Молекулярная и кристаллическая структура 1-(4-фторфенил)-1,4-дигидро-5-тетразол-5-тиона и его комплекса с кадмием(II)

The molecular and crystal structures of 1-(4-fluorophenyl)-1,4-dihydro-1 H -tetrazole-5-thione (I) and its complex with cadmium(II) (II) are studied by single crystal XRD. Free ligand I is thione; it has a non-planar structure (the torsion angle between the tetrazole and benzene rings is 54.99(7)°) and forms H-bonded centrosymmetric dimers via two N-H…S hydrogen bonds in the crystal. The dimers contain a central planar eight-membered {S=C-N-H…S=C-N-H…} ring. Complex II has a chain structure with the composition [(C7H4N4FS)2Cd] n. The environment of the Cd(II) atom consists of two nitrogen atoms and two sulfur atoms from four ligands I and represents a distorted tetrahedron. When complex II forms, ligand I converts into the thiol form. Infinite 1D chains contain eight-membered {S=C-N-CdS=C-N-Cd} rings in a chair conformation. The chains in the crystal are arranged in layers parallel to the (101) plane due to secondary intermolecular F…F and p-p-stacking interactions.Методом РСА изучена молекулярная и кристаллическая структура 1-(4-фторфенил)-1,4-дигидро-5-тетразол-5-тиона (I) и его комплекса с кадмием(II) (II). Свободный лиганд I является тионом, имеет неплоское строение (угол скручивания между тетразольным и бензольным циклами равен 54.99(7)°) и образует в кристалле H-связанные центросимметричные димеры посредством двух N-H…S водородных связей. Димеры включают центральный плоский восьмичленный цикл {S=C-N-H…S=C-N-H…}. Комплекс II имеет цепочечное строение состава [(C7H4N4FS)2Cd] n. Окружение атома Сd(II) состоит из двух атомов азота и двух атомов серы от четырех лигандов I и представляет искаженный тетраэдр. Лиганд I при образовании комплекса II переходит в тиольную форму. Бесконечные 1D цепочки содержат восьмичленные циклы {S=C-N-CdS=C-N-Cd} в конформации кресло. В кристалле цепочки связаны в слои, параллельные плоскости (101), за счет межмолекулярных вторичных F…F и p-p-стэкинг-взаимодействий

Bromination of bis(pyridin-2-yl) diselenide in methylene chloride: The reaction mechanism and crystal structures of 1H-pyridine-2-selenenyl dibromide and its cycloadduct with cyclopentene(3aSR,9aRS)-2,3,3a,9a-tetrahydro-1H-cyclopenta[ 4,5][1,3]selenazolo[3,2-a]pyridinium bromide

1H-Pyridine-2-selenenyl dibromide, C5H5NSeBr2, 1, is a product of the bromination of bis(pyridin-2-yl) diselenide in methylene chloride recrystallization from methanol. Compound 1 is essentially zwitterionic: the negative charge resides on the SeBr2 moiety and the positive charge is delocalized over the pyridinium fragment. The C - Se distance of 1.927(3)Å is typical of a single bond. The virtually linear Br - Se - Br moiety of 178.428(15)° has symmetrical geometry, with Se - Br bonds of 2.5761(4) and 2.5920(4)Å, and is twisted by 63.79(8)° relative to the pyridinium plane. The Se atom forms an intermolecular Se⋯Br contact of 3.4326(4)Å, adopting a distorted square-planar coordination. In the crystal, molecules of 1 are linked by intermolecular N - H⋯Br and C - H⋯Br hydrogen bonds, as well as by non-covalent Se⋯Br interactions, into a three-dimensional framework. (3aSR,(9aRS)-2,3,3a,9a-Tetrahydro-1H-cyclopenta[4,5][1,3]selenazolo[3,2-a]pyridinium-9 bromide, C10H12NSe + ·Br - , 2, is a product of the cycloaddition reaction of 1 with cyclopentene. Compound 2 is a salt containing a selenazolopyridinium cation and a bromide anion. Both five-membered rings of the cation adopt envelope conformations. The dihedral angle between the basal planes of these rings is 62.45(11)°. The Se atom of the cation forms two additional non-covalent interactions with the bromide anions at distances of 3.2715(4) and 3.5683(3)Å, attaining a distorted square-planar coordination. In the crystal, the cations and anions of 2 form centrosymmetric dimers by non-covalent Se⋯Br interactions. The dimers are linked by weak C - H⋯Br hydrogen bonds into double layers parallel to (001). © 2019

