Synthesis, characterization and X-ray structure of the adducts of bis(O-butyldithiocarbonato)nickel(II) with substituted pyridines.

Some mixed ligand complexes of Ni(II) with O-butyldithiocarbonate as a primary ligand and substituted pyridines as secondary ligands have been isolated and characterized on the basis of analytical data, molar conductance, magnetic susceptibility, electronic and infrared spectral studies. The molar conductance studies show their non-electrolytic behavior. Magnetic and electronic spectral studies suggest octahedral stereochemistry around Ni(II) ions. Infrared spectral studies suggest bidentate chelating behavior of O-butyldithiocarbonate monoanion while other ligands show unidentate behavior in their complexes. One of the adduct bis(O-butyldithiocarbonato)bis(3,5-dimethylpyridine)nickel(II) crystallizes in the monoclinic space group P21/c with unit cell parameters. The crystal structure has been solved by direct methods and refined by full matrix least-squares procedures to a final R-value of 0.0379 for 2460 observed reflections. The Ni2+ ion is in a octahedral coordination environment formed by an N2S4 donor set, defined by two chelating dithiocarbonate anions as well as two 3,5-dimethylpyridine ligands with the Ni2+ ion located at the inversion centre. The packing of layers of molecules is stabilized by weak pi-pi and C-H---pi interactions.

(R)-2-Cyano-N-(1-phenyl-eth-yl)acetamide.

In the title compound, C11H12N2O, the dihedral angle between the acetamide group and the benzene ring is 68.7 (1)°. In the crystal, N-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into chains along the a-axis direction.

5-Bromo-2-chloro-pyrimidin-4-amine.

In the title compound, C4H3BrClN3, the pyrimidine ring is essentially planar (r.m.s. deviation from the plane = 0.087 Å). In the crystal, pairs of N-H⋯N hydrogen bonds connect the mol-ecules into inversion dimers; these are connected by further N-H⋯N hydrogen bonds into a two-dimensional framework parallel to the bc plane.

Ethyl 2-(quinolin-8-yl-oxy)acetate monohydrate.

In the title compound, C13H13NO3·H2O, the dihedral angle between the ethyl ester group [C-C-O-C(=O); maximum deviation = 0.003 (2) Å] and the quinoline ring system is 7.94 (12)°. The water solvent mol-ecule is linked to the title mol-ecule via O-H⋯O and O-H⋯N hydrogen bonds. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming chains propagating along [100].

9-(4-Hy-droxy-3-meth-oxy-phen-yl)-3,3,6,6-tetra-methyl-1,2,3,4,5,6,7,8,9,10-deca-hydro-acridine-1,8-dione.

In the title mol-ecule, C24H29NO4, the central ring of the acridinedione system adopts a flat boat conformation and the four essentially planar atoms of this ring [maximum deviation = 0.001 (2) Å] form a dihedral angle of 85.99 (12)° with the benzene ring. The two outer rings of the acridinedione system adopt sofa conformations. In the crystal, O-H⋯O and N-H⋯O hydrogen bonds link the mol-ecules, forming a two-dimensional network parallel to (100).

9-(3-Fluoro-phen-yl)-3,3,6,6-tetra-methyl-1,2,3,4,5,6,7,8,9,10-deca-hydro-acridine-1,8-dione.

In the title mol-ecule, C23H26FNO2, the central ring of the acridinedione system adopts a slight boat conformation and the four essentially planar atoms of this ring [maximum deviation = 0.019 (1) Å] form a dihedral angle of 89.98 (6)° with the benzene ring. The two outer rings of the acridinedione system adopt sofa conformations. In the crystal, N-H⋯O hydrogen bonds link the mol-ecules, forming chains along [001].

2-Amino-7,7-dimethyl-5-oxo-4-[3-(trifluoro-meth-yl)phen-yl]-1,4,5,6,7,8-hexa-hydro-quinoline-3-carbonitrile.

In the title mol-ecule, C19H18F3N3O, the dihydro-pyridine and cyclo-hexene rings both adopt sofa conformations. The five essentially planar atoms of the dihydro-pyridine ring [maximum deviation = 0.039 (2) Å] form a dihedral angle of 88.19 (8)° with the benzene ring. The F atoms of the trifluoro-methyl group were refined as disordered over two sets of sites in a 0.840 (3):0.160 (3) ratio. In the crystal, N-H⋯O and N-H⋯N hydrogen bonds link mol-ecules into a two-dimensional network parallel to (100).

A second monoclinic polymorph of 4-[(E)-(4-benzyl-oxybenzyl-idene)amino]-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one.

In the title compound, C25H23N3O2, the central benzene ring makes dihedral angles of 77.14 (8) and 87.7 (2)° with the terminal benzene rings and an angle of 1.9 (1)° with the pyrazolone ring. The benzene ring and the N atom of the pyrazole ring bearing the phenyl substituent are disordered over two sets of sites with an occupancy ratio of 0.71 (2):0.29 (2). The N atoms of the pyrazole ring have a pyramidal environment, the sums of the valence angles around them being 354.6 (3) and 352.0 (6)/349.5 (15)°. In the crystal, mol-ecules are packed into layers parallel to the ac plane. The other monoclinic polymorphic form was reported recently [Dutkiewicz et al. (2012 ▶). Acta Cryst. E68, o1324].

