Benzylidene-isophorone hybrids with strong anticancer activity.

Isophorone is a cyclic ketone that has gained significant attention in the field of organic chemistry due to its versatile reactivity and structural attributes. Derivatives of isophorone offer a broad spectrum of applications ranging from pharmaceuticals to polymer chemistry. With the aim of developing novel hybrid structures based on benzylidene by combining with isophorone scaffold, we report 3 derivatives of the benzylidene-isophorone hybrids and its potent anticancer activity. In order to optimize the anticancer activity of hybrids di-substitution of -Cl group in C2 and C6 position of phenyl ring (compound1), -OCH3 group in C2 and C5 position of phenyl ring (compound2), and -OCH3 group in C2 and C3 position of phenyl ring (compound3) of benzylidene (PhCH=) moiety were made. The structure of Compounds1,2 and 3 were elucidated using spectral and XRD methods. Compounds1,2 and 3 exhibit space group P c a 21, P-1, and P 1 21/n 1 respectively. Compounds1,2 and 3 were tested for the potent anticancer activity on MDA MB-231 cell line. All the three compounds exhibit good anticancer activity on the breast cancer cells. The parent hybrid with ortho, ortho directing -Cl (1) exhibits strong antiproliferation effect (IC50 = 0.028 µM) on MDA-MB 231 cell line. However, hybrid structures with ortho, meta directing -OCH3 (2) group showed moderate effect (IC50 = 0.061 µM) and hybrid with ortho, meta directing -OCH3 (3) substitution showed the least potent anticancer activity (IC50 = 0.074 µM). The benzylidene-isophorone hybrids exhibit anticancer effects in the following order: 1 > 2 > 3.

Crystal structures of (12E)-12-(4-benzyl-idene)-7,7,16-trimethyl-3-(4-methyl-phen-yl)-1-oxa-16-aza-tetra-cyclo-[11.2.1.02,11.04,9]hexa-deca-2(11),4(9)-dien-5-one and (12E)-12-(4-bromo-benzyl-idene)-73-(4-bromo-phen-yl)-,7,16-trimethyl-10-oxa-16-aza-tetra-cyclo-[11.2.1.02,11.04,9]hexa-deca-2(11),4(9)-dien-5-one.

The title compounds, C32H35NO2, (I), and C30H29Br2NO2, (II), differ by the presence of a bromine atom instead of a methyl atom in the para position of two benzene rings of compound (II). The two compounds have a structural overlap r.m.s. deviation of 0.27 Å. The pyran and seven-membered cyclo-heptene rings in both structures adopt boat and boat-sofa conformations, respectively. Intra- and inter-molecular C-H⋯O hydrogen bonds are responsible for the consolidation of the crystal packing of both mol-ecules. In addition to this, weak C-H⋯π inter-actions are also observed. The inter-molecular inter-actions were qu-anti-fied and analysed using Hirshfeld surface analysis.

Ethyl 2-cyano-2-{(Z)-2-[2,2-di-cyano-1-(4-methyl-phen-yl)eth-yl]cyclo-hexyl-idene}acetate.

In the title compound, C22H23N3O2, the cyclo-hexane ring adopts a chair conformation. The methyl-phenyl ring is oriented at an angle of 36.2 (1)° with respect to the best plane of cyclo-hexane moiety. In the crystal, mol-ecules associate via C-H⋯N hydrogen bonds, forming a three-dimensional network.

2,6-Diphenyl-3-(prop-2-en-1-yl)piperidin-4-one.

In the title compound, C20H21NO, the dihedral angle between the phenyl ring is 47.5 (1)° and the piperidine ring adopts a chair conformation. In the crystal, mol-ecules are linked by C-H⋯π inter-actions into dimers with the mol-ecules related by twofold symmetry.

Crystal structures of 6a,6b,7,11a-tetra-hydro-6H,9H-spiro-[chromeno[3',4':3,4]pyrrolo-[1,2-c]thia-zole-11,3'-indoline]-2',6-dione and 5'-methyl-6a,6b,7,11a-tetra-hydro-6H,9H-spiro-[chromeno[3',4':3,4]pyrrolo-[1,2-c]thia-zole-11,3'-indoline]-2',6-dione.

