(E)-5-(4-Methyl-benzyl-idene)-1-phenyl-4,5,6,7-tetra-hydro-1H-indazol-4-one.

In the title compound, C21H18N2O, the non-aromatic six-membered ring adopts a distorted envelope conformation with one of the methyl-ene-C atoms being the flap atom. The dihedral angle between the phenyl and 4-tolyl rings is 75.3 (1)°. The 1,2-diazole ring forms dihedral angles of 41.9 (1) and 65.5 (1)° with the phenyl and 4-tolyl rings, respectively. In the crystal, stabilizing C-H⋯O, C-H⋯π and π-π inter-actions are evident. The calculated Hirshfeld surfaces highlight the prominent role of C-H⋯O inter-actions (8.6%), along with H⋯H (51.7%) and C⋯H/H⋯C (29.2%) surface contacts.

Cesium-Fluoride-Promoted Synthesis of Stable Organocesium Reagents and Their Ambident Reactivities with Arynes.

Described are the diverse reactivities of novel, stable, ambident thio-organocesium reagents (bearing electron withdrawing groups) against benzynes. Reactions at reflux temperature predominantly led to the generation of various functionalized stable sulfonium ylides and at 40 °C the same reaction underwent direct c-arylation. Furthermore, lack of internal hydrogen on the cesium reagent helped to produce different ortho-bifunctional arynes in both the reactions. Interestingly, depending on the reactivities of substrates, the one-pot tri-component procedure generated either ylides or σ-bond insertion products.

Biosynthesis and Characterization of a Novel Fibrinolytic Alkaline Serine Protease from Newly Isolated Bacillus flexus BF12 for Biomedical Applications.

BACKGROUND: Cardiovascular Diseases (CVDs) such as stroke, high blood pressure, peripheral vascular disease, ischemic heart disease and acute myocardial infarction are some of the leading causes of death. To treat CVDs, commercially available thrombolytic agents are widely used. However, these thrombolytic agents have various side effects. Alternatively, fibrinolytic enzymes from bacterial sources are highly safe and have direct blood clot lytic activity. METHODS: A fibrinolytic enzyme producing bacterial strain, Bacillus flexus BF12, was isolated from a solar saltpan in Kanyakumari District, Tamilnadu, India. Enzyme production was improved by optimizing physical factors and nutritional factors. RESULTS: A novel fibrinolytic enzyme was isolated from a strain of the studied B. flexus BF12. Enzyme production was enhanced significantly by optimizing process parameters. The critical physical factors (pH and salinity) and influencing nutritional factors (carbon, nitrogen and ions) were optimized by one variable at a time approach, followed by the statistical method. The strain BF12 was highly active at alkaline pH (>7.0) and between 4 and 6% NaCl concentration. The nutrients such as fructose (carbon source), beef extract (nitrogen source) and CaCl2 significantly influenced enzyme production. Central composite design and response surface methodology improved 3.2-fold enzyme yield than unoptimized culture medium. Fibrinolytic protease was purified by ammonium sulphate precipitation, dialysis and gel filtration chromatography. DISCUSSION: The molecular weight of an enzyme was found to be 23 kDa. It was active at a broad temperature (40-60 °C) and pH (7.0-9.0) ranges. Enzyme activity was enhanced by Ca2+ and Co2+ ions. The purified protease retained 100% enzyme activity in the presence of ethanol and acetone. Acetonitrile, butanol, DMSO, methanol and chloroform showed enzyme activity of 63%, 92.5%, 94.7%, 92.3% and 90.4%, respectively. The purified enzyme degraded 100% of human blood clot. CONCLUSION: The Bacillus flexus BF12 fibrinolytic enzyme shows promising potentials in nutraceutical and food fortification applications. The application of fibrinolytic enzymes could prevent CVDs.

(E)-5-(4-Chloro-benzyl-idene)-1-phenyl-4,5,6,7-tetra-hydro-1H-indazol-4-one: crystal structure and Hirshfeld surface analysis.

