Supramolecular aggregation in three 4‐aryl‐6‐(1H‐indol‐3‐yl)‐3‐methyl‐1‐phenyl‐1H‐pyrazolo[3,4‐b]pyridine‐5‐carbonitriles

Both 6‐(1H‐indol‐3‐yl)‐3‐methyl‐4‐(4‐methylphenyl)‐1‐phenyl‐1H‐pyrazolo[3,4‐b]pyridine‐5‐carbonitrile and 6‐(1H‐indol‐3‐yl)‐3‐methyl‐4‐(4‐methoxyphenyl)‐1‐phenyl‐1H‐pyrazolo[3,4‐b]pyridine‐5‐carbonitrile crystallize from dimethylformamide solutions as stoichiometric 1:1 solvates, viz. C₂₉H₂₁N₅·C₃H₇NO, (I), and C₂₉H₂₁N₅O·C₃H₇NO, (II), respectively; however, 6‐(1H‐indol‐3‐yl)‐3‐methyl‐1‐phenyl‐4‐(3,4,5‐trimethoxyphenyl)‐1H‐pyrazolo[3,4‐b]pyridine‐5‐carbonitrile, C₃₁H₂₅N₅O₃, (III), crystallizes in the unsolvated form. The heterocyclic components of (I) are linked by C—H...π(arene) hydrogen bonds to form cyclic centrosymmetric dimers, from which the solvent molecules are pendent, linked by N—H...O hydrogen bonds. In (II), the heterocyclic components are linked by a combination of C—H...N and C—H...π(arene) hydrogen bonds into chains containing two types of centrosymmetric ring, and the pendent solvent molecules are linked to these chains by N—H...O hydrogen bonds. Molecules of (III) are linked into simple C(12) chains by an N—H...O hydrogen bond, and these chains are weakly linked into pairs by an aromatic π–π stacking interaction.     

Synthesis and characterization of (6‐{[2‐(pyridin‐2‐yl)hydrazinylidene]methyl}pyridin‐2‐yl)methanol: a supramolecular and topological study

Hydrazones exhibit a versatile chemistry and are of interest for their potential use as functional molecular systems capable of undergoing reversible changes of configuration, i.e. E/Z isomerization. The title compound, C₁₂H₁₂N₄O, has an E configuration with respect to the hydrazone C=N bond. The crystal packing is formed by N—H...N and O—H...N hydrogen bonds that give a two‐dimensional layer structure and C—H...C interactions associated with layer stacking to produce the three‐dimensional supramolecular structure. These intermolecular interactions were analyzed and quantified by the Hirshfeld surface method and the two‐dimensional supramolecular arrangement was topologically simplified as a hcb network.     

Exo conformers of N‐(pyridin‐2‐yl)‐ and N‐(pyridin‐3‐yl)norbornene‐5,6‐dicarboximide crystals

Two isomeric pyridine‐substituted norbornenedicarboximide derivatives, namely N‐(pyridin‐2‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (I), and N‐(pyridin‐3‐yl)‐exo‐norbornene‐5,6‐dicarboximide, (II), both C₁₄H₁₂N₂O₄, have been crystallized and their structures unequivocally determined by single‐crystal X‐ray diffraction. The molecules consist of norbornene moieties fused to a dicarboximide ring substituted at the N atom by either pyridin‐2‐yl or pyridin‐3‐yl in an anti configuration with respect to the double bond, thus affording exo isomers. In both compounds, the asymmetric unit consists of two independent molecules (Z′ = 2). In compound (I), the pyridine rings of the two independent molecules adopt different conformations, i.e. syn and anti, with respect to the methylene bridge. The intermolecular contacts of (I) are dominated by C—H...O interactions. In contrast, in compound (II), the pyridine rings of both molecules have an anti conformation and the two independent molecules are linked by carbonyl–carbonyl interactions, as well as by C—H...O and C—H...N contacts.     