The title compounds, C20H16N2O3S, (I), and C21H18N2O3S, (II), differ by the presence of a methyl group in position 5 on the 1H-indole-2-one ring of compound (II). The two compounds have a structural overlap r.m.s. deviation of 0.48 Å. There is a significant difference in the conformation of the thia-zolidine ring: it has a twisted conformation on the fused N-C bond in (I), but an envelope conformation in compound (II) with the S atom as the flap. The planar pyrrolidine ring of the indole ring system is normal to the mean plane of the five-membered pyrrolidine ring of the pyrrolo-thia-zole unit in both compounds, with dihedral angles of 88.71 (9) and 84.59 (8)°. The pyran rings in both structures have envelope conformations with the methyl-ene C atom adjacent to the C=O group as the flap. In both compounds, there is a short intra-molecular C-H⋯O contact present. In the crystal of (I), mol-ecules are linked by C-H⋯O hydrogen bonds forming chains propagating along the b-axis direction. The chains are linked by N-H⋯π inter-actions, forming layers parallel to (10). In the crystal of (II), mol-ecules are linked by pairs of N-H⋯O hydrogen bonds, forming inversion dimers which are linked by C-H⋯O hydrogen bonds to form a three-dimensional structure.

Crystal structures of 3-meth-oxy-4-{[5-(4-meth-oxy-phen-yl)-1,3,4-oxa-diazol-2-yl]meth-oxy}benzo-nitrile and N-(4-{[5-(4-chloro-phen-yl)-1,3,4-oxa-diazol-2-yl]meth-oxy}phen-yl)acetamide.

The title compounds, C18H15N3O4 and C17H14ClN3O3, are heterocyclic 1,3,4-oxa-diazole derivatives which differ from each other in the groups attached to the carbon atoms: a meth-oxy-phenyl ring and a benzo-nitrile group in (I) and a chloro-phenyl ring and an acetamide group in (II). Short intra-molecular C-H⋯O hydrogen bonds occur in both mol-ecules. The crystal structure of (I) features C-H⋯N hydrogen bonds, while in the crystal structure of (II), N-H⋯N, C-H⋯N and C-H⋯O hydrogen bonds are observed.

Investigation of Electrochemical Studies of Magnesium Ion Conducting Poly(vinyl alcohol)-Poly(vinyl pyrrolidone) Based Blend Polymers.

Polymer blend electrolytes based on magnesium ion conducting PVA-PVP-MgCl2 polymer were prepared at different compositions by solution casting techniques. The prepared films were characterised by various techniques such as XRD and FTIR. Amorphous nature and structural coordination of polymer electrolyte were confirmed by X-ray diffraction and Fourier transform infrared spectroscopy studies. The ionic conductivity of the prepared polymer electrolytes were analysed through ac impedance spectroscopy. The highest conductivity was found to be in the order of ~10-6 Scm-1 at an ambient temperature for the composition of 50PVA:50PVP:5 wt% MgCl2. Conductivity versus temperature plot was found to follow an Arrhenius nature. The dielectric behaviour and ionic transport properties of the polymer electrolytes were also analyzed.

Crystal structures of salen-type ligands 2-[(1E)-({1-(3-chloro-phen-yl)-2-[(E)-(2-hy-droxy-benzyl-idene)amino]-prop-yl}imino)-meth-yl]phenol and 2-[(1E)-({1-(4-chloro-phen-yl)-2-[(E)-(2-hy-droxy-benzyl-idene)amino]-prop-yl}imino)-meth-yl]phenol.

The title compounds, C23H21ClN2O2, differ from each other only by the position of the Cl atom on the corresponding benzene ring: meta relative to the central sp3 C atom for (I) and para for (II). In (I), the hy-droxy-phenyl rings are almost parallel, the dihedral angle between the mean planes being 9.2 (2)°, but in (II), the relative position of the ring is different, characterized by a dihedral angle of 48.5 (1)°. Compound (I) features intra-molecular O-H⋯N and inter-molecular C-H⋯O hydrogen bonds, while in (II), intra-molecular O-H⋯N, C-H⋯N hydrogen bonds and weak inter-molecular C-H⋯π inter-actions are observed. Compound (I) was refined as an inversion twin.