Molecular and Crystal Structure of 1-(4-Fluorophenyl)-1,4-Dihydro-1H-Tetrazole-5-Thione and Its Complex with Cadmium(II)

The molecular and crystal structures of 1-(4-fluorophenyl)-1,4-dihydro-1H-tetrazole-5-thione (I) and its complex with cadmium(II) (II) are studied by single crystal XRD. Free ligand I is thione; it has a nonplanar structure (the torsion angle between the tetrazole and benzene rings is 54.99(7)°) and forms H-bonded centrosymmetric dimers via two N–H…S hydrogen bonds in the crystal. The dimers contain a central planar eight-membered {S=C–N–H…S=C–N–H…} ring. Complex II has a chain structure with the composition [(C7H4N4FS)2Cd]n. The environment of the Cd(II) atom consists of two nitrogen atoms and two sulfur atoms from four ligands I and represents a distorted tetrahedron. When complex II forms, ligand I converts into the thiol form. Infinite 1D chains contain eight-membered {←S=C–N–Cd←S=C–N–Cd} rings in a chair conformation. The chains in the crystal are arranged in layers parallel to the (101) plane due to secondary intermolecular F…F and π–π-stacking interactions. © 2018, Pleiades Publishing, Ltd

Cadmium(II) and Nickel(II) 1-Oxypyridyl-2-Selenolates: Synthesis and Molecular and Crystal Structures

Abstract: Cadmium (C20H16Cd2N4O4Se4) (I) and nickel (C10H8N2NiO2Se2) (II) selenolates are synthesized by the exchange reactions of sodium 1-oxypyridyl-2-selenolate and cadmium(II) and nickel(II) chlorides. The molecular and crystal structures of the complexes are determined by X-ray structure analysis (CIF files CCDC nos. 1585246 (I) and 1585251 (II)). Complex I forms a centrosymmetric dimer in which the coordination polyhedron of the cadmium atom is a distorted trigonal bipyramid and the selenium atoms take the trans configuration. Complex II containing the solvate C2H5OH molecule has a square structure and is a monomer. Unlike complex I, in complex II the selenium atoms of the ligands take the cis configuration. The crystal packings in complexes I and II are formed by weak intermolecular hydrogen bonds C–H···O and C–H···Se. © 2019, Pleiades Publishing, Ltd

4-Phenyl-5-(2-Thienylmethyl)-2,4-Dihydro-3H-1,2,4-Triazole-3-Selone and 3,3'-Di[4-Phenyl-5-(2-Thienylmethyl)-4H-1,2,4-Triazolyl] Diselenide: Synthesis, Structures, and Biocidal Properties

Abstract: Three new organoselenium compounds are synthesized: N-phenyl-2-(2-thienylacetyl)hydrazinecarboselenoamide (I), 4-phenyl-5-(2-thienylmethyl)-2,4-dihydro-3H-1,2,4-triazole-3-selone (II), and 3,3'-di[4-phenyl-5-(2-thienylmethyl)-4H-1,2,4-triazolyl] diselenide (III). Two of them (compounds II and III) are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1956602 (II) and 1956603 (III)). Compound II crystallizes in the monoclinic crystal system (space group P21/n) with two crystallographically independent molecules A and B being different conformers relative to rotation about the NTrz–CTrz–C(H2)–CTph bond, where Trz is triazole and Tph is thiophene (gauche-A (51.4(3)°) and cis-B (4.2(4)°)). In the crystal of compound II, molecules A and B form chains along the crystallographic axis a due to strong hydrogen bonds N–H···Se. Then the chains are bound into a three-dimensional framework via intermolecular nonvalent interactions Se···S (3.3857(11) Å). Owing to the anomeric effect, diselenide III is characterized by the typical gauche conformation of the substituents at the Se–Se bond (torsion angle СSeSeС 83.5(4)°) stabilized by a weak intramolecular hydrogen bond С–H···π. In the crystal of compound III, the molecules form chains along the crystallographic acid b due to intermolecular noncovalent interactions Se···π(C–C) (3.404(6) and 3.458(12) Å), Se···Se (3.8975(11) Å), and S···N (3.250(5) Å). Bactericidal and fungicidal activity of the synthesized compounds is studied. © 2021, Pleiades Publishing, Ltd

4-(3-Methoxyphenyl)-5-(2-thienylmethyl)-2,4-dihydro-3H-1,2,4-triazole-3-selone: Synthesis, structural characteristics and reactions