In the title compound, C20H15ClN2O, the non-aromatic six-membered ring adopts a distorted envelope conformation with methyl-ene-C atom nearest to the five-membered ring being the flap atom. The dihedral angle between the phenyl and chloro-benzene rings is 74.5 (1)°. The heterocyclic ring forms dihedral angles of 37.9 (1) and 64.3 (1)° with the phenyl and chloro-benzene rings, respectively. In the crystal, weak C-H⋯O inter-actions feature predominantly within the three-dimensional architecture. The inter-molecular inter-actions are further analysed with the calculation of the Hirshfeld surfaces highlighting the prominent role of C-H⋯O inter-actions, along with H⋯H (36.8%) and C⋯H/H⋯C (26.5%) contacts.

Crystal structure and Hirshfeld surface analysis of 2-amino-pyridinium hydrogen phthalate.

Amino-pyridine and phthalic acid are well known synthons for supra-molecular architectures for the synthesis of new materials for optical applications. The 2-amino-pyridinium hydrogen phthalate title salt, C5H7N2 +·C8H5O4 -, crystallizes in the non-centrosymmetric space group P21. The nitro-gen atom of the -NH2 group in the cation deviates from the fitted pyridine plane by 0.035 (7) Å. The plane of the pyridinium ring and phenyl ring of the anion are oriented at an angle of 80.5 (3)° to each other in the asymmetric unit. The anion features a strong intra-molecular O-H⋯O hydrogen bond, forming a self-associated S(7) ring motif. The crystal packing is dominated by inter-molecular N-H⋯O hydrogen bonds leading to the formation of 21 helices, with a C(11) chain motif. They propagate along the b axis and enclose R 2 2(8) ring motifs. The helices are linked by C-H⋯O hydrogen bonds, forming layers parallel to the ab plane. Hirshfeld surface analysis and two-dimensional fingerprint plots were used to investigate and qu-antify the inter-molecular inter-actions in the crystal.

Structural, Spectroscopic Investigation and Computational Study on Nitrate and Hydrogen Oxalate Salts of 2-Aminopyrimidine.

The proton transfer salts of 2-aminopyrimidine with nitric acid (2APNO) and oxalic acid (2APOX) were synthesized and crystallized successfully by solvent evaporation solution growth technique. The crystal packing is stabilized through intricate three dimensional hydrogen bonded network. Both, the molecular structures were optimized with Density Functional Theory (DFT) using B3LYP function and Hartree-Fock method with a 6-311++G(d,p) basis set. Optimized molecular parameters between the methods were compared for the cation showing appreciable agreement. The computed vibrational spectra are compared with experimental result which clearly demonstrates the strong N-H··· O vibrational behaviour. Thermal stability of the crystals were analyzed with TGA/DTA and the melting points of the salts, viz. 2APNO and 2APOX, were identified at 189.5 and 210.9 °C, respectively. The chemical hardness, electronegativity, chemical potential and electrophilicity index of the two crystals were determined by HOMO-LUMO plot. The lower band gap value obtained from the Frontier Molecular Orbital (FMO) analysis favours the possible pharmaceutical/biological activity of the salts.

Multicomponent Dipolar Cycloaddition Strategy: Combinatorial Synthesis of Novel Spiro-Tethered Pyrazolo[3,4-b]quinoline Hybrid Heterocycles.

The stereoselective syntheses of a library of novel spiro-tethered pyrazolo[3,4-b]quinoline-pyrrolidine/pyrrolothiazole/indolizine-oxindole/acenaphthene hybrid heterocycles have been achieved through the 1,3-dipolar cycloaddition of azomethine ylides generated in situ from α-amino acids and 1,2-diketones to dipolarophiles derived from pyrazolo[3,4-b]quinoline derivatives.

Crystal structure of ethyl 2-[2-(4-methyl-benzo-yl)-5-p-tolyl-1H-imidazol-1-yl]acetate.

