A set of new di(thiophen-2-yl)-(1,2,3-triazol-4-yl)thiazole compounds 6a-g were synthesized in excellent yields, 90-95 %, via the cyclization reaction of thioamide 4 (obtained through the reaction of (E)-1,3-di(thiophen-2-yl) prop-2-en-1-one 3 with thiosemicarbazide in sodium ethoxide) with seven different 4-bromomacetyl-5-methyl-1-aryl-1,2,3-triazoles 5a-g. The structures of the new synthesized compounds were elucidated via variable spectroscopic studies and confirmed by single-crystal X-ray studies for five compounds (6a,b,d,e,g). The antimicrobial activity was evaluated for the new compounds using the agar well diffusion method. Compounds 6a-g showed moderate activity against two Gram-positive bacteria (S. aureus and L. monocytogenes) and fungal strain of C. albicans.

This study employed 9,9'-bifluorenyl-9,9'-diol (H) as a host compound for the separation of mixed anilines through host-guest chemistry strategies. H successfully enclathrated aniline (ANIL), N-methylaniline (NMA) and N,N-dimethylaniline (DMA) with 1 : 1, 1 : 1 and 3 : 2 H : G ratios, respectively, when it was crystallized independently from each of these guest solvents. In the equimolar guest competition experiments, H preferentially included NMA, followed by ANIL, while DMA was consistently disfavoured. The binary guest competition experiments demonstrated that H possesses the ability to separate all NMA/DMA solutions (favouring NMA), since significant host selectivities were observed in these experiments. SCXRD analyses showed that the preferred guest, NMA, in its complex with H, experienced both classical and non-classical hydrogen bonding with the host molecule, while ANIL (second preferred), in the H·ANIL complex, engaged only in classical hydrogen bonds with H; DMA (least favoured) in 3(H)·2(DMA), on the other hand, did not experience significant hydrogen bonding with the host molecule. Moreover, it was also noted that the H·NMA complex possessed the highest crystal density of the three inclusion compounds, reflecting a denser packing and a greater thermodynamic stability compared with the ANIL- and DMA-containing complexes. Hirshfeld surface analyses revealed that the three-dimensional surfaces surrounding the ANIL and NMA guest molecules had pronounced red regions, consistent with the hydrogen bonding observed in their crystal structures, while the surface around DMA showed only a small red area, reflecting the absence of any significant hydrogen bonding. Finally, thermal experiments confirmed that, of the three complexes, H·NMA possessed the highest thermal stability, followed by H·ANIL, while 3(H)·2(DMA) was least stable, in accordance with the host selectivity behaviour in guest mixtures. In summary, this investigation demonstrated that H has exceptional separation potential for all NMA/DMA mixtures when employing a host-guest chemistry approach.

The crystallization of N,N '-bis(9-(4-methoxyphenyl)-9H-xanthen-9-yl)ethane-1,2-diamine (H) from each of the xylene and ethylbenzene isomers (o-Xy, m-Xy, p-Xy and EB) revealed that only the xylenes formed inclusion compounds with this host species, while EB was not included. The host : guest (H : G) ratios of the successfully formed complexes were 1 : 1, 1 : 1 and 1 : 2 for the o-Xy, m-Xy and p-Xy complexes, respectively. Guest solvents were also permitted to compete and crystallizations of H from such solutions revealed an unequivocal host selectivity in the order o-Xy > EB > m-Xy > p-Xy. Further binary guest competition experiments also demonstrated that this host species may serve as a purification tool, through host-guest chemistry protocols, of EB and m-Xy solvents that are tainted with small quantities of o-Xy and EB, correspondingly. Single crystal X-ray diffraction (SCXRD) analyses of the three single solvent complexes were employed in order to understand the host selectivity behaviour. The guest molecules in H & centerdot;o-Xy and H & centerdot;m-Xy (with guest solvents more preferred by H in the guest competition experiments) were accommodated in endless and unidirectional channels, and all of these guest species experienced (guest)C-H & ctdot;pi(host) stabilizing interactions with H. This was not the case for the guest species in H & centerdot;2(p-Xy) (with the least favoured guest solvent). Here, two distinct types of guest molecules were observed, one being ordered and the other displaying positional disorder over two positions. Both of the latter disorder guest components were involved in this kind of interaction ((guest)C-H & ctdot;pi(host)) with H, while the ordered guest species appeared to be held in the complex through, predominantly, steric effects alone, and no (guest)C-H & ctdot;pi(host) or other close contacts were identified in this instance. This observation explained the distinct lack of selectivity of H for p-Xy relative to the remaining isomers in the guest competition experiments. Interestingly, the ordered and disordered guest molecules in this complex also occupied separate channel voids in the inclusion compound which were aligned along different axes in the unit cell. Finally, thermal analyses demonstrated that the three single solvent complexes in this investigation possessed comparable relative thermal stabilities as their guest release onset temperatures spanned a narrow range (T-on 39.2-41.7 degrees C).

