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Ionic salts with the formulae {3[BPMTU]+ 3[X]- nH2O} (BPMTU = 1,3-bis(3-pyridylmethyl)-2-thiourea, X = Cl - and n = 1.5 (1), X = Br-and n = 1 (2), X = I- and n = 1 (3)) were synthesized. The compounds have been characterized by elemental anaylses, TG-DTA, FT-IR, far-IR, Raman, ESI-MS and 1H, 13C-NMR spectroscopic methods, and X-ray powder diffraction techniques. The crystal structures of 1 and 2 have also been determined by X-ray diffraction at 120(2) and 100(2) K, respectively. In 1, weak lp(Cl-) → σ*(O-H) hyperconjugative interactions and OH⋯Cl- hydrogen-bonding interactions lead to the formation of 1-D zigzag tetrameric complexes consisting of four chlorides bridged by four waters. Two oxygens of the bridging waters are also coordinated to Cl- of the complex forming a parallelogram-shaped ring. Two chlorides are also anchored by NH⋯Cl - hydrogen bonds in the free space between four tetrameric complexes. Heating 1 at 100C for 4 h does not remove lattice water and the framework structure is retained. In 2, NH⋯Br- hydrogen-bonding interactions stabilize the supramolecular architecture. In this case, however, only two bromides are bridged by one water through OH⋯Br- hydrogen bonds. The supramolecular interactions existing in the crystal packing of the ionic salts have been analyzed at the density functional theories and ab initio CCSD(T) levels of the theory. © 2011 Taylor & Francis. 64 2 202 221

2-Nitrosopyridine, 1, 3-methyl-2-nitrosopyridine, 2, and 4-methyl-2-nitrosopyridine, 3, exist in org. solvents as monomer-azodioxy dimer equil. with the dimers predominating at ambient temps. In the case of compds. 1 and 3 only the Z-dimers co-exist with the monomers, whereas for compd. 2 both Z- (major) and E- (minor) dimers are present with the monomer. Variable temp. 1H NMR bandshape anal. and 2D-EXSY spectra of 1-3 provided thermodn. and kinetic data for the dissocn. equil. Z- (or E-) dimer .dblharw. 2 monomer, ΔH values being in the range 53-58 kJ mol-1 and ΔG ‡ (298.15 K) values in the range 70-82 kJ mol-1. An X-ray crystal structure of 1 identified the compd. as a Z-dimeric species with the two pyridine rings twisted by 62.7° and their heterocyclic N atoms pointing towards each other.

Ionic salts with the formulae {3[GBPMTU]ΓΎ 3[X] nH2O} (BPMTUΒΌ1,3-bis(3-pyridylmethyl)-2-thiourea, XΒΌCl and nΒΌ1.5 (1), XΒΌBr and nΒΌ1 (2), XΒΌI and nΒΌ1 (3)) were synthesized. The compounds have been characterized by elemental anaylses, TG-DTA, FT-IR, far-IR, Raman, ESI-MS and 1H, 13C-NMR spectroscopic methods, and X-ray powder diffraction techniques. The crystal structures of 1 and 2 have also been determined by X-ray diffraction at 120(2) and 100(2) K, respectively. In 1, weak lp(Cl )! *(O-G) hyperconjugative interactions and OH Cl hydrogen-bonding interactions lead to the formation of 1-D zigzag tetrameric complexes consisting of four chlorides bridged by four waters. Two oxygens of the bridging waters are also coordinated to Cl of the complex forming a parallelogramshaped ring. Two chlorides are also anchored by NH Cl hydrogen bonds in the free space between four tetrameric complexes. Heating 1 at 100 C for 4 h does not remove lattice water and the framework structure is retained. In 2, NH Br hydrogen-bonding interactions stabilize the supramolecular architecture. In this case, however, only two bromides are bridged by one water through OH Br hydrogen bonds. The supramolecular interactions existing in the crystal packing of the ionic salts have been analyzed at the density functional theories and ab initio CCSD(T) levels of the theory. Journal of Coordination Chemistry

