structural Characterization of Novel Diiodine Adducts with the Heterocyclic Thioamides, Thiazolidine-2-thione (tzdtH), Benzothiazole-2-thione (bztzdtH) and Benzimidazole-2-thione (bzimtH)

The Thiocarbonyl Group

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