S.I. Orysyk

cis-Bis[1-allyl-3-(2-pyrid­yl-κN)thio­ureato-κS]palladium(II)

Yellow plate-like shaped crystals of the title compound, [Pd(C9H10N3S)2], were obtained by ligand-exchange reaction between palladium(II) acetylacetonate and the corresponding organic reagent at room temperature. The PdII atom shows a slightly distorted square-planar coordination geometry consisting of two ligand molecules in a cis conformation that bind in their thiolic tautomeric form. Weak intermolecular Pd⋯H interactions with Pd—H distances of 3.328 (2) Å were observed in the crystal structure. The three-dimensional network of the crystal structure is realized by weak intermolecular C—H⋯N, N—H⋯N and C—H⋯S hydrogen bonds.

Palladium(II) complexes with 1-allyl-3-(2-pyridyl)thiourea: Synthesis and spectroscopic characterization

New Pd(II) complexes with 1-allyl-3-(2-pyridyl)thiourea (APTU) of the formulas [Pd(C9H11N3S)Cl2] (I) and [Pd(C9H11N3S)2]Cl2 (II) were obtained and examined by UV-Vis, IR, and 1H NMR spectroscopy. The conditions for the complexation reactions were optimized. The instability constants and molar absorption coefficients of these complexes were calculated. Comparison of the characteristic bands in the UV-Vis and IR spectra of the complexes and free APTU revealed that the ligand in both complexes is coordinated to the metal atom in the thione form in the bidentate chelating mode through the S atom of the thiourea group and the pyridine N atom. In the UV-Vis spectra of the complexes, the charge transfer bands (π → π* Py) and n → π* (C=NPy), (C=S) experience hypsochromic shifts by 450–470 cm−1 caused by the coordination of APTU to the metal ion, which gives rise to ligand-metal charge-transfer bands (C=NPy → Pd, n → π* (C=S)) and (SPd). The protons in the 6-, 4-, and 3-positions of the pyridine ring and the thiourea NH proton in the chelate ring are most sensitive to the complexation.

[Cu3(C11H12N3OS)3(C11H10N3OS)]SO4 · 3H2O, a trinuclear heteroleptic copper(II) complex with N-allyl-N′-salicylidenethiosemicarbazone and its cyclization product: Synthesis and X-ray diffraction study

Single crystals of a trinuclear copper(II) complex with N-allyl-N′-salicylidenethiosemicarbazone and its cyclization product were obtained and examined by X-ray diffraction. Prolonged keeping of the reaction mixture in aqueous ethanol at room temperature resulted in partial cyclization of the starting ligand into 2-(4-allyl-5-mercapto-4H-1,2,4-triazol-3-yl)phenol followed by coordination of both ligands to copper ions, giving a cluster-type trinuclear complex of the empirical formula C44H50N12O11S5Cu3. The crystals are monoclinic, space group P21/n, a = 14.1169(4) Å, b = 20.1006(5) Å, c = 19.6852(5) 0A, β = 107.065(2)°, Z = 4, R1 = 0.0586 (I > 4σ(I)). The structure of the complex consists of three square fragments; in each fragment, the Cu atom is coordinated in a tridentate fashion by the starting organic ligand in the thione form. The cyclization product of this ligand is coordinated through two triazole N atoms and the thiol S atom, thus extending the square environment of copper. The cluster structure of the complex is formed by the bridging bonds Cu-O-Cu between the Cu(1) and Cu(2) atoms and by the bridging bonds Cu-S-Cu between the Cu(2) and Cu(3) atoms.

Crystal structure of di­chlorido­{4-[(E)-(meth­oxy­imino-κN)meth­yl]-1,3-thia­zol-2-amine-κN3}palladium(II)

In the title compound, [PdCl2(C5H7N3OS)], the PdII atom adopts a distorted square-planar coordination sphere defined by two N atoms of the bidentate ligand and two Cl atoms. The mean deviation from the coordination plane is 0.029 Å. The methyl group is not coplanar with the plane of the metallacycle [torsion angle C—O—N—C = 20.2 (4)°]. Steric repulsion between the methyl group and atoms of the metallacycle is manifested by shortened intramolecular H⋯C contacts of 2.27, 2.38 and 2.64 Å, as compared with the sum of the van der Waals radii of 2.87 Å. The amino group participates via one H atom in the formation of an intramolecular N—H⋯Cl hydrogen bond. In the crystal, the other H atom of the amino group links molecules via bifurcated N—H⋯(Cl,O) hydrogen bonds into chains parallel to [001].