2-Amino-7,7-dimethyl-5-oxo-4-[3-(trifluoro-meth-yl)phen-yl]-5,6,7,8-tetra-hydro-4H-chromene-3-carbonitrile.

In the title mol-ecule, C19H17F3N2O2, the fused cyclo-hexene and pyran rings adopt sofa and flattened boat conformations, respectively. The four essentially planar atoms of the pyran ring [maximum deviation = 0.008 (2) Å] form a dihedral angle of 88.13 (9)° with the benzene ring. The F atoms of the trifluoro-methyl group were refined as disordered over three sets of sites in a 0.507 (7):0.330 (7):0.163 (3) ratio. In the crystal, mol-ecules are connected into inversion dimers via pairs of N-H⋯N hydrogen bonds and these dimers are further linked by N-H⋯O hydrogen bonds into a two-dimensional network parallel to (100).

2-[(Dimethyl-amino)-methyl-idene]propane-dinitrile.

In the title moleclue, C6H7N3, the mean plane of the dimethyl-amino group [maximum deviation = 0.006 (2) Å] forms a dihedral angle of 7.95 (18)° with the mean plane of the propane-dinitrile fragment [maximum deviation = 0.008 (2) Å]. In the crystal, weak C-H⋯N hydrogen bonds link the mol-ecules into a three-dimensional network.

5-Benzoyl-4-(4-fluoro-phen-yl)-3,4-dihydro-pyrimidin-2(1H)-one.

In the title mol-ecule, C(17)H(13)FN(2)O(2), the 3,4-dihydro-pyrimidine ring adopts a flattened sofa conformation with the flap atom (which bears the fluoro-phenyl substituent) deviating from the plane defined by the remaining five ring atoms by 0.281 (2) Å. This plane forms dihedral angles of 85.98 (6) and 60.63 (6)° with the 4-fluoro-phenyl and benzoyl-phenyl rings, respectively. The dihedral angle between the 4-fluoro-phenyl group and the benzene ring is 71.78 (6)°. In the crystal, N-H⋯O hydrogen bonds link mol-ecules into inversion dimers that are further connected by another N-H⋯O inter-action into a two-dimensional supra-molecular structure parallel to (101).

9-(3,4-Dimeth-oxy-phen-yl)-3,3,6,6-tetra-methyl-1,2,3,4,5,6,7,8,9,10-deca-hydro-acridine-1,8-dione.

The asymmetric unit of the title compound, C(25)H(31)NO(4), contains two independent mol-ecules. In one mol-ecule, the benzene ring and an attached meth-oxy group were refined as disordered over two sets of sites in a 0.65 (4): 0.35 (4) ratio. In both mol-ecules, the central ring of the acridinedione system adopts a flattened boat conformation. The four essentially planar atoms of this ring [maximum deviations = 0.006 (5) Šin both mol-ecules] forms dihedral angles of 86.8 (2) and 87.6 (2)°, respectively, with the major and minor components in the disordered benzene ring and 87.3 (2)° with the benzene ring in the fully ordered mol-ecule. The two outer rings of the acridinedione system adopt sofa conformations in both mol-ecules. In the crystal, N-H⋯O hydrogen bonds form two independent chains along [100]. C-H⋯O hydrogen bonds link the chains, forming a three-dimensional network.

Tubulin inhibitors from an endophytic fungus isolated from Cedrus deodara.

From an endophytic fungus, a close relative of Talaromyces sp., found in association with Cedrus deodara, four compounds including two new ones (2 and 4) were isolated and characterized. The structures of two compounds (1 and 4) were confirmed by X-ray crystallography. The compounds displayed a range of cytotoxicities against human cancer cell lines (HCT-116, A-549, HEP-1, THP-1, and PC-3). All the compounds were found to induce apoptosis in HL-60 cells, as evidenced by fluorescence and scanning electron microscopy studies. Also, the compounds caused significant microtubule inhibition in HL-60 cells.

N-(2-{[5-Bromo-2-(piperidin-1-yl)pyrimidin-4-yl]sulfan-yl}-4-meth-oxy-phen-yl)-4-methyl-benzene-sulfonamide.

In the title compound, C(23)H(25)BrN(4)O(3)S(2), the benzene rings bridged by the sulfonamide group are tilted relative to each other by 69.7 (1)° and the dihedral angle between the sulfur-bridged pyrimidine and benzene rings is 70.4 (1)°. The mol-ecular conformation is stabilized by a weak intra-molecular π-π stacking inter-action between the pyrimidine and the 4-methyl benzene rings [centroid-centroid distance = 3.633 (2) Å]. The piperidine ring adopts a chair conformation. In the crystal, mol-ecules are linked into inversion dimers by pairs of N-H⋯O hydrogen bonds.