In the title compound, C22H22N2O3, the plane of the five-membered ring is oriented at dihedral angles of 45.4 (1) and 52.5 (1)° to the phenyl rings. Furthermore, this ring makes an angle of 85.2 (2)° with the plane of the ethyl acetate substituent. The mol-ecular structure is affected by an intra-molecular C-H⋯O hydrogen bond between an H atom from the p-tolyl group and the carbonyl O atom of the acetate. The methyl group of the ethyl acetate residue is disordered over two sites with equal occupancies. The crystal structure features inter-molecular C-H⋯O and C-H⋯N inter-actions. One of the C-H⋯O hydrogen bonds forms a C(5) chain motif extending along the a axis. In addition, C-H⋯N contacts form inversion dimers with R 2 (2)(12) ring motifs, linking the imidazole ring system to the benzene ring of the p-tolyl substituent.

Divergent Reactivity of Amino Acid Alkyl Ester Hydrochlorides with 2-Oxoaldehydes: Role of Selenium Dioxide To Promote Regioselective Synthesis of Imidazoles.

Novel amino acid substituted imidazoles engendered from amino acid alkyl ester hydrochlorides and 2-oxoaldehydes as a result of selenium dioxide promoted unconventional reaction in a basic environment is presented for the first time. Despite the nature of the 2-oxoaldehydes/amino acids used, the imidazoles generated had a functional core structure, and all of the reactions meticulously retained regioselectivity. The imperative feature of these reactions was the uniqueness of selenium dioxide in fixing two nitrogen atoms from amino acids through an in situ generated ArCOCHN1N2 system.

Single crystal XRD, vibrational and quantum chemical calculation of pharmaceutical drug paracetamol: A new synthesis form.

The common house hold pharmaceutical drug, paracetamol (PAR), has been synthesized from 4-chloroaniline as a first ever report. After the synthesis, good quality single crystals were obtained for slow evaporation technique under the room temperature. The crystal and molecular structures were re-determined by the single crystal X-ray diffraction. The vibrational spectral measurements were carried out using FT-IR and FT-Raman spectroscopy in the range of 4000-400 cm(-1). The single crystal X-ray studies shows that the drug crystallized in the monoclinic system polymorph (Form-I). The crystal packing is dominated by N-H⋯O and O-H⋯O classical hydrogen bonds. The ac diagonal of the unit cell features two chain C(7) and C(9) motifs running in the opposite directions. These two chain motifs are cross-linked to each other to form a ring R4(4)(22) motif and a chain C2(2)(6) motif which is running along the a-axis of the unit cell. Along with the classical hydrogen bonds, the methyl group forms a weak C-H⋯O interactions in the crystal packing. It offers the support for molecular assembly especially in the hydrophilic regions. Further, the strength of the hydrogen bonds are studied the shifting of vibrational bands. Geometrical optimizations of the drug molecule were done by the Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The factor group analysis of the molecule was carried out by the various molecular symmetry, site and factor group species using the standard correlation method. The Natural Bond Orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical softness, chemical hardness, electro-negativity, chemical potential and electrophilicity index of the molecule were found out first time by HOMO-LUMO plot. The frontier orbitals shows lower band gap values signify the possible biological/pharmaceutical activity of the molecule. The thermodynamical properties are also obtained from the calculated frequencies of the optimized structures.

XRD, vibrational spectra and quantum chemical studies of an anticancer drug: 6-Mercaptopurine.

The single crystal of the hydrated anticancer drug, 6-Mercaptopurine (6-MP), has been grown by slow evaporation technique under room temperature. The structure was determined by single crystal X-ray diffraction. The vibrational spectral analysis was carried out using Laser Raman and FT-IR spectroscopy in the range of 3300-100 and 4000-400 cm(-1). The single crystal X-ray studies shows that the crystal packing is dominated by N-H⋯O and O-H⋯N classical hydrogen bonds leading to a hydrogen bonded ensemble. This classical hydrogen bonds were further connected through O-H⋯S hydrogen bond to form two primary ring R4(4)(16) and R4(4)(12) motifs. These two primary ring motifs are interlinked with each other to build a ladder like structure. These ladders are connected through N-H⋯N hydrogen bond along c-axis of the unit cell through chain C(5) motifs. Further, the strength of the hydrogen bonds is studied through vibrational spectral measurements. The shifting of bands due to the intermolecular interactions was also analyzed in the solid crystalline state. Geometrical optimizations of the drug molecule were done by Density Functional Theory (DFT) using the B3LYP function and Hartree-Fock (HF) level with 6-311++G(d,p) basis set. The optimized molecular geometry and computed vibrational spectra are compared with experimental results which show significant agreement. The natural bond orbital (NBO) analysis was carried out to interpret hyperconjugative interaction and intramolecular charge transfer (ICT). The chemical hardness, electro-negativity and chemical potential of the molecule are carried out by HOMO-LUMO plot. In which, the frontier orbitals has lower band gap value indicating the possible pharmaceutical activity of the molecule.