Rhodium(III), palladium(II), and platinum(II) complexes with 2-(2-hydroxybenzoyl)-N-methylhydrazinecarbothioamide: Syntheses, structures, and spectral characteristics

The syntheses and spectral (IR, UV-VIS, XPS, and 1H and 13C NMR) characteristics of the rhodium(III), palladium(II), and platinum(II) complexes with 2-(2-hydroxybenzoyl)-N-methylhydrazinecarbothioamide (HBMHCTA) are described. The coordination of HBMHCTA to the central metal ion and its intraligand rearrangement in the complex formation of rhodium(III) ions are studied. The structure of the mixed-ligand complex [Pd(H2L)PPh3] is determined by X-ray diffraction analysis.

trans-Dichloridobis(4-methoxyaniline-κN)palladium(II)

In the title compound, [PdCl2(C7H9NO)2], the Pd atom is situated on a crystallographic centre of inversion. The coordination environment of the Pd atom shows a slightly distorted square-planar geometry. The crystal structure exhibits weak intermolecular Pd⋯Cl interactions, with Pd⋯Cl distances of 3.6912 (6) Å. A chain-like arrangement of molecules realized by intermolecular N—H⋯Cl hydrogen bonds is observed along [010].

Novel Hybrid Compound 4-[(E)-2-phenylethenesulfonamido]-N-hydroxybutanamide with Antimetastatic and Cytotoxic Action: Synthesis and Anticancer Screening

BACKGROUND One of the most promising strategies to develop multi-targeted anticancer therapeutics is to introduce to the structure of a potential drug two or more pharmacophores (functional groups or structural fragments), which have antiproliferative, proapoptotic or antimetastatic properties acting via different mechanisms. OBJECTIVE To design, synthesize and perform screening of a novel hybrid anticancer compound. METHOD A novel hybrid compound 4-[(E)-2-phenylethenesulfonamido]-N-hydroxybutanamide, combining butanehydroxamate and styrenesulfonamide moieties, was designed, synthesized and investigated as a potent antimetastatic and antiproliferative agent. The structure and purity of the synthesized compound were confirmed by 1H NMR, 13C NMR, LC/MS spectroscopy and elemental analysis. The compound was screened for the anticancer activity in vitro against HeLa and in vivo against Lewis lung carcinoma tumor, using an antitumor metalloenzyme inhibitor GM6001 (Ilomastat, Galardin) and Pifithrin-μ as control anticancer agents. RESULTS It was found that the application of our compound resulted in a high fraction of apoptotic cells in the cell population, along with disruption in the cell cycle profile manifested as arrest of proliferative phases. Furthermore, changes of the morphological properties (i.e., an enhancement of adhesive properties and reduction of the nuclear-to-cytoplasm ratio) were found. The in vivo screening revealed that the compound significantly inhibited the metastasizing process that was manifested by a reduction in the number and volume of metastases. CONCLUSIONS The obtained results demonstrate that our compound can serve as a base for further structure optimization in order to design new highly-effective antimetastatic and antitumor agents.

cis-(Pyridin-2-ylcarbonimidodithio­ato-κ2S,S′)bis­(triphenyl­phosphane-κP)palladium(II)

The title compound, [Pd(C6H4N2S2)(C18H15P)2], was obtained as a minor product from the reaction of trans-PdCl2(PPh3)2 with piperazine-1,4-dicarbothioic acid bis(pyridin-2-yl)amide. The PdII atom displays a slightly distorted square-planar PdP2S2 geometry with a bidentately coordinated pyridin-2-ylcarbonimidodithioate ligand and two triphenylphosphine molecules, coordinated in cis positions. The crystal structure features weak π–π [centroid–centroid distance =3.7327(15) Å] and C–H⋯π interactions and contains an almost spherically shaped void of 50.4 Å3 per unit cell.

Poly[[μ2-(1Z,N′E)-2-(1,3-benzothia­zol-2-ylsulfan­yl)-N′-(2-oxidobenzyl­idene-κ2O:O)acetohydrazidato-κ2O,N′](pyridine-κN)copper(II)]

In the title compound, [Cu(C16H11N3O2S2)(C5H5N)]n, the CuII atom displays a square-pyramidal CuN2O3 coordination geometry with strong elongation in the vertex direction. The hydrazone molecule is coordinated to the CuII atom in a tridentate manner in the enolic form, creating five- and six-membered chelate metallarings. The pyridine molecule completes the square-planar base of the copper coordination environment. The crystal structure displays zigzag polymeric Cu—O—Cu chains along [001]. Several weak π–π interactions between benzothiazole rings were found in the same direction [centroid–centroid distances = 3.7484 (16), 3.7483 (16), 3.6731 (17) and 3.7649 (17) Å].

[1-(2-Oxidobenzyl­idene)-4-phenyl­thio­semicarbazidato-κ3O,N1,S](pyridine-κN)copper(II)

In the structure of the title compound, [Cu(C14H11N3OS)(C5H5N)], the CuII atom exhibits a slightly distorted square-planar CuN2OS coordination polyhedron consisting of a phenyl O, an azomethine N and a thioamide S atom from the tridentate thiosemicarbazonate dianion, and the N atom of a pyridine molecule. The thiosemicarbazonate ligand exists in the thiol tautomeric form as an E isomer. Rotational disorder of the pyridine and phenyl rings in a 1:1 ratio of the respective components is observed. An extensive network of weak N—H⋯S, C—H⋯O, C—H⋯N and C—H⋯S hydrogen-bonding interactions consolidates the structure.