The title compound 4-(3-methoxyphenyl)-3-(2-thienylmethyl)-4,5-dihydro-3H-1,2,4-triazole-3-selone 2 was synthesized by two-step procedure including condensation of 1-isoselenocyanato-3-methoxybenzene with 2-(2-thienyl)acetohydrazide to selenosemicarbazide 1 and its intramolecular cyclization. Oxidation of selone 2 by atmospheric oxygen or hydrogen peroxide furnished corresponding diselenide 3 or product of elimination of selenium 1,2,4-triazole 4. Alkylation of compound 2 by benzyl chloride leads to the formation of selenide 5. The synthesized compounds have been characterized by spectroscopic techniques and the structures of 3,4 and 5 were confirmed by X-ray diffraction techniques and the supramolecular contacts were analyzed by Hirshfeld surface analyses. © 2020 Elsevier B.V

Novel cationic 1,2,4-selenadiazoles: synthesisviaaddition of 2-pyridylselenyl halides to unactivated nitriles, structures and four-center Se⋯N contacts

2-Pyridylselenyl halides undergo facile coupling with a triple CN bond of unactivated nitriles. Unprecedented heterocyclization allowed the preparation of a novel class of cationic 1,2,4-selenadiazoles in remarkably high yields. Cationic 1,2,4-selenadiazoles form supramolecular dimers in the crystalviaSe⋯N chalcogen bonding, which was studied theoretically. © The Royal Society of Chemistry 2021

Erratum: Novel cationic 1,2,4-selenadiazoles: synthesisviaaddition of 2-pyridylselenyl halides to unactivated nitriles, structures and four-center Se⋯N contacts (Dalton Transactions (2021) 50 (10689-10691) DOI: 10.1039/D1DT01322J)

The authors regret that funding information was omitted from the original publication of this paper. Funding for this research was provided by RFBR (project number 21-53-54001) and RUDN University Strategic Academic Leadership Program. This study was supported by the VAST under grant no. QTRU01.04/21-22. The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers. © The Royal Society of Chemistry 2021

Complexes of 1-(2-R(F, CH3, Cl)-phenyl)-1,4-dihydro-5H-tetrazole-5-thiones with cadmium chloride: Synthesis, molecular, crystal structures and computational investigation approach

New complex compounds (I) - (IV) were synthesized by the reaction of 1-(2-fluorofluorophenyl) -1,4-dihydro-5H-tetrazole-5-thione (HL1), 1-(2-methylphenyl)-1,4-dihydro-5H-tetrazole-5-thione (HL2) and 1-(2-chlorochlorophenyl)-1,4-dihydro-5H-tetrazole-5-thione (HL3) with cadmium chloride. By X-ray diffraction analysis, molecular and crystal structures of complexes (I), (II), (III) and (IV) are determined. (CIF files CCDC № 2,003,797 (I), 1,993,454 (II), 2,151,359 (III), 2,098,997 (IV)). Hirshfeld surface analysis, frontier orbital analysis, atomic charges, electrostatic potential, nonlinear optical properties, and natural bond analysis of all three‑cadmium metal-organic complexes were discussed. A molecular docking study was used to investigate compounds' binding and interactions with DNA molecules, which predicted compound I as the best binder at the DNA minor groove and demonstrated closed distance interactions. In a long run of molecular dynamics simulations, the compound I complex was also depicted with good dynamics. © 2022 Elsevier Inc

Adducts of 2-Pyridylselenenyl Halides and Nitriles as Novel Supramolecular Building Blocks: Four-Center Se···N Chalcogen Bonding versus Other Weak Interactions

Supramolecular chemistry of chalcogenadiazoles is attracting an increasing attention due to its applications in materials chemistry. Chalcogen bonding allows a fine-tuning of the self-assembly and, therefore, modulation of physical properties when these compounds are employed. Here, we report a facile preparation of a broad scope of 1,2,4-selenadiazoles via coupling of 2-pyridylselenenyl halides with unactivated nitriles, that represent a novel type of supramolecular building blocks which eagerly engage in a variety of chalcogen bonding interactions. The substituent-dependent propensity of novel selenadiazoles for the formation of four-center Se···N chalcogen bonding is analyzed. Other weak interactions, which in some cases outcompete the formation of 2Se-2N squares, are described. The discovery of the adducts derived from α-halogenated nitriles, which form robust dimers featuring a very specific combination of 2Se-2N square, two Hal···Hal, and two Se···Hal noncovalent interactions, is presented. © 2021 American Chemical Society