Chemical structure of new nine molecules was supported by X-ray crystallography data. 3,5-Bis(4-bromophenyl)-4,5-dihydro-1H-pyrazole-1-carbothioamide 4 was used as precursor for preparation of the nine novel 2-(3,5-bis (4-bromophenyl)-4,5-dihydro-1H-pyrazol-1-yl)-4-arylthiazoles 7a-f and 9a-c. The preparation involved the reaction of thioamide 4 with different alpha-bromoketones 6a-f and 8a-c. The structures of the synthesized compounds were determined using spectral spectroscopy and elemental analyses. The antimicrobial activity was evaluated for the new compounds using the agar well diffusion method. Compounds 7a-f and 9a-c showed moderate activity against Staphylococcus aureus, while 9a-c showed moderate activity Bacillus cereus. Only 7c and 7d showed moderate activity against E. coli.

The title complex, [RuCl 2 (C 6 H 6 )(C 21 H 33 P)] or (η 6 -C 6 H 6 )((C 6 H 11 ) 2 ( i PrC 6 H 4 )P)RuCl 2 crystallizes in the space group P 1 with one molecule in the asymmetric unit. The Ru II atom is located at distances of 2.3830 (7), 2.3925 (8), 2.4269 (8), and 1.6919 (3) Å from the P, the two Cl ligands, and the centroid of the benzene molecule, respectively. A cone angle of 159° was calculated for the steric pocket of the phosphane ligand. Positional disorder over two sets of sites in the methine and one of the methyl groups of the isopropyl substitutent resulted in a refined 0.528 (5):0.472 (5) ratio. The crystal packing is consolidated by non-classical C—H...Cl interactions.

Herein we report on the host ability of di-(9-(p-chlorophenyl)xanthen-9-yl) peroxide (H) for the four isomers of the C8H10 aromatic crude oil fraction, namely o-, m- and p-xylene (o-Xy, m-Xy and p-Xy) and ethylbenzene (EB). Crystallization of H from each of these solvents revealed that both o-Xy and p-Xy formed complexes with this host species, while m-Xy and EB were not enclathrated. 1H-NMR spectroscopic analysis of the resultant solids demonstrated that the host : guest (H : G) ratios for the two complexes were 1 : 1 and 4 : 1, respectively. The host compound was subsequently crystallized from various equimolar and binary non-equimolar mixtures of these isomers, and a remarkable selectivity for o-Xy was observed. In fact, it was demonstrated that H has the ability to separate the 20/80 and 40/60 o-Xy/m-Xy as well as the 40/60, 50/50, 60/40 and 80/20 o-Xy/EB mixtures: extremely high selectivity coefficients (K), in favour of o-Xy, were calculated in each of these instances. This is an extraordinary finding given the difficulty of separating such mixtures by the more conventional fractional distillations owing to the comparable physical properties of these guest solvents. The two complexes as well as guest-free H were subjected to both single crystal X-ray diffraction and thermal analyses. The former technique demonstrated that the preferred guest species, o-Xy, was accommodated in the complex in discrete cavities, while disfavoured p-Xy experienced wide open channel occupation. This observation explains the affinity of H for the ortho isomer relative to p-Xy when guests competed, since enhanced thermal stabilities of complexes are associated with the former type of accommodation (isolated voids). Furthermore, o-Xy experienced nonclassical H-bonding with the host molecule, an interaction type not observed in the case of the para isomer. Additionally, from the thermal experiments, the p-Xy-containing inclusion compound, plausibly as a result of its retention in wide open channels, possessed an extremely low thermal stability at ambient temperature and pressure, while the complex with o-Xy, which occupied discrete cavities, was stable in analogous conditions.

