Novel triazine-functionalized tetra-imidazolium hexafluorophosphate salt: Synthesis, crystal structure and DFT study (original) (raw)
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Journal of the Turkish Chemical Society, Section A: Chemistry, 2016
The synthesized compound 5, (C13H15N2S2)[PF6], was fully characterized with Xray diffraction method. In this compound, the asymmetric unit contains a 1,3-(2thiophenylmethyl)-4,5-dihydroimidazolidinium cation and a hexafluorophosphate anion. Due to an 180° rotation about the thiophene-CH2 bonds, the thiophene rings in the cation are disordered [site-occupancy factors = 0.903(4)/0.097(4) and 0.837(5)/0.163(5), respectively]. The short C-N bond lengths [1.303(4) and 1.287(4) Å] in the imidazolidine ring display partial electron delocalization within the N-C-N fragment. Anion and cations are connected through intermolecular C-H...F hydrogen bonds and three π-π stacking interactions [centroid-centroid distances = 3.890(3), 3.852(5) and 3.816(7) Å] between the thiophene rings of the adjacent cations, forming layers parallel to (011). Furthermore, we studied theoretical studies of this compound, too. Geometry optimization was carried out in gas phase by Density Functional Theory (DFT) method with B3LYP applying 6-311++G ** basis set. The obtained results from experimental and theoretical structural properties of compound 5 had been compared to each other.
Synthesis and crystal structure of 1,3-bis(4-hydroxyphenyl)-1H-imidazol-3-ium chloride
Acta Crystallographica Section E Crystallographic Communications, 2019
Imidazolium salts are common building blocks for functional materials and in the synthesis of N-heterocyclic carbene (NHC) as σ-donor ligands for stable metal complexes. The title salt, 1,3-bis(4-hydroxyphenyl)-1H-imidazol-3-ium chloride (IOH·Cl), C15H13N2O2 +·Cl−, is a new imidazolium salt with a hydroxy functionality. The synthesis of IOH·Cl was achieved in high yield via a two-step procedure involving a diazabutadiene precursor followed by ring closure using trimethylchlorosilane and paraformaldehyde. The structure of IOH·Cl consists of a central planar imidazolium ring (r.m.s. deviation = 0.0015 Å), with out-of-plane phenolic side arms. The dihedral angles between the 4-hydroxyphenyl substituents and the imidazole ring are 55.27 (7) and 48.85 (11)°. In the crystal, O—H...Cl hydrogen bonds connect the distal hydroxy groups and Cl− anions in adjacent asymmetric units, one related by inversion (−x + 1, −y + 1, −z + 1) and one by the n-glide (x − {1\over 2}, −y + {1\over 2}, z − {1\...
Zeitschrift für Kristallographie - New Crystal Structures, 2011
Source of material 4-Amino-1-heptyl-1,2,4-triazolium bromide was prepared by refluxingas olution of 4-amino-1,2,4-triazole and 1-bromoheptane in acetonitrile for 24 h[1]. The crystalline product was deaminated using NaNO 2 /HCl [2] to yield 1-heptyl-1,2,4-triazole as ay ellowish liquid (n D 20 1.4614). This intermediate was quaternized with 1-iodo-1H,1H,2H,2H-perfluorooctane in acetonitrile with microwave heating (2 h, 160°C). The resulting 1-heptyl-4-(1H,1H,2H,2H-perfluorooctyl)-1,2,4-triazolium iodide (m.p. 277 C) was subjected to ion metathesis with lithium triflimide in at wo-phase H 2O/CH2Cl2 mixture to give the title compound in 45 %o verall yield (four steps). Suitable crystals were obtained by slow evaporation of amethanol solution (m.p. 65-66°C). Spectroscopic characteristics are in accordance with published data [3,4]. Experimental details The heptyl group of one cation is disordered and described with two split positions (approximate ratio 1:1). Atoms C23-C28 and C23A-C28A were refined with bond restraints and isotropic displacement parameters. Atoms C27 and C27A were refined with identical coordinates. Hydrogen atoms were calculated in ideal geometric positions. The Flack parameter x of 0.35(9) indicates a racemic twinning of this crystal. Ar efinement, including this twinning, offers atwin ratio of 2:1 without any change of the R value. Because the higher R value is influenced more by the disorder of the alkyl group, we decide on ar efinement as ar acemic twin. Discussion In the course of our search for liquid salts which combine affinity to fluorous solvents with acertain degree of hydrophilicity [5,6], we came across 1-heptyl-4-(1H,1H,2H,2H-perfluorooctyl)-1,2,4-triazolium bis(trifluoromethanesulfonyl)imide [3,4] as a possible candidate with areported melting point of 22°C. However, we discovered that this compound, when sythesized by the old-fashioned regioselective method [2] (in contrast to the new method [3,4], which is prone to give amixture of isomers), had a
Indian Journal of Pure & Applied Physics
Synthesis of N-((1H-benzo[d]imidazol-1-yl)methyl)-N-(2-(trifluoromethyl)phenyl)-4,5-dihydrothiazol-2-amine was done followed by its characterization by various spectral techniques. DFT studies of the compound were performed at B3LYP level to study various structural parameters and thermodynamic variables. The correlation of observed transitions with the electronic transitions had been done via NBO analysis. In addition to it, the HOMO and LUMO energy gaps and identification of sites liable for electrophilic and nucleophilic attack were done by MESP and ESP plots.
