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)
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Ημερομηνία
Τίτλος Εφημερίδας
Περιοδικό ISSN
Τίτλος τόμου
Εκδότης
Wiley
Περίληψη
Τύπος
Είδος δημοσίευσης σε συνέδριο
Είδος περιοδικού
peer reviewed
Είδος εκπαιδευτικού υλικού
Όνομα συνεδρίου
Όνομα περιοδικού
European Journal of Inorganic Chemistry
Όνομα βιβλίου
Σειρά βιβλίου
Έκδοση βιβλίου
Συμπληρωματικός/δευτερεύων τίτλος
Περιγραφή
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)(2)I+}.I-3(-).2I(2)] (1), whereas the reaction of benzothidzole-2-thione (bztzdtH) with diiodine in a molar ratio of 1:2 and 1:1 resulted in the formation of the [{(bztzdtH)I-2}.I-2} (2) and [(bztzdtH)I-2] (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)I-2}(2).I-2.2H(2)O] (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 H-1 NMR spectroscopy. Crystal structures of the named complexes have been determined by X-ray diffraction at -103 degreesC (1), 20 degreesC (2 and 3) and -168 degreesC (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-Rdman spectra of the complexes, Compound 1 (C3H5NS2I4) is monoclinic with a space group P2(1)/n and a = 9.145(2) Angstrom, b = 13.259(2) Angstrom, c = 10.615(2) Angstrom, beta = 106.30(2)degrees, Z = 4. The complex is ionic, containing an S-I+-S linkage and an I-3(-) Compound 2 3 counter anion. {C7H5NS2I4, monoclinic, space group P2(1)/n, a = 8.357(2) Angstrom, b = 17.829(4) Angstrom, c = 9.603(2) Angstrom, Z = 4, beta = 94.39(3)degrees] consists of a benzothiazole-2-thione ligand bonded with an iodine atom through a sulfur atom. A neutral diiodine molecule is also cocrystallized. A benzothiazole-2-thione ligand is also bonded through its sulfur atom to an iodine atom in molecule 3 [C7H5NS2I2, orthorhombic, space group P2(1)2(1)2(1), a = 4.189(1) Angstrom, b = 9.770(3) Angstrom, c = 27.704(8) Angstrom, 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 P2(1)/c and a = 13.4828(14) Angstrom, b = 4.6704(4) Angstrom, c = 21.267(2) Angstrom, beta = 101.029(8)degrees, 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. (C) Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
Περιγραφή
Λέξεις-κλειδιά
bioinorganic chemistry, charge-transfer complexes, iodine, s ligands, sulfur heterocycles, charge-transfer complexes, correlated chemical-systems, ray crystal-structures, x-ray, antithyroid drugs, ft-raman, thermodynamic parameters, molecular-interactions, iodine monobromide, derivatives
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<Go to ISI>://000176717700022
Γλώσσα
en
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Όνομα επιβλέποντος
Εξεταστική επιτροπή
Γενική Περιγραφή / Σχόλια
Ίδρυμα και Σχολή/Τμήμα του υποβάλλοντος
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας