Mononuclear copper(II) nitrato complexes with methyl-substituted 4-nitropyridine N-oxide. Physicochemical and cytotoxic characteristics.

Three new complexes, products of the interaction of Cu(NO(3))(2) and methyl-substituted 4-nitropyridine N-oxides were synthesized and characterized by elemental analysis, magnetic, spectroscopic (IR, FIR and EPR), thermal and X-ray methods. The complexes (magnetic moments 1.70-1.81 BM at 300K) of general formula [Cu(H(2)O)(NO(3))(2)L(2)], L=2-methyl-4-nitropyridine N-oxide and [Cu(NO(3))(2) L'(2)], where L'=2,6-dimethyl- and 2,3,6-trimethyl-4-nitropyridine N-oxide were obtained. The compounds were unstable upon dissolution. The X-ray single crystal structure of Cu(II) complex with 2,6-dimethyl-4-nitropyridine N-oxide was determined and analysed. The compounds and free ligands were tested in vitro on the cytotoxic activity against MCF-7 and SW-707 human cancer cell lines. The complexes with 4-nitropyridine N-oxide (a reference) and 2-methyl-4-nitropyridine N-oxide show a significant anti-proliferative activity against studied cell lines. A reciprocal relationship between the activity and the number of methyl groups was observed. Both ligands and complexes are cytotoxic active but to the different cell lines.

Supramolecular motifs in the first structures of organic carboxylate salts of 1-(diaminomethylene)thiourea (HATU).

The structures of the first two organic carboxylate salts of 1-(diaminomethylene)thiourea (HATU), namely 1-(diaminomethylene)thiouron-1-ium formate, C2H7N4S+.HCOO-, (I), and bis[1-(diaminomethylene)thiouron-1-ium] oxalate dihydrate, 2C2H7N4S+.C2O(4)(2-).2H2O, (II), in which the oxalate lies on a symmetry centre, possess different extended hydrogen-bonding networks with different graph-set motifs. The R(2)(2)(8) motif present in (I) does not appear in (II), but an R(2)(1)(6) motif is present in both (I) and (II). Compound (I) has a three-dimensional hydrogen-bonding network, whereas (II) has a layered structure with layers joined by hydrogen-bonding motifs that form R(4)(2)(8) patterns. This work extends the known supramolecular structural data for HATU to include these organic carboxylates in addition to the previously characterized salts with inorganic acids.

Products of the interaction of (1-diaminomethylene)thiourea with hydrofluoric acid.

The salts 1-(diaminomethylene)thiouron-1-ium hydrogen difluoride, C(2)H(7)N(4)S(+).HF(2)(-), (I), and bis[1-(diaminomethylene)thiouron-1-ium] hexafluoridosilicate, 2C(2)H(7)N(4)S(+).SiF(6)(2-), (II), have both been obtained from the reaction of (1-diaminomethylene)thiourea (HATU) with hydrofluoric acid. Both compounds contain extensive networks of N-H...F hydrogen bonds. The hydrogen difluoride salt contains four independent asymmetric [HF(2)](-) anions. In the hexafluoridosilicate salt, the centrosymmetric [SiF(6)](2-) anion is distorted, although this distortion is not clearly correlated with the N-H...F hydrogen-bonding network.

[The occurrence of tobacco smoking and obesity in schizophrenia women]. / Wystepowanie palenia tytoniu i otylosci w grupie kobiet ze schizofrenia.

The aim of this study was to assess the occurrence of tobacco smoking and obesity in 58 schizophrenia women aged 45.1 +/- 9.9 years. 72% of women declared tobacco dependence as well as 14% smoked dependently on mood and 14% didn't smoke. There were statistically significant differences between women whose smoke or not in the case of BMI. The smoking women had significant higher BMI than non-smoking women (27.81 +/- 3.51 vs. 22.35 +/- 4.29, respectively). We didn't observe such comparisons between period smoking women and smoking women as well as non-smoking women. In the case of frequency distribution of schizophrenia women according to BMI we observed significant differences in this parameter. In the little underweight women (BMI below 20, n = 5) 60% didn't smoke. In the group of normal weight women (BMI = 21-25, n = 14) 64% smoked and 22% didn't. In the groups of overweight women (BMI = 26-30, n = 28) and obese women (BMI > 30) most of them were smoked. In the first of those groups 79% were smoking women and only 7% nonsmoking as well as in the second--all of women were smoked. These results show that the tobacco dependence and obesity could strongly correlate in schizophrenia and we need more studies in this case.

Products of the oxidation of 1-(diaminomethylene)thiourea with hydrogen peroxide.

Two oxidation products of 1-(diaminomethylene)thiourea (HATU) are reported, obtained from reactions with hydrogen peroxide at two different concentrations; these are 3,5-diamino-1,2,4-thiadiazole, C(2)H(4)N(4)S, (I), related to HATU by intramolecular N-S bond formation, and 1-(diaminomethylene)uronium hydrogen sulfate, C(2)H(7)N(4)O(+).HSO(4)(-), (II). In (I), molecular hydrogen-bonded chains could be distinguished, further organized in a herring-bone-like pattern. The structure of (II) is stabilized by an extensive network of N-H...O and O-H...O hydrogen bonds, where hydrogen-bonded anion chains and characteristic cation-anion motifs are present. The compounds are of importance not only with respect to crystal engineering, but also in the design of new synthetic routes to HATU transition metal complexes.

Methyl-substituted 4-nitropyridine N-oxides as ligands: structural, spectroscopic, magnetic and cytotoxic characteristics of copper(II) complexes.

Seven new mono- and dinuclear Cu(II) complexes containing various methyl substituted 4-nitropyridine N-oxides as ligands were isolated and characterized physicochemically and biologically. The characterization included elemental analysis, magnetic and spectroscopic methods (diffuse reflectance and UV-visible absorption, IR, FIR). A single crystal X-ray diffraction analysis was performed for the complex with 2,5-dimethyl-4-nitropyridine N-oxide. Trans- and cis-square planar configuration around Cu ion was established for mono- and dinuclear species, respectively. In methanolic solutions the dinuclear species decompose into mononuclear ones with increasing 4-->6 coordination number with attachment of two solvent molecules. The IR spectra showed that the strength of the Cu-ligand bond gauged by the degree of N-O elongation changed irregularly with position and number of methyl groups. Cytotoxic studies on the MCF-7 human breast cancer line revealed a structure-activity relationship: double blocking of the NO(2) group with two CH(3) groups rendered the complex completely inactive.

Synthesis, structural, physico-chemical and biological properties of new palladium(II) complexes with 2,6-dimethyl-4-nitropyridine.

This paper describes the synthesis and properties of two new palladium(II) complexes with 2,6-dimethyl-4-nitro-pyridine (dmnp): mononuclear [Pd(dmnp)2Cl2] and dinuclear [Pd2(dmnp)2Cl4]. Complexes were characterized on the basis of chemical and chromatographic analyses, MS and conductometric measurements, as well as by IR and NMR (1H and 13C) spectral studies. The crystal structures of ligand and mononuclear complex, trans-dichlorobis(2,6-dimethyl-4-nitro-pyridine)palladium(II), were determined by three-dimensional X-ray methods. The crystals of both compounds are monoclinic, space groups P21/c with a=19.075(4), b=5.419(1), c=15.045(3) A and beta=108.15(3)degrees for (dmnp), and a=7.544(2), b=14.509(3), c=8.032(2) A and beta=90.32(3)degrees for [Pd(dmnp)2Cl2]. In the (dmnp) there are two crystallographically independent molecules in the unit cell. The nitro groups and methyl C atoms are coplanar with the ring plane. The hydrogen bond of the type C-H...O links the molecules into pairs around center of symmetry. These dimers are held together by contacts of the van der Waals type. In the crystal structure of [Pd(dmnp)2Cl2] the Pd atom lies on an inversion center and is four-coordinated by two pyridine N atoms and by two Cl atoms in trans positions. The coordination geometry is square-planar, with Pd-N and Pd-Cl distances of 2.033(2) and 2.311(1) A, respectively. The two pyridine rings are mutually parallel, but they are twisted from the PdN2Cl2 coordination plane by about 88.5degrees. The preliminary assessments of anti-tumor properties of both complexes and ligand were evaluated as in vitro anti-proliferative activity in four human cancer cell lines: SW707 (adenocarcinoma of the rectum), T47D (breast cancer), HCV (bladder cancer) and A549 (non-small cell lung carcinoma). The [Pd(dmnp)2Cl2] exhibits strong cytotoxic activity against all cell lines whereas the free ligand and dinuclear [Pd2(dmnp)2Cl4] are only moderate active.