Ionic salts with the formulae {3[GBPMTU](+)center dot 3[X](-)center dot nH(2)O} (BPMTU = 1,3-bis(3-pyridylmethyl)- 2-thiourea, X = Cl- and n = 1.5 (1), X = Br- and n = 1 (2), X = I- and n = 1 (3)) were synthesized. The compounds have been characterized by elemental anaylses, TG-DTA, FT-IR, far-IR, Raman, ESI-MS and H-1, C-13-NMR spectroscopic methods, and X-ray powder diffraction techniques. The crystal structures of 1 and 2 have also been determined by X-ray diffraction at 120(2) and 100(2) K, respectively. In 1, weak 1p(Cl-) -> sigma*(O-H) hyperconjugative interactions and OH center dot center dot center dot Cl- hydrogen-bonding interactions lead to the formation of 1-D zigzag tetrameric complexes consisting of four chlorides bridged by four waters. Two oxygens of the bridging waters are also coordinated to Cl- of the complex forming a parallelogram-shaped ring. Two chlorides are also anchored by NH center dot center dot center dot Cl- hydrogen bonds in the free space between four tetrameric complexes. Heating 1 at 100 degrees C for 4 h does not remove lattice water and the framework structure is retained. In 2, NH center dot center dot center dot Br- hydrogen-bonding interactions stabilize the supramolecular architecture. In this case, however, only two bromides are bridged by one water through OH center dot center dot center dot Br- hydrogen bonds. The supramolecular interactions existing in the crystal packing of the ionic salts have been analyzed at the density functional theories and ab initio CCSD(T) levels of the theory. Journal of Coordination Chemistry

Ionic salts with the formulae {3[GBPMTU](+)center dot 3[X](-)center dot nH(2)O} (BPMTU = 1,3-bis(3-pyridylmethyl)- 2-thiourea, X = Cl(-) and n = 1.5 (1), X = Br(-) and n = 1 (2), X = I(-) and n = 1 (3)) were synthesized. The compounds have been characterized by elemental anaylses, TG-DTA, FT-IR, far-IR, Raman, ESI-MS and (1)H, (13)C-NMR spectroscopic methods, and X-ray powder diffraction techniques. The crystal structures of 1 and 2 have also been determined by X-ray diffraction at 120(2) and 100(2) K, respectively. In 1, weak 1p(Cl(-)) -> sigma*(O-H) hyperconjugative interactions and OH center dot center dot center dot Cl(-) hydrogen-bonding interactions lead to the formation of 1-D zigzag tetrameric complexes consisting of four chlorides bridged by four waters. Two oxygens of the bridging waters are also coordinated to Cl(-) of the complex forming a parallelogram-shaped ring. Two chlorides are also anchored by NH center dot center dot center dot Cl(-) hydrogen bonds in the free space between four tetrameric complexes. Heating 1 at 100 degrees C for 4 h does not remove lattice water and the framework structure is retained. In 2, NH center dot center dot center dot Br(-) hydrogen-bonding interactions stabilize the supramolecular architecture. In this case, however, only two bromides are bridged by one water through OH center dot center dot center dot Br(-) hydrogen bonds. The supramolecular interactions existing in the crystal packing of the ionic salts have been analyzed at the density functional theories and ab initio CCSD(T) levels of the theory. Journal of Coordination Chemistry