A strong NH Br vibrational behaviour studied through X-ray, vibrational spectra and quantum chemical studies in an isomorphous crystal: 2-Nitroanilinium bromide.

A needle shaped transparent light brown crystals of 2-nitroanilinium bromide were successfully synthesized and crystallized from an aqueous mixture by slow evaporation technique. Single crystal XRD studies confirm the crystalline phase of this isomorphous compound which contains a positively charge 2-nitroanilinium cation and a negatively charged bromide anion. The solid phase FT-IR and FT-Raman spectra of the compound have been recorded in the range of 4000-400cm(-1). The observed modes are correlated by the factor group theory analysis and different IR and Raman active species were identified. Geometrical optimisations were carried out and harmonic vibrational wave numbers were computed for the minimum energy molecular structure at RHF level invoking 6-311++G(d,p) and SDD basis sets. Optimised molecular geometry was compared with the crystallographic data. The calculated wavenumbers were compared with the experimental values. The NH vibrational bands are shifted from its normal range and the shifting is associated with the influence of the intermolecular hydrogen bonds in the crystal. A strong intensity peak in theoretical and corresponding band in experimental confirms the presence of NH…Br interaction as predicted in crystalline state.

4-Sulfamoylanilinium perchlorate.

In the crystal of the title salt, C6H9N2O2S(+)·ClO4 (-), the components are linked by N-H⋯O hydrogen bonds, forming a three-dimensional network. The cations are connected along a and b axes, leading to linear and zigzag C(3) and C(8) chain motifs, respectively. A cation-anion inter-action along the c axis leads to a C 2 (2)(12) chain motif. R 3 (3)(18) and R 3 (3)(20) ring motifs are observed as cation-anion-type inter-actions. These hydrogen-bonding ring and chain motifs are localized at z = 0 or 1, leading to alternate hydro-philic and hydro-phobic regions along the c axis as a result of the stacking of anions and the aromatic cationic parts.

Ethyl 3-(4-chloro-benzo-yl)-1-(4-chloro-benz-yl)-4-(4-chloro-phen-yl)-2,2-dioxo-3,4,6,7,8,8a-hexa-hydro-1H-pyrrolo-[2,1-c][1,4]thia-zine-1-carboxyl-ate.

In the title compound, C30H28Cl3NO5S, the pyrrolidine ring adopts an envelope conformation (with the N atom as the flap) and the thia-zine ring is in a distorted chair conformation. The mol-ecular structure shows three intra-molecular C-H⋯O inter-actions leading to self-associated ring S(6) and two S(7) motifs. In the crystal, the molecules are linked by C-H⋯O and C-H⋯Cl inter-actions. Two R 2 (2)(10) and one R 2 (2)(16) centrosymmetrically related ring motifs are observed in the unit cell and they are connected through C(6) and C(11) chain motifs extending along the b and c axes, respectively.

(E)-3-(4-Meth-oxy-phen-yl)-3-[3-(4-meth-oxy-phen-yl)-1H-pyrazol-1-yl]prop-2-enal.

In the title mol-ecule, C20H18N2O3, the pyrazole ring forms a dihedral angle of 2.2 (1)° with its meth-oxy-phenyl substituent and a dihedral angle of 67.2 (1)° with the benzene substituent on the propenal unit. In the crystal, mol-ecules are connected by weak C-H⋯O hydrogen bonds, forming R 2 (2)(26) and R 2 (2)(28) cyclic dimers that lie about crystallographic inversion centres. These dimers are further linked through C-H⋯O and C-H⋯N hydrogen bonds, forming C(8), C(9), C(10) and C(16) chain motifs. These primary motifs are further linked to form secondary C 2 (2)(15) chains and R 2 (2)(18) rings.