Crystal structure of 2-(2,4-diphenyl-3-aza-bicyclo-[3.3.1]nonan-9-yl-idene)aceto-nitrile.

In the title 3-aza-bicyclo-nonane derivative, C22H22N2, both the fused piperidine and cyclo-hexane rings adopt a chair conformation. The phenyl rings attached to the central aza-bicylononane fragment in an equatorial orientation are inclined to each other at 23.7 (1)°. The amino group is not involved in any hydrogen bonding, so the crystal packing is stabilized only by van der Waals forces.

Crystal structure of 2-[4(E)-2,6-bis-(4-chloro-phen-yl)-3-ethyl-piperidin-4-yl-idene]acetamide.

In the title piperidine derivative, C21H22Cl2N2O, the piperidine ring adopts a chair conformation. The chloro-phenyl rings are oriented at an angle of 45.59 (14)° with respect to each other. In the crystal, mol-ecules are linked via N-H⋯O hydrogen bonds, forming C(4) chains along [100]. The chains are linked by C-H⋯O hydrogen bonds, forming sheets parallel to the ab plane. Within the sheets, there are N-H⋯π inter-actions present. The crystal studied was refined as an inversion twin.

Crystal structure of 2'-[(2',4'-di-fluoro-biphenyl-4-yl)carbon-yl]-1'-phenyl-1',2',5',6',7',7a'-hexa-hydro-spiro-[indole-3,3'-pyrrolizin]-2(1H)-one.

In the title pyrrolizidine derivative, C33H26F2N2O2, both pyrrolidine rings of the pyrrolizidine moiety adopt an envelope conformation. The di-fluoro-phenyl group is oriented at an angle of 54.3 (1)° with respect to the oxindole moiety. The crystal packing features an N-H⋯O hydrogen bond, which forms an R 2 (2)(8) motif, and a C-H⋯O inter-action, which generates a C(8) chain along [010]. In addition, this chain structure is stabilized by C-H⋯π inter-actions. In one of the pyrrolidine rings, the methyl-ene group forming the flap of an envelope and the H atoms of the adjacent methyl-ene groups are disordered over two sets of sites, with site-occupancy factors of 0.571 (4) and 0.429 (4).

Crystal structure of methyl (2Z)-3-(4-chloro-phen-yl)-2-[(3-methyl-1H-indol-1-yl)meth-yl]prop-2-enoate.

In the title indole derivative, C20H18ClNO2, the chloro-phenyl ring is almost perpendicular to the indole moiety, making a dihedral angle of 87.6 (1)°. The mol-ecular packing is stabilized by C-H⋯π inter-actions, which form a C(9) chain motif along [10-1]. In addition, there are weak π-π inter-actions [centroid-centroid distance 3.851 (1) Å] between the chains, involving inversion-related chloro-phenyl rings.

Growth, structure, spectral and optical properties of semiorganic crystal: Pyridine-1-ium-2-carboxylatehydrogenbromide.

Pyridine-1-ium-2-carboxylatehydrogenbromide (PHBr) crystal was grown from aqueous solution by slow evaporation method. The calculated lattice parameters of single crystal X-ray diffraction have shown the triclinic crystal system with centrosymmetric space group of Pi. The interaction of functional groups and their importance in their application was identified by FTIR spectral analysis. The material is optically transparent and the grown crystal is having lower cut off wavelength as 294nm, thereby confirming the enhancement of non-linear optical (NLO) property and optical band gap of the PHBr have been determined as 2.49eV by UV-Vis-NIR studies. The (1)H NMR spectrum confirms the molecular structure and the presence of different kinds of protons.

Crystal structure of 1-(2,4-di-methyl-phen-yl)urea.

In the title urea derivative, C9H12N2O, the dihedral angle between the benzene ring and the mean plane of the urea group, N-C(=O)-N, is 86.6 (1)°. In the crystal, the urea O atom is involved in three N-H⋯O hydrogen bonds. Mol-ecules are linked via pairs of N-H⋯O hydrogen bonds, forming inversion dimers with an R (2) 2(8) ring motif. The dimers are linked by further N-H⋯O hydrogen bonds, forming two-dimensional networks lying parallel to (100).