The reaction between 2-thiobarbituric acid (H(2)TBA), which was treated with an equimolar amount of potassium hydroxide, in a water with triphenytin chloride in methanol, results in the formation of the {[Ph3Sn(O-HTBA)]}(n) (1) complex. Crystals of the hydrated 1 with formula {[Ph3Sn(O-HTBA)]center dot 0.7(H2O)}(n) were growth from methanol/acetonitrile solution, of the white precipitation, filtered off, from the reaction. The crystal structure of complex 1 has been determined by X-ray diffraction at 120K. Complex 1 is polymeric. The geometry around the tin(IV) ions is trigonal bi-pyramidal with coordination to three C atoms from phenyl groups and one O atom from a de-protonated HTBA ligand. Complex 1 and the already known [(n-Bu)(3)Sn(O-HTBA)center dot H2O] (2) were evaluated for their in vitro cytotoxic activity (cell viability) against human cancer cell lines: HeLa (cervical), OAW-42 (ovarian), MCF-7 (breast, ER positive), MDA-MB-231 (breast, ER negative), A549 (lung), Caki-1 (renal) and additionally, the normal human lung cell line MRC-5 (normal human fetal lung fibroblast cells) and normal immortalized human mammary gland epithelial cell line MTSV17 with a Trypan Blue assay. Moreover complex I was evaluated for its in vitro cell growth proliferation activity against leiomyosarcoma cells (LMS), MCF-7 and MRC-5 cells with a Thiazolyl Blue Tetrazolium Bromide (MU) assay. The type of cell death caused by complexes 1 and 2 was also evaluated by use of flow cytometry assay. The results showed that these compounds mediate a strong cytotoxic response to normal and cancer cell lines tested through apoptosis and induce cell cycle arrest in S phase of the cell cycle, suggesting DNA intercalation (direct or indirect) with the complexes. Finally, the influence of these complexes 1 and 2 upon the catalytic peroxidation of linoleic acid to hydroperoxylinoleic acid by the enzyme lipoxygenase (LOX) was kinetically and theoretically studied. (C) 2011 Elsevier Masson SAS. All rights reserved. Eur J Med Chem

J. Coord. Chem.

The reactions of tetrachloroauric(III) acid (HAuCl(4)) with the thioamides; 2-mercapto-benzothiazole (mbztH) and 5-ethoxy-2-mercapto-benzimidazole (EtmbzimH) lead to the desulfuration of the ligands and the formation of the ionic complexes {[AuCl(4)](-)[bztH(2)](+)} (1), and {[AuCl(4)](-)[EtbzimH(2)](+)(H(2)O)} (2) (where bztH(2)(+) and EtbzimH(2)(+) are the desulfurated cations of the starting ligands). The reaction of HAuCl(4) with 2-mercapto-nicotinic acid (mnaH(2)), however results in the formation of 2-sulfonate-nicotininc acid (C(6)H(5)NO(5)S) (3) with the simultaneous oxidation of the sulfur atom. On the other hand, the reactions of the gold(I) complex [Au(tpp)Cl] (4) (tpp = triphenylphosphine (Ph(3)P)) with the thioamides; 2-mercapto-thiazolidine (mtzdH), 2-mercapto-benzothiazole (mbztH) and 5-chloro-2-mercapto-benzothiazole (ClmbztH) in the presence of potassium hydroxide resulted in the formation of the gold(I) complexes of formulae [Au(tpp)(mtzd)] (5), [Au(tpp)(mbzt)] (6) and [Au(tpp)(Clmbzt)] (7) without ligand desulfuration. All complexes have been characterized by elemental analysis, FT-IR, far-FT-IR, (1)H-NMR, spectroscopic techniques and X-Ray crystallography. The electrochemical behavior of 1, 2 and 4-7 complexes and the ligands EtmbzimH, mbztH and mnaH(2) was also studied in acetonitrile and DMF using cyclic voltammetry. The results are in support of a mechanism of desulfuration of the ligands by Au(III), involving a first oxidation of S to -SO(3)(-), followed by a C-S bond cleavage. This is also supported by PM6 calculations of bond dissociation energies of the various compounds involved. Complexes 1, 2 and 4-7 were tested for in vitro cytotoxicity against leiomyosarcoma cells and the results are discussed in relation with the geometry of the complexes and compared with those of cisplatin and other metals. Complexes 1 and 5 showed higher activity than that of cisplatin, while HAuCl(4) was inactive against sarcoma cells. Dalton Transactions