N-[2-({[1-(4-Chloro-phen-yl)-1H-pyrazol-3-yl]-oxy}meth-yl)phen-yl]-N-meth-oxy-hydrazinecarboxamide.

In the title compound, C(18)H(18)ClN(5)O(3), the hydrazinecarboxamide N-N-C(O)-N unit is nearly planar [maximum deviation = 0.074 (2) Å] and is inclined at a dihedral angle of 57.43 (7)° with respect to the plane of the attached benzene ring. The chloro-phenyl group makes dihedral angles of 19.71 (7) and 34.07 (6)° with the pyrazole and benzene rings, respectively. In the crystal, pairs of N-H⋯O hydrogen bonds link the mol-ecules into inversion dimers that are further linked into chains along the a-axis direction by N-H⋯N hydrogen bonds. In addition, π-π stacking inter-actions are observed between benzene rings [centroid-centroid distance = 3.680 (1) Å].

Ethyl 6-(4-bromo-phen-yl)-4-(4-fluoro-phen-yl)-2-oxocyclo-hex-3-ene-1-carboxyl-ate.

There are two independent mol-ecules in the asymmetric unit of the title compound, C(21)H(18)BrFO(3), in which the dihedral angles between the fluoro-phenyl and bromo-phenyl groups are 77.0 (1) and 85.8 (1)°. In one of the mol-ecules, two methine C-H groups of the cyclo-hexene ring are disordered over two sets of sites in a 0.53 (2):0.47 (2) ratio. In both mol-ecules, the atoms of the ethyl group were refined as disordered over two sets of sites with occupancies of 0.67 (2):0.33 (2) and 0.63 (4):0.37 (4). The cyclo-hexene rings have slightly distorted sofa conformations in both mol-ecules. In the crystal, C-H⋯O inter-actions link mol-ecules into chains along the b axis.

N'-[(E)-4-Hy-droxy-benzyl-idene]-2-(naph-tha-len-2-yl-oxy)acetohydrazide.

The asymmetric unit of the title compound, C(19)H(16)N(2)O(3), contains two independent mol-ecules in which the dihedral angles between the naphthalene ring system and the benzene ring are 10.0 (1) and 35.3 (1)°. In the crystal, mol-ecules are linked by N-H⋯O and O-H⋯O hydrogen bonds, forming a two-dimensional framework parallel to (001). Weak C-H⋯O and C-H⋯N hydrogen bonds complete a three-dimensional network.

2-Meth-oxy-imino-2-{2-[(2-methyl-phen-oxy)meth-yl]phen-yl}ethanol.

In the title compound, C(17)H(19)NO(3), the dihedral angle between the benzene rings is 68.0 (1)°. The C-O-C-C torsion angle of the atoms joining these rings is 179.7 (2)°. The atoms of the methanol group were refined as disordered over two sets of sites with fixed occupancies of 0.86 and 0.14. The H atoms of the hy-droxy group in the major component are disordered over a further two sets of sites with equal occupancies. This is a necessary arrangement to allow for hydrogen bonding without unrealistic H⋯H contacts. In the crystal, O-H⋯N and O-H⋯O hydrogen bonds connect mol-ecules into chains along [001].

N-(2-{[5-Bromo-2-(piperidin-1-yl)pyrimidin-4-yl]sulfan-yl}-4-meth-oxy-phen-yl)-2,4,6-trimethyl-benzene-sulfonamide.

In the title compound, C(25)H(29)BrN(4)O(3)S(2), the benzene rings bridged by the sulfonamide group are tilted relative to each other by 63.9 (1)° and the dihedral angle between the sulfur-bridged pyrimidine and benzene rings is 64.9 (1)°. The mol-ecular conformation is stabilized by a weak intra-molecular π-π stacking inter-action between the pyrimidine and the 2,4,6-trimethyl-benzene rings [centroid-centroid distance = 3.766 (2) Å]. The piperidine ring adopts a chair conformation. In the crystal, mol-ecules are linked into inversion dimers by pairs of N-H⋯O hydrogen bonds and these dimers are further linked by C-H⋯O hydrogen bonds into chains propagating along [010].

N-(2-{[5-Bromo-2-(morpholin-4-yl)pyrimidin-4-yl]sulfan-yl}-4-meth-oxy-phen-yl)-4-chloro-benzene-sulfonamide.

In the title compound, C(21)H(20)BrClN(4)O(4)S(2), the benzene rings bridged by the sulfonamide group are tilted relative to each other by a dihedral angle of 70.2 (1)° and the dihedral angle between the sulfur-bridged pyrimidine and benzene rings is 69.5 (1)°. The mol-ecular conformation is stabilized by a weak intra-molecular π-π stacking inter-action between the pyrimidine and the 4-chloro-benzene rings [centroid-centroid distance = 3.978 (2) Å]. The morpholine ring adopts a chair conformation. In the crystal, mol-ecules are linked into inversion dimers by pairs of C-H⋯N hydrogen bonds and these dimers are further connected by N-H⋯O hydrogen bonds, forming a tape along the a axis.