Crystal structure of (E)-2-(4-meth-oxy-styr-yl)-2,3-di-hydro-1H-perimidine aceto-nitrile monosolvate.

The title compound, C20H18N2O·CH3CN, a perimidine deriv-ative, crystallized as an aceto-nitrile monosolvate. The planes of the naphthalene ring system and the meth-oxy-phenyl ring are oriented almost perpendicular to one another, with a dihedral angle of 87.61 (6)°. The conformation about the C=C bond is E. The hexa-hydro-pyrimidine ring has an envelope conformation, with the methine C atom as the flap. In the crystal, the mol-ecules are linked by N-H⋯N hydrogen bonds involving the aceto-nitrile solvent mol-ecule as acceptor, forming zigzag chains propagating along [100].

Methyl (2Z)-2-[(2-formyl-3-methyl-1H-indol-1-yl)meth-yl]-3-(4-meth-oxy-phen-yl)prop-2-enoate.

In the title indole derivative, C22H21NO4, the dihedral angle between the benzene and pyrrole rings of indole moiety is 1.8 (1)°. The plane of the 4-meth-oxy-phenyl ring is oriented with a dihedral angle of 60.7 (1)° with respect to the plane of the indole moiety. The mol-ecular packing is stabilized by C-H⋯O hydrogen bonds which form a V-shaped chain arrangement along the bc plane of the unit cell. In addition to this, C-H⋯π and π-π inter-actions [centroid-centroid distances = 3.8102 (11) and 3.8803(12) Å], which run along the b-axis direction, stabilize the mol-ecular packing.

Crystal structure of 9-butyl-3-(9-butyl-9H-carbazol-3-yl)-9H-carbazole.

In the title carbazole derivative, C32H32N2, the mol-ecule resides on a crystallographic twofold axis, which runs through the central C-C bond. The carbazole ring system is almost planar, with a maximum deviation of 0.041 (1) Šfor one of the ring-junction C atoms. The crystal packing is stabilized by C-H⋯π inter-actions only, which form a C(7) chain-like arrangement along [110] in the unit cell.

Bis{N-benzyl-N-[2-(thio-phen-2-yl)eth-yl]di-thio-carbamato-κ(2) S,S'}lead(II).

The mol-ecule of the title compound, [Pb(C14H14NS3)2], is located on a twofold rotation axis. The di-thio-carbamate anion S,S'-chelates to the Pb(II) atom, which shows a Ψ-trigonal-bipyramidal coordination. The thio-phene ring is disordered over two positions, the major component having 71.3 (7)% occupancy. The mol-ecular conformation is stabilized by intra-molecular C-H⋯S inter-actions.

1-(2-Chloro-phen-yl)-3-(2-ethyl-hexa-noyl)thio-urea.

In the title compound, C15H21ClN2OS, the central chromophore moiety (C2N2OS) is approximately planar, with a maximum deviation of -0.027 (1) Å, and is oriented at a dihedral angle of 86.7 (1)° with respect to the chloro-phenyl ring. An intra-molecular N-H⋯O hydrogen bond stabilizes the mol-ecular conformation. In the crystal, mol-ecules associate via N-H⋯S hydrogen bonds, forming inversion dimers with motif R 2 (2)(8). These dimers are further connected by N-H⋯O hydrogen bonds, forming R 2 (2)(12) dimers. As a result, hydrogen-bonded chains running along [110] are formed. C-H⋯S inter-actions also occur. The terminal two C atoms of the butyl chain are disordered over two positions with an occupancy ratio of 0.54:0.46.

Methyl 9-(4-meth-oxy-phen-yl)-19-methyl-3,12-di-aza-penta-cyclo-[10.7.0.0(2,10).0(3,8).0(13,18)]nona-deca-1(19),13(18),14,16-tetra-ene-10-carboxyl-ate.

The title ester, C27H30N2O3, crystallizes with two independent mol-ecules in the asymmetric unit whose geometrical features are similar. In each mol-ecule, the pyrrolidine ring adopts an envelope conformation, with the fused C atom shared with the piperidine ring as the flap, and the piperidine ring adopts a chair conformation. In the crystal, C-H⋯π inter-actions link the inversion-related molecules and form a dimeric arrangement in the unit cell.