A novel tri-n-butyl(IV) derivative of 2-thiobarbituric acid (HTBA) of formula [(n-Bu)(3)Sn(TBA) center dot H(2)O] ( 1) has been synthesized and characterized by elemental analysis and (119)Sn-NMR and FT-IR spectroscopic techniques. The crystal structure of complex 1 has been determined by single crystal X-ray diffraction analysis at 120( 2) K. The geometry around Sn( IV) is trigonal bipyramidal. Three n-butyl groups and one oxygen atom from a deprotonated 2-thiobarbituric ligand are bonded to the metal center. The geometry is completed with one oxygen from a water molecule. Compound 1 exhibits potent, in vitro, cytotoxicity against sarcoma cancer cells (mesenchymal tissue) from the Wistar rat, polycyclic aromatic hydrocarbons (PAH, benzo[a] pyrene) carcinogenesis. In addition, the inhibition caused by 1, in the rate of lipoxygenase (LOX) catalyzed oxidation reaction of linoleic acid to hyperoxolinoleic acid, has been also kinetically and theoretically studied. The results are compared to that of cisplatin. Copyright (c) 2008. Bioinorg Chem Appl

The reaction of [Ru2(CO)6Cl4], 1, with excess THZ (1,3-thiazole) in absolute ethanol at 55 degrees C produces fac-[Ru(CO)3Cl2(THZ)], 2, in high yield. [Ru(CO)2Cl2(THZ)2], 3, is formed at higher temperature (ca 70 degrees C) and higher concentration of THZ. The X-ray structures of the new compounds have been determined, and density functional studies performed at the hybrid B3LYP/(Lanl2DZ, Ru; 6-311+G**, CHClNOS) level allowed the estimation of the structures of several conformers as well as that of their relative total electronic energies. Compound 2 is soluble (slowly) in aqueous media, where it reacts with the transport proteins bovine serum albumin (BSA) and human apotransferrin (HTF), and at a lower extent with calf thymus DNA (CT-DNA) and with guanosine-5'-monophosphate (GMP). The complex molecule is adsorbed by certain synthetic acryloyl polymers that have terminal carboxylate functions and is embedded in silica gels when these latter are prepared in the presence of a solution of 2. Ruthenium species are slowly released from the loaded gels into physiological solutions at pH 7.4. The reactivity of 2 with biomolecules and synthetic hydrogels makes it a compound of interest for anticancer and antimetastases tests.

Similar In(μ-Br) 2M bridging motifs are found in the crystal structures of the diindium and mixed lithium/indium species [{(η 5-C 5H 5)Fe(CO) 2} 2InBr] 2 (1) and [(η 5-C 5H 5)Fe(CO) 2]2In(μ-Br) 2Li(OEt 2) 2 (2). The metric parameters for 1 are in close agreement with those found for the analogous chloride and iodide complexes, but differ from those found in monomelic [(η 5-C 5Me 5)Fe(CO) 2] 2InBr, on account of the four coordinate geometry at indium and the bridging nature of the bromide ligands.

The crystal structures of [XnE]+[(η7-C7H7)Mo(CO)2GaI3]- [XnE = (C4H8O)4Li (1), (C6H11)3PH (2)] are reported, revealing: (1) monoclinic, P21/c, a = 11.2388(1), b = 17.3201(3), c = 17.5473(2)Å, β = 101.623(1)°, Z = 4, R = 0.038 and wR2 = 0.090 for 7614 observed reflections [I>2σ(I)]; (2) monoclinic, P21/n, a = 9.2979(5), b = 18.4632(8), c = 19.9789(9)Å, β = 99.325(3)°, Z = 4, R = 0.073 and wR2 = 0.184 for 5554 observed reflections [I > 2σ (I)]. 2007 © The Japan Society for Analytical Chemistry.