In the present investigation, 9,9’-bifluorenyl-9,9’-diol ( H ) was assessed for its host potential for anisole (ANI) and the three methylanisole isomers (2MA, 3MA and 4MA), through crystallization experiments, and it was thus demonstrated that H has the ability to enclathrate each of these four guest solvents. Additionally, the selectivity behaviour of H was evaluated when presented with mixtures of these anisoles, and the results suggested that each of the methylated anisoles was preferred in one or another instance, dependent upon the other guest solvent/s present, while, more notably, ANI remained consistently disfavoured. However, the observed host selectivity was not appropriate to suggest that H may serve as a host candidate for the separation of ANI/MA solutions through host‒guest chemistry protocols. Single crystal X-ray diffractometric analyses on each of the complexes produced in this work showed that, with the exception of H ·0.75(4MA 2 ), extreme guest disorder and/or severe twinning of the crystals existed, and Platon’s SQUEEZE routine was required in most instances. As such, these experiments did not provide explanations for the selectivity behaviour of the host compound in the mixed guest solutions through a consideration of the host···guest interactions present in each complex. However, from the successful obtention of the crystal structure of H ·0.75(4MA 2 ), it was observed that the guest species was retained in the crystals of the complex by means of both (host)O–H···O(guest) and (host/guest)C–H···C–C(guest/host) close contacts. Thermal analysis demonstrated that, while the ANI, 2MA and 3MA inclusion complexes were unstable at ambient conditions, the two 4MA-containing inclusion compounds possessed stability, and comparably so, since similar guest release onset temperatures for their guest release events were observed (T on , 65.9 and 68.8°C). These observations provide some explanation for the preference of H for 4MA in a number of the guest competition experiments, more especially those that were equimolar and binary in nature.

The title compound, C8H8N2S, is a rhodanided derivative of ortho-toluidine. Classical hydrogen bonds of the N-H⋯N type, as well as C-H⋯N contacts, connect mol-ecules of the title compound into a three-dimensional network in the crystal structure.

In the present investigation, the wheel-and-axle host compound, 1,4-phenylene-bis(di-p-fluorophenylmethanol) (H1), was revealed to have inclusion ability for three saturated heterocyclic organic solvents, namely DIO, MOR and PIP, in addition to the previously reported complex with PYR. Guest competition experiments demonstrated H1 to possess an affinity for PIP and PYR while, in 20:80 PYR/DIO, 40:60 PYR/DIO and 20:80 PIP/DIO binary solutions, the host affinity for PYR, PYR and PIP, respectively, was overwhelming (K > 10). Crystal structure analysis of the complexes showed that favoured PYR was held in the crystals of its complex by means of a much shorter (guest)N‒H···O(host) hydrogen bond compared with the other nitrogen-containing guest solvents (DIO was also retained in its complex by means of a classical hydrogen bond). Plausibly as a result of this observation, the PYR-containing complex had the higher crystal density and was thermally more stable than the other complexes, explaining the affinity of H1 for PYR. The reasons for the host selectivity for PIP was less clear.