4‐(2‐Fluorophenyl)‐6‐(1H‐indol‐1‐yl)‐3‐methyl‐1‐phenyl‐1H‐pyrazolo[3,4‐b]pyridine‐5‐carbonitrile: a chain of rings built from N—H...N,C—H...N and C—H...π(arene) hydrogen bonds

In the title compound, C₂₈H₁₈FN₅, molecules are linked by a combination of N—H...N, C—H...N and C—H...π(arene) hydrogen bonds into complex double chains. The chains enclose cavities, four per unit cell, each of volume ca 102 ų and apparently containing disordered solvent.     

Structural comparison of group 7 tricarbonyl complexes of 2‐{[2‐(1H‐imidazol‐4‐yl)ethyl]iminomethyl}‐5‐methylphenolate

Two tricarbonyl complexes of rhenium(I) and manganese(I) coordinated by the ligand 2‐{[2‐(1H‐imidazol‐4‐yl)ethyl]iminomethyl}‐5‐methylphenolate are reported, viz. fac‐tricarbonyl(2‐{[2‐(1H‐imidazol‐4‐yl‐κN³)ethyl]iminomethyl‐κN}‐5‐methylphenolato‐κO)rhenium(I) methanol monosolvate, [Re(C₁₆H₁₄N₃O₄)(CO)₃]·CH₃OH, (I), and fac‐tricarbonyl(2‐{[2‐(1H‐imidazol‐4‐yl‐κN³)ethyl]iminomethyl‐κN}‐5‐methylphenolato‐κO)manganese(I), fac‐[Mn(C₁₆H₁₄N₃O₄)(CO)₃], (II), display facial coordination in a distorted octahedral environment. The crystal structure of (I) is stabilized by O—H...O, N—H...O and C—H...O hydrogen‐bond interactions, while that of (II) is stabilized by N—H...O hydrogen‐bond interactions only. These interactions result in two‐dimensional networks and π–π stacking for both structures.     

Syntheses of N‐[3‐(1‐methyl‐1H‐2‐imidazolyl)propyl]benzamides and N‐[3‐(1‐methyl‐1H‐2‐imidazolyl)propyl]benzenesulfonamides

A series of substituted N‐(4‐substituted‐benzoyl)‐N‐[3‐(1‐methyl‐1H‐imidazol‐2‐yl)propyl]amines ( 13 ) and N‐arylsulfonyl‐N‐[3‐(1‐methyl‐1H‐imidazol‐2‐yl)propyl]amines ( 14 ) were prepared from the reaction of 3‐(1‐methyl‐1H‐imidazol‐2‐yl)propan‐1‐amine ( 7 ) with substituted benzoyl chloride or substituted‐benzene sulfonyl chloride respectively. Compound 7 was prepared by two independent methods.     

Design,Synthesis and Antifungal Evaluation of N‐Substituted‐1‐(3‐chloropyridin‐2‐yl)‐N‐(pyridin‐4‐yl)‐5‐(trifluoromethyl)‐1H‐pyrazole‐4‐carboxamide Derivatives

A series of 1‐(3‐chloropyridin‐2‐yl)‐5‐(trifluoromethyl)‐1H‐pyrazole‐4‐carboxamide derivatives which have di‐substituents on nitrogen were designed and synthesized. Bioassay results showed that all the synthetic compounds exhibited lower antifungal activities against Gibberella zeae, Cytospora mandshurica, and Fusarium oxysporum than T ₃ (14.7, 21.1, and 32.7 μg/mL), but some of them exhibited better activities against Botrytis cinerea, Phytophthora infestans, and Sclerotinia sclerotiorum than T ₃ (>200, >200, and >200 μg/mL); the EC₅₀ values of 7d and 7c against B. cinerea were 94.9 and 56.2 μg/mL, respectively. The EC₅₀ values of 7a , 7d , and 7c against S. sclerotiorum were 73.5, 78.7, and 68.5 μg/mL, respectively.     

8‐tert‐Butyl‐7‐(4‐chlorophenyl)‐10‐phenyl‐5,6‐dihydro‐10H‐benzo[h]pyrazolo[3,4‐b]quinoline

The title compound, C₃₀H₂₆ClN₃, crystallizes with Z′ = 3 in the P space group. The three independent molecules have very similar, although not identical, conformations, with almost perfect screw‐boat forms adopted by the non‐aromatic carbocyclic rings. Four independent C—H...π(arene) hydrogen bonds link the molecules into centrosymmetric six‐component aggregates.     

Cocrystallization of two tautomers: 4‐(1‐{[4‐(dimethylamino)benzylidene]hydrazono}ethyl)benzene‐1,3‐diol and 6‐[(E)‐1‐{[4‐(dimethylamino)benzylidene]hydrazino}ethylidene]‐3‐hydroxycyclohexa‐2,4‐dien‐1‐one (1/1)

Two different tautomeric forms of a new Schiff base, C₁₇H₁₉N₃O₂·C₁₇H₁₉N₃O₂, are present in the crystal in a 1:1 ratio, namely the enol–imine form 4‐(1‐{[4‐(dimethylamino)benzylidene]hydrazono}ethyl)benzene‐1,3‐diol and the keto–amine form 6‐[(E)‐1‐{[4‐(dimethylamino)benzylidene]hydrazino}ethylidene]‐3‐hydroxycyclohexa‐2,4‐dien‐1‐one. The tautomers are formed by proton transfer between the hydroxy O atom and the imine N atom and are hydrogen bonded to each other to form a one‐dimensional zigzag chain along the crystallographic b axis via intermolecular hydrogen bonds.     

N,N′‐Dicyclohexyl‐N‐[4‐(1H‐indol‐3‐yl)butanoyl]urea

The title compound, C₂₅H₃₅N₃O₂, is a novel urea derivative. Pairs of intermolecular N—H...O hydrogen bonds join the molecules into centrosymmetric R₂²(12) and R₂²(18) dimeric rings, which are alternately linked into one‐dimensional polymeric chains along the [010] direction. The parallel chains are connected via C—H...O hydrogen bonds to generate a two‐dimensional framework structure parallel to the (001) plane. The title compound was also modelled by solid‐state density functional theory (DFT) calculations. A comparison of the molecular conformation and hydrogen‐bond geometry obtained from the X‐ray structure analysis and the theoretical study clearly indicates that the DFT calculation agrees closely with the X‐ray structure.     

Antibacterial 4‐amino‐N‐(5‐methyl­isoxazol‐3‐yl)‐N‐[(4‐oxo‐2‐phenyl‐4H‐1‐benzopyran‐6‐yl)methyl]benzenesulfonamide

In the mol­ecule of the title compound, C₂₆H₂₁N₃O₅S, a new type of sulfonamide derivative with potential antibacterial activity, the flavone moiety is almost planar. The isoxazole and amino­phenyl rings are also planar and make dihedral angles of 77.0 (2) and 81.4 (1)°, respectively, with the best plane of the flavone ring system. The crystal structure is stabilized by intra‐ and inter­molecular hydrogen bonds.     

Construction and photocatalytic properties of two metal‐mediated coordination polymers based on benzene‐1,3,5‐tricarboxylic acid and trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene

With the rapid development of modern industry, water pollution has become an intractable environmental issue facing humans worldwide. In particular, the organic dyes discharged into natural water from dyestuffs, dyeing and the textile industry are the main sources of pollution in wastewater. To eliminate these types of pollutants, degradation of organic contaminants through a photocatalytic technique is an effective methodology. To exploit more crystalline photocatalysts for the degradation of organic dyes, two coordination polymers, namely catena‐poly[[(3,5‐dicarboxybenzene‐1‐carboxylato‐κO ¹)silver(I)]‐μ‐trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene‐κ²N :N ′], [Ag(C₉H₅O₆)(C₁₂H₁₀N₂)]_n or [Ag(H₂BTC)(3,4′‐bpe)]_n , (I), and poly[[(μ₃‐5‐carboxybenzene‐1,3‐dicarboxylato‐κ⁴O ¹,O ^1′:O ³:O ³)[μ‐trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene‐κ²N :N′ ]cadmium(II)] monohydrate], {[Cd(C₉H₄O₆)(C₁₂H₁₀N₂)]·H₂O}_n or {[Cd(HBTC)(3,4′‐bpe)]·H₂O}_n , (II), have been prepared by the hydrothermal reactions of benzene‐1,3,5‐tricarboxylic acid (H₃BTC) and trans‐1‐(pyridin‐3‐yl)‐2‐(pyridin‐4‐yl)ethene (3,4′‐bpe) in the presence of AgNO₃ or Cd(NO₃)₂·4H₂O, respectively. These two title compounds have been structurally characterized by IR spectroscopy, elemental analysis, single‐crystal X‐ray diffraction and powder X‐ray diffraction. In (I), the Ag^I ions and organic ligands form a one‐dimensional coordination chain, and adjacent coordination chains are connected by Ag…O interactions to give rise to a two‐dimensional supramolecular network. Each two‐dimensional network is entangled with other equivalent networks to generate an infrequent interlocked 2D→3D (2D and 3D are two‐ and three‐dimensional, respectively) supramolecular framework. In (II), the Cd^II ions are bridged by the HBTC²⁻ and 3,4′‐bpe ligands, which lie across centres of inversion, to give a two‐dimensional coordination network. The thermal stabilities and photocatalytic properties of the title compounds have also been studied.     

CdII and CoII coordination polymers constructed from benzene‐1,4‐dicarboxylic acid and 2‐(pyridin‐3‐yl)‐1H‐benzimidazole ligands

In poly[aqua(μ₃‐benzene‐1,4‐dicarboxylato‐κ⁵O¹,O^1′:O¹:O⁴,O^4′)[2‐(pyridin‐3‐yl‐κN)‐1H‐benzimidazole]cadmium(II)], [Cd(C₈H₄O₄)(C₁₂H₉N₃)(H₂O)]_n, (I), each Cd^II ion is seven‐coordinated by the pyridine N atom from a 2‐(pyridin‐3‐yl)benzimidazole (3‐PyBIm) ligand, five O atoms from three benzene‐1,4‐dicarboxylate (1,4‐bdc) ligands and one O atom from a coordinated water molecule. The complex forms an extended two‐dimensional carboxylate layer structure, which is further extended into a three‐dimensional network by hydrogen‐bonding interactions. In catena‐poly[[diaquabis[2‐(pyridin‐3‐yl‐κN)‐1H‐benzimidazole]cobalt(II)]‐μ₂‐benzene‐1,4‐dicarboxylato‐κ²O¹:O⁴], [Co(C₈H₄O₄)(C₁₂H₉N₃)₂(H₂O)₂]_n, (II), each Co^II ion is six‐coordinated by two pyridine N atoms from two 3‐PyBIm ligands, two O atoms from two 1,4‐bdc ligands and two O atoms from two coordinated water molecules. The complex forms a one‐dimensional chain‐like coordination polymer and is further assembled by hydrogen‐bonding interactions to form a three‐dimensional network.     

2‐(3,4‐Dichlorophenylimino)‐5‐((3‐(p‐substitutedphenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)methylene)thiazolidin‐4‐one as an Antibacterial,Antifungal and Antimycobacterial Agent

2‐(3,4‐Dichlorophenylimino)‐5‐((3‐(p‐substitutedphenyl)‐1‐phenyl‐1H‐pyrazol‐4‐yl)methylene) thiazolidin‐4‐one has been selected as a target bio‐active molecules. Newly synthesized compounds were screened with Eschericha coli (MTCC 443), Pseudomonas aeruginosa (MTCC 1688), Staphylococcus aureus (MTCC 96), Streptococcus pyogenes (MTCC 442) for antibacterial, Candida albicans (MTCC 227), Aspergillus niger (MTCC 282), Aspergillus clavatus (MTCC 1323) for antifungal activity and H ₃₇ Rv for antimycobacterial activity. Compounds 3a , 3c , 3d , 3e , and 3h are potentially active against Staphylococcus aureus , while 3h is active against C. albicans . Compounds 3d and 3f are active against H ₃₇Rv for mycobacterium tuberculosis. Other possesses moderate to good activity. The structures of synthesized compounds were firmly established by well‐defined elemental analyses (C, H, N, S/O) and spectral analysis technique likes, IR, ¹H NMR and GC–MS.     