Bis(4-sulfamoylanilinium) sulfate.

In the title salt, 2C6H9N2O2S(+)·SO4 (2-), the sulfate S atom is situated on a crystallographic twofold axis (the symmetry of the anion is 2). The anion exerts intense libration, which is manifested by shortening of the observed sulfate S-O bonds, as well as by features in the electron-density map. The crystal structure is stabilized through a three-dimensional hydrogen-bonding network formed by strong N-H⋯O hydrogen bonds.

1-(2,4-Dinitro-phen-yl)-3-phenyl-4-phenyl-sulfanyl-1H-pyrazole.

In the title mol-ecule, C(21)H(14)N(4)O(4)S, the pyrazole ring forms dihedral angles of 45.6 (1), 87.7 (1) and 27.4 (1)° with the phenyl, sulfur-substituted benzene and nitro-substituted benzene rings, respectively. In the crystal, mol-ecules are connected by weak C-H⋯O and C-H⋯N hydrogen bonds into layers parallel to (010).

Intermolecular C-H···O and C-H···X interactions in substituted spiroacenaphthylene structures.

In the three spiroacenaphthylene structures 5''-[(E)-2,3-dichlorobenzylidene]-7'-(2,3-dichlorophenyl)-1''-methyldispiro[acenaphthylene-1,5'-pyrrolo[1,2-c][1,3]thiazole-6',3''-piperidine]-2,4''-dione, C(35)H(26)Cl(4)N(2)O(2)S, (I), 5''-[(E)-4-fluorobenzylidene]-7'-(4-fluorophenyl)-1''-methyldispiro[acenaphthylene-1,5'-pyrrolo[1,2-c][1,3]thiazole-6',3''-piperidine]-2,4''-dione, C(35)H(28)F(2)N(2)O(2)S, (II), and 5''-[(E)-4-bromobenzylidene]-7'-(4-bromophenyl)-1''-methyldispiro[acenaphthylene-1,5'-pyrrolo[1,2-c][1,3]thiazole-6',3''-piperidine]-2,4''-dione, C(35)H(28)Br(2)N(2)O(2)S, (III), the substituted aryl groups are 2,3-dichloro-, 4-fluoro- and 4-bromophenyl, respectively. The six-membered piperidine ring in all three structures adopts a half-chair conformation, the thiazolidine ring adopts a slightly twisted envelope and the pyrrolidine ring an envelope conformation; in each case, the C atom linking the rings is the flap atom. In all three structures, weak intramolecular C-H···O interactions are present. The crystal packing is stabilized through a number of intermolecular C-H···O and C-H···X interactions, where X = Cl in (I) and F or S in (II), and C-H···O interactions are observed predominantly in (III). In all three structures, molecules are linked through centrosymmetric ring motifs, further tailored through a relay of C-H···X [Cl in (I), Br in (II) and O in (III)] interactions.

4-Chloro-anilinium 3-carb-oxy-prop-2-enoate.

In the title compound, C(6)H(7)ClN(+)·C(4)H(3)O(4) (-), the cations and anions lie on mirror planes and hence only half of the mol-ecules are present in the asymmeric unit. The 4-chloro-anilinium cation and hydrogen maleate anion in the asymmetric unit are each planar and are oriented at an angle of 15.6 (1)° to one another and perpendicular to the b axis. A characterestic intra-molecular O-H⋯O hydrogen bond, forming an S(7) motif, is observed in the maleate anion. In the crystal, the cations and anions are linked by N-H⋯O hydrogen bonds, forming layers in the ab plane. The aromatic rings of the cations are sandwiched between hydrogen-bonded chains and rings formed through the amine group of the cation and maleate anions, leading to alternate hydro-phobic (z = 0 or 1) and hydro-philic layers (z = 1/2) along the c axis.