In the present investigation, the wheel-and-axle compound 1,4-phenylene-bis(di-p-tolylmethanol) (H) was demonstrated to have efficient host ability for the saturated heterocyclic guest solvents dioxane, morpholine and piperidine (DIO, MOR and PIP), known toxins in wastewater. Host: guest (H: G) ratios varied, and from 1H-NMR experiments, were calculated to be 1:4, 1:1 and 1:2, respectively. Previously, H was reported to form a complex also with the unsaturated heterocyclic solvent pyridine (PYR, H:G 1:3). When H was crystallized from mixtures containing two or more of the four guests, MOR and PYR were found to be favoured solvents, with DIO and PIP being less likely to be selected by the host species. In order to understand these selectivity observations, single crystal X-ray diffraction (SCXRD) experiments were performed on each single solvent inclusion compound, as well as thermogravimetric (TG) and differential scanning calorimetric (DSC) analyses. These latter two analytical techniques provided an understanding for the host selectivity behaviour in mixed guest crystallization experiments in that the MOR- and PYR-containing complexes were significantly more stable than those with DIO and PIP, which were not stable even at ambient conditions. Furthermore, least favoured DIO formed crystals with the lowest density of the four, alluding to a looser molecular packing in the complex, explaining the low host selectivity for this guest species. A brief comparison of these results with earlier reports pertaining to related host compounds 1,4-phenylene-bis(diphenylmethanol) (H1) and 1,4-phenylene-bis(di-p-fluorophenylmethanol) (H2) in the same guest solvents was also undertaken and is reported upon here.

N,N '-Bis(9-(4-chlorophenyl)-9-thioxanthenyl)ethylenediamine (H1) and N,N '-bis(9-(4-chlorophenyl)-9-xanthenyl)ethylenediamine (H2) were investigated as possible separation agents for mixtures of pyridine (PYR) and methylpyridine isomers (2MP, 3MP, and 4MP) through supramolecular chemistry. MPs are present as mixtures in the chemical industry, but fractional distillation is challenging since they have a narrow boiling range, and so alternative and greener separation strategies are necessary. Initially, the host ability of H1 and H2 was assessed for these solvents; each pyridine was enclathrated by both host compounds. When guests competed, H1 and H2 behaved selectively: host affinities were in the order 3MP > PYR > 4MP >> 2MP (H1) and 2MP > 3MP > PYR >> 4MP (H2). Moreover, H1 was able to separate the 80 : 20, 60 : 40 and 50 : 50 PYR/2MP, 20 : 80 3MP/PYR and 60 : 40 PYR/4MP mixtures: high selectivity coefficients were calculated (K >= 10). H2 fared even better: each of the 20 : 80 2MP/PYR, 40 : 60 and 20 : 80 3MP/PYR, all mixtures of PYR/4MP except 20 : 80, all solutions of 2MP/4MP and 20 : 80 3MP/4MP mixtures may be purified in this fashion. Thermal experiments demonstrated that the favoured guest solvents formed the more stable complexes with H1 and H2. Furthermore, the SCXRD analyses provided reasons for the host affinity of H1 for 3MP, relative to the least preferred 2MP, when presented with guest mixtures. 3MP experienced three C-H & ctdot;pi close contacts with the host molecule, while this type of interaction was not observed in the 2MP-containing complex. Finally, 4MP was consistently disfavoured by H2 as a result of the fact that this guest solvent was accommodated in wide open multidirectional channels and, as a result, was the least stable complex, confirmed by thermal analysis, while the favoured 2MP formed the most stable complex of the four, being housed in unidirectional channels.

The present investigation focussed on assessing the ability of (4R,5R)-bis(diphenylhydroxymethyl)-2-spiro-1’-cyclohexane-1,3-dioxolane (TADDOL6) to separate pyridine/methylpyridine (picoline) mixtures through supramolecular chemistry protocols. At the outset, TADDOL6 was revealed to possess the ability...

The title compound, C28H20O4·C4H4O, is the cyclic ester anhydride of benzilic acid. A disordered solvent molecule is present in the structure. The asymmetric unit contains half the acid-derived molecule. C—H...O contacts connect the constituents of the title compound into a three-dimensional network.

The title compound, C14H18O6·H2O, is a partially protected derivative of D-glucopyranose. The asymmetric unit contains one sugar molecule and one water molecule of crystallization. Classical hydrogen bonds of the O—H...O type form a cooperative set and are observed next to a C—H...O(water) contact, connecting the entities of the asymmetric unit into a three-dimensional network.

The title compound, C8H8N2S, is a rhodanided derivative of ortho-toluidine. Classical hydrogen bonds of the N—H...N type, as well as C—H...N contacts, connect molecules of the title compound into a three-dimensional network in the crystal structure.

The present investigation focused on the complexation behavior of a peroxide, specifically di(9-(p-trifluoromethylphenyl)xanthen-9-yl) peroxide (H), as a host compound for the potential guest species anisole (ANI) and 2-, 3- and 4-methylanisole (2MA, 3MA and 4MA) through crystallization experiments from each of these organic solvents. The results obtained demonstrate that H has the ability to form 1:1 host:guest inclusion complexes with each of ANI and 4MA, while no enclathration was observed when the potential guests were 2MA and 3MA. Furthermore, it was established from crystallization experiments from mixed guests that H possesses an overwhelming affinity for ANI followed by 4MA; equimolar mixed guest experiments showed the host selectivity to thus be in the order ANI > 4MA > 3MA > 2MA. Importantly, H was also shown to have the ability to separate 20:80 ANI/2MA and 60:40 4MA/2MA mixtures, in favor of ANI and 4MA, respectively (high selectivity coefficients, K, were calculated in these two instances). Single crystal X-ray diffraction (SCXRD) analyses indicated that 4MA engages in one (host)C-Hpi(guest) and one (guest)C-Hpi(host) interaction, while the overwhelming selectivity for ANI was attributed to the existence of two stabilizing (host)C-Fpi(guest) bonds to each guest molecule. Furthermore, thermoanalytical experiments demonstrated that the ANI-containing inclusion complex was significantly more stable than that with 4MA, explaining the host selectivity witnessed in the mixed guest experiments. Molecular modeling at the molecular mechanics and density functional theory levels showed that the geometries adopted by H in the crystals obtained without guest inclusion, as well as for the complexes with ANI and 4MA, are essentially the same, and correspond to a conformer that is 13.4 kJmol(-1) higher in energy than the global energy minimum conformer for the peroxide.

Refractory sulfur compounds in fuel oils combust, releasing sulfur oxides (SOx) into the atmosphere, which is a significant source of pollution. In this study, we focused on comparing the surface properties and hydrodesulfurization (HDS) activity of CoMo-(L)/γ-Al2O3 containing chelating ligands (L), specifically acetic acid (AA), with those of ethylenediaminetetraacetic acid (EDTA), citric acid (CA). CoMo/γ-Al2O3, CoMo-AA/γ-Al2O3, CoMo-EDTA/γ-Al2O3 and CoMo/γ-Al2O3 were prepared by hydrothermal treatment of the mixtures of Co(NO3)2.6H2O and (NH4)6Mo7O24.4H2O with stoichiometric Co/Mo ratios and enriched with chelating ligands (L=AA, CA and EDTA). Based on the product distributions of the hydrodesulfurization (HDS) of dibenzothiophene (DBT), a reaction pathway of dibenzothiophene (DBT) HDS was proposed to follow hydrogenation (HYD) and direct desulfurization (DDS) routes. In addition, the ligand modification of CoMo/γ-Al2O3 catalysts resulted in enhancement of surface properties and HDS activity which is in the order of CoMo-CA/γ-Al2O3 (98 %)> CoMo-AA/γ-Al2O3 (94 %) > CoMo-EDTA/γ-Al2O3 (90 %) > CoMo/γ-Al2O3 (43 %). CoMo-AA/γ-Al2O3 presented a higher HYD/DDS ratio compared to CoMo-CA/γ-Al2O3, CoMo-EDTA/γ-Al2O3, and CoMo/γ-Al2O3, respectively which makes it a promising HDS catalyst.

This study presents the synthesis, structural characterization, and multifunctional applications of a novel 4,5 ' bithiazole derivative (3), obtained in 88% yield via a piperidine-catalyzed reaction. Single-crystal X-ray diffraction revealed its monoclinic P21/c structure, stabilized by intermolecular C-H center dot center dot center dot S/N interactions, while Hirshfeld surface analysis clarified the supramolecular arrangement. Density Functional Theory (DFT) calculations validated the experimental data, showing excellent agreement between theoretical and observed geometries. The compound exhibited promising optoelectronic properties, including a wide band gap (5.1 eV), high refractive index, and wavelength-dependent dielectric behavior, emphasizing its potential for sensing and optoelectronic applications. Biologically, compound 3 demonstrated remarkable antibiofilm activity against methicillin-resistant Staphylococcus aureus (MRSA), achieving 98.1% inhibition, and relatively selective cytotoxicity against Caco2 cancer cells (IC50 = 297.36 mu g/mL) compared to normal Wi38 cells (IC50 = 336.47 mu g/mL). Molecular docking revealed strong binding to the epidermal growth factor receptor (EGFR, PDB:1M17), highlighting its dual therapeutic potential. These findings suggest compound 3 as a multipurpose candidate for both biomedical and materials science applications.