Crystallography Reports, 2010
The titled compound (1), has been synthesized and characterized by IR and 1 H NMR spectroscopy, and single crystal X ray diffraction. The compound crystallizes in the triclinic space group P 1. The crystal structure is stabilized by C-H···π and aromatic π-π interactions. There are also intramolecular N-H···N and C-H···N hydrogen bonds in the molecule. The use of quantum chemical calculations to characterise and optimise the choice of material is illustrated by ab initio treatments. Vibrational frequencies and LUMO HOMO energy difference of 1 have also been investigated by Density functional theory (DFT) and Hartree-Fock (HF) calculations. Calculated frequencies are in good agreement with the corresponding experimental data.
Synthesis and Characterization of Imidazolium Salts Bearing Fluorinated Anions
Zeitschrift für anorganische und allgemeine Chemie, 2012
The reaction of 1-methylimidazole and α,α-dibromo-p-xylene was followed by a metathesis reaction with fluorinated anion sources, which yielded new fluorinated imidazolium salts [C 6 H 4 (CH 2 (C 4 H 6 N 2 ) 2 ] 2+ 2[A]where A = BF 4 (2), PF 6 (3), CF 3 SO 3 (4), and CF 3 COO (5). The compounds were characterized by 1 H-, 13 C-, 19 F-, 31 P NMR, and IR spectroscopy. Single crystal X-ray diffraction data of compounds 2, 3, and 4 were also reported, whereas compound 5 was found to be a liquid. The solid compounds crystallized in the
Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2010
A series of new N′-3-(1H-imidazol-1-yl)propylcarbamoyl-4-halogenebenzo hydrazonate (3a–b) were obtained by reaction Ethyl 2-((4-halogene phenyl) (ethoxy) methylene) hydrazinecarboxylate (1) and N-(3-aminopropyl)imidazole (2) at 120–140 °C. Compounds (4a–b) were obtained by the reaction compound 1 and N-(3-aminopropyl)imidazole (2) at 160–180 °C. The structures of compounds 3,4 have been inferred through UV–Vis, IR, 1H/13C NMR, mass spectrometry, elemental analyses, and X-ray crystallography. DFT level 6-31G (d) calculations provided structural information. The electronic structure of compound 3a has been studied by DFT level 6-31G (d) calculations using the X-ray data. The results are accordance with X-ray data.
Acta Crystallographica Section E Crystallographic Communications, 2016
In the cation of the title hydrated molecular salt, C10H12N3O3S+·Cl−·H2O, the benzimidazolium ring system is almost planar (r.m.s. deviation = 0.006 Å) and the nitro group is inclined at an angle of 4.86 (9)° to this plane. In the crystal, C—H...O hydrogen bonds form centrosymmetricR22(20) dimers and these are further aggregated through N—H...O and O—H...Cl hydrogen bonds involving the water molecules and chloride anions. Aromatic π–π stacking interactions are also found between two parallel benzene rings or the benzene and imidazolium rings, with centroid–centroid distances of 3.5246 (9) and 3.7756 (9) Å, respectively. Analysis of the bond lengths and comparison with related compounds show that the nitro substituent is not involved in conjugation with the adjacent π-system and hence has no effect on the charge distribution of the heterocyclic ring.