Isomeric 3‐ and 4‐chloro‐N‐[1‐(1H‐pyrrol‐2‐yl)ethylidene]aniline

The title isomers, namely 3‐chloro‐N‐[1‐(1H‐pyrrol‐2‐yl)ethylidene]aniline, (I), and 4‐chloro‐N‐[1‐(1H‐pyrrol‐2‐yl)ethylidene]aniline, (II), both C₁₂H₁₁ClN₂, differ in the position of the chlorine substitution. Both compounds have the basic iminopyrrole structure, which shows a planar backbone with similar features. The dihedral angle formed by the planes of the pyrrole and benzene rings is 75.65 (7)° for (I) and 86.56 (8)° for (II). The H atom bound to the pyrrole N atom is positionally disordered and partial protonation occurs at the imino N atom in (I), while this phenomenon is absent from the structure of (II). Packing interactions for both compounds include intermolecular N—H...N hydrogen bonds and C—H...π interactions, forming centrosymmetric dimers for both (I) and (II).     

Octyl 1‐(5‐tert‐butyl‐1H‐pyrazol‐3‐yl)‐2‐(4‐chlorophenyl)‐1H‐benzimidazole‐5‐carboxylate: complex sheets built from N—H...N,C—H...N and C—H...O hydrogen bonds

In the title compound, C₂₉H₃₅ClN₄O₂, the bond lengths provide evidence for aromatic delocalization in the pyrazole ring but bond fixation in the fused imidazole ring, and the octyl chain is folded, rather than adopting an all‐trans chain‐extended conformation. A combination of N—H...N, C—H...N and C—H...O hydrogen bonds links the molecules into sheets, in which the hydrogen bonds occupy the central layer with the tert‐butyl and octyl groups arranged on either side, such that the closest contacts between adjacent sheets involve only the octyl groups. Comparisons are made with the supramolecular assembly in some simpler analogues.     

N‐(3‐tert‐Butyl‐1‐phenyl‐1H‐pyrazol‐5‐yl)‐N‐(4‐methoxybenzyl)acetamide: a hydrogen‐bonded chain of centrosymmetric rings

The molecule of the title compound, C₂₃H₂₇N₃O₂, adopts a conformation having no internal symmetry so that the compound exhibits conformational chirality. The molecules are linked by a combination of C—H...O and C—H...π(arene) hydrogen bonds into a chain of rings in which two types of centrosymmetric ring alternate.     

Synthesis and antimicrobial evaluation of new 1‐{[4‐(4‐Halogenophenyl)‐4H‐1,2,4‐ triazol‐3‐yl]sulfanyl}acetyl‐4‐substituted thiosemicarbazides and products of their cyclization

By the reaction of hydrazides of 4‐(4‐halogenophenyl)‐4H‐1,2,4‐triazol‐3‐yl‐sulfanyl acetic acid with isothiocyanate, 1‐acyl‐4‐substituted thiosemicarbazide derivatives ( 7–19 ) were obtained. The cyclization of compounds ( 7–19 ) in the presence of 2% NaOH led to the formation of compounds ( 20–26 ) containing two 1,2,4‐triazole rings connected by a methylenesulfanyl group. The new compounds were tested for their in vitro antimicrobial activity. Some of the tested compounds ( 9, 12, 18, 21, 22 ) showed activity against the reference strains of Gram‐positive bacteria with the MIC (minimal inhibitory concentration) = 125 to >1000 μg/mL. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 23:117–121, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20758     

Synthesis and Antimicrobial Activity of N‐Aryl‐4‐(cyano/alkoxycarbonyl)‐5‐(pyridin‐3‐yl)‐1H/3H‐1,2,3‐triazole Derivatives

A convenient synthesis of a new series of N‐aryl‐5‐(pyridin‐3‐yl)‐1H/3H‐1,2,3‐triazole‐4‐carbonitriles and alkyl N‐aryl‐5‐(pyridin‐3‐yl)‐1H/3H‐1,2,3‐triazole‐4‐carboxylic acid esters is reported. The newly synthesized 5‐(pyridin‐3‐yl)‐1,2,3‐triazole derivatives are evaluated for their antibacterial and antifungal activity. Some of these triazole derivatives have exhibited moderate antimicrobial activity.