The study investigates the synthesis, structure, optical features, and bioactivity of a new bis(thienylpyrazolyl)carbohydrazide derivative (compound 3). The compound 3 was prepared, in 90 % yield, via condensation of 1-phenyl-5-(thiophen-2-yl)-1H-pyrazole-3-carbohydrazide 1 with 1-phenyl-3-(thiophen-2-yl)-1H-pyrazole-4-carbaldehyde 2. X-ray crystallography analysis indicated a monoclinic crystal structure stabilized by hydrogen bonding and noncovalent interactions. Density functional theory (DFT) correlated effectively with experimental results, revealing unique molecular electrostatic potential (MEP) results. Experimental and DFT investigations indicated a large energy gap (5.18 eV; DFT: 4.08 eV), highlighting its stability and potential for light-sensitive applications. Optical investigations demonstrated a wavelength-dependent reflectance and adjustable dielectric characteristics, indicating stability and advantageous in optoelectronic and biological applications. Bioactivity revealed significant antibiofilm activity with up to 97.1 % inhibition at elevated doses. It exhibited selective cytotoxicity, with an IC50 of 331.81 μg/mL against normal Wi38 cells, and 147.57 μg/mL for Caco2 cancer cells, indicating potential for treatment with fewer side effects. These results establish it as a viable medical agent for combating infections, and cancer, especially in immunocompromised patients. Molecular docking revealed a strong binding affinity toward the epidermal growth factor receptor (EGFR), with a docking score of -9.8 kcal mol-1, confirming stable ligand-receptor interactions support its observed anticancer.

The present investigation centred around the host ability of two novel compounds, N,N '-bis(5-phenyl-5-dibenzo[a,d]cycloheptenyl)propane-1,3-diamine (DB3) and N,N '-bis(9-phenyl-9-thioxanthenyl)butane-1,4-diamine (S4), for guest solvents cyclohexanone and its methylcyclohexanone isomers (Cyc, 2MeCyc, 3MeCyc and 4MeCyc). While DB3 formed complexes with each of these organic solvents, S4 only included 4MeCyc. All complexes were characterized by 1 : 1 host : guest ratios. With the view to assessing whether these host compounds have the potential to separate mixtures of the cyclohexanones, each one was crystallized from various guest mixtures. It was determined that such separations would not be feasible through supramolecular chemistry strategies with these two host species owing to low calculated selectivity coefficients (K). This was despite the observed selectivity of DB3 for 4MeCYC and Cyc in the mixed guest experiments. However, a thorough scrutiny of the five novel complexes was subsequently undertaken, and the crystal structures, through SCXRD analysis, demonstrated that Cyc, a preferred guest solvent, when included by DB3, occupied highly constricted channels, while these were comparatively wider and more open in the complexes with the MeCycs. Furthermore, preferred Cyc was the only guest molecule that engaged in a classical hydrogen bond with DB3, and Hirshfeld surface analyses showed this guest (which only has 10 hydrogen atoms) to be involved in the greater quantity of (guest)H & ctdot;H(host) interactions (the MeCyc molecules have 12 hydrogen atoms and experienced less of this type of interaction). All of these observations provide an explanation for the affinity of DB3 for Cyc (but not for 4MeCyc). These SCXRD analyses further demonstrated that the geometry of the diamino linker in the DB3 complexes was more folded in nature while, in S44MeCyc, this was in an extended zig-zag orientation. Finally, thermal analyses on each of the complexes, unsurprisingly, demonstrated the Cyc-containing complex with DB3 to be the most stable one.