Crystal structure of (Z)-ethyl 2-{5-[(2-benzyl-idene-3-oxo-2,3-di-hydro-benzo[b][1,4]thia-zin-4-yl)meth-yl]-1H-1,2,3-triazol-1-yl}acetate.

The title compound, C22H20N4O3S, features two fused six-membered rings linked to a 1,2,3-triazole ring which is attached to an ethyl acetate group. The heterocycle in the benzo-thia-zine residue has an envelope conformation with the S atom being the flap. The conformation of the ethyl acetate side chain, which is directed to the same side of the mol-ecule as the C6 ring of the fused-ring system, may be partially established by a pair of weak intra-molecular C-H⋯O(carbon-yl) inter-actions. The three-dimensional packing is aided by inter-molecular C-H⋯O and C-H⋯N inter-actions.

Crystal structure of 4-benzyl-2H-benzo[b][1,4]thia-zin-3(4H)-one.

In the title compound, C15H13NOS, the thia-zine ring adopts a twisted boat conformation and the dihedral angle between the aromatic rings is 86.54 (4)°. In the crystal, mol-ecules are linked by weak C-H⋯O inter-actions, resulting in chains along [010].

Bis(2-amino-4-methyl-pyrimidin-1-ium) hexa-aqua-cobalt(II) disulfate dihydrate.

In the title hydrated mixed-cation salt, (C(5)H(8)N(3))(2)[Co(H(2)O)(6)](SO(4))(2)·2H(2)O, the complete octa-hedral hexa-aqua complex cation is generated by crystallographic inversion symmetry. In the crystal, the components are linked by O-H⋯O and N-H⋯O hydrogen bonds, the latter, involving pyrimidinium cations and sulfate anions, generating R(2) (2)(8) loops. These, together with π-π inter-actions between centrosymmetrically related pyrimidinium cations [centroid-centroid separation = 3.5460 (8) Å], lead to the formation of a three-dimensional network.

Bis-(µ-pyridine-2,3-dicarboxyl-ato)bis-[aqua-(3-carb-oxy-pyridine-2-carboxyl-ato)indium(III)] tetra-hydrate.

In the binuclear centrosymmetric title compound, [In(2)(C(7)H(3)NO(4))(2)(C(7)H(4)NO(4))(2)(H(2)O)(2)]·4H(2)O, which contains both pyridine-2,3-dicarboxyl-ate and 3-carb-oxy-pyridine-2-carboxyl-ate ligands, the In(III) atom is six-coordinated in a distorted octa-hedral geometry. One pyridine ligand is N,O-chelated while the other is N,O-chelated and at the same time bridging to the other via the second carboxyl group. In the crystal, an extensive O-H⋯O hydrogen-bonding network, involving the coordinated and lattice water mol-ecules and the carboxyl groups of the ligands, together with C-H⋯O and π-π inter-actions [centroid-centroid distance = 3.793 (1) Å], leads to the formation of a three-dimensional structure.

Bis(benzenethiolato-S)(2,9-dimethyl-1,10-phenanthroline-N,N')cadmium(II).

The title compound, [Cd(C6H5S)2(C14H12N2)], exists as monomeric molecules with offset pi-stacking interactions between the phenanthroline ligands in adjacent molecules.

New 10-membered inorganic heterocyclic diphosphanes, PhN(PX)(2)[(-OC(6)H(2)((T)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)] (x = cl, f). Synthesis and transition metal complexes (molybdenum(0), ruthenium(II), palladium(II), and platinum(II)) of heterocyclic diphosphanes. crystal and molecular structures of the chloro derivative, PhN(PCl)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)], and of a molybdenum(0) complex of the fluoro derivative, [Mo(CO)(3)[eta(3)-PhN(PF)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)]-kappa P,kappa P,kappa S]].

Bis(dichlorophosphino)aniline, PhN(PCl(2))(2), reacts with stoichiometric amounts of 2,2'-thiobis(4,6-di-tert-butylphenol) to afford a 10-membered heterocycle, PhN(PCl)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t))Bu)(2)C(6)H(2)O-)] (1), in high yield. The structure of the heterocycle has been determined by a single-crystal X-ray analysis. The 10-membered heterocycle 1 reacts with SbF(3) to afford the corresponding fluoro derivative 2 in good yield. The compounds 1 and 2 act as tridentate ligands with molybdenum carbonyl derivatives, forming complexes of the type [Mo(CO)(3)[eta(3)-PhN(PX)(2)[(-OC(6)H(2)((t)Bu)(2))(mu-S)(((t)Bu)(2)C(6)H(2)O-)]-kappa P,kappa P,kappa S]] (3 X = Cl, 4 X = F). A crystal structure of the fluoro derivative 4 showed the facial tricarbonyl complex comprising a relatively strain-free tetracyclic structure with molybdenum in an octahedral environment; the two phosphorus and the sulfur centers were the donor atoms. Compound 2 readily reacts with Ru(II), Pd(II), and Pt(II) derivatives to form chelate complexes, demonstrating the eta(2) mode of coordination.

Diastereoselective synthesis of polysubstituted tetrahydropyrans and thiacyclohexanes via indium trichloride mediated cyclizations.

Polysubstituted tetrahydropyrans and thiacyclohexanes were synthesized in high yields with excellent diastereoselectivities via indium trichloride mediated cyclizations between homoallyl alcohols and mercaptans with aldehydes. In the case of tetrahydropyran products, the stereochemistry of the product was found to be directly correlated with the geometry of the homoallyl alcohols; whereas the cross-cyclization of aldehydes with trans-homoallyl alcohols generated (up-down-up) 2,3,4-trisubstituted tetrahydropyran products exclusively, the reaction of aldehydes with cis-homoallyl alcohols provided mainly (up-up-up) 2,3,4-trisubstituted products. When a trisubstituted homoallyl alcohol was used, its cross-cyclization with aldehydes generated (up-down-up-down-up) pentasubstituted tetrahydropyran derivatives with simultaneous controlling of five stereogenic centers. On the other hand, a cyclization-decyclization equilibrium was observed in the formation of thiacyclohexanes. The reaction of both cis- and trans-homoallyl mercaptans with aldehydes provided the same major diastereomers.

Synthetic and structural studies of the coordination behavior of 2-pyridylbis(diphenylphosphino)methane.

The coordination chemistry of the potentially semilabile tridentate ligand 2-pyridylbis(diphenylphosphino)methane (NPP) has been investigated. Bidentate (N, P) coordination occurs in CoCl(2)(NPP) (1) and [CdX(mu-X)(NPP)](2) (X = Cl (2); OAc (3)), prepared from the corresponding metal salts, in fac-Re(CO)(3)Br(NPP) (4) and in Fe(CO)(2)(MA)(NPP) (6). The last is one of three products from the reaction of Fe(CO)(4)(MA) (MA = maleic anhydride) with NPP, the other two being Fe(CO)(3)(NPP) (7; P, P coordinated) and the unusual cyclic ylid Ph2PC(2-C5H4N)PPh2C(CH2CO2H)C(=O)(5). The ligand shows tridentate coordination in Cr(CO)(3)(NPP) (9), RuCl(2)(PPh(3))(NPP) (10), and possibly in PtCl(2)(NPP) (8). Carbon monoxide displaces one phosphorus arm of the ligand in 10. Anhydrous NiCl(2) and NPP react in the presence of methanol to give NiCl(2)(P(OMe)Ph(2))(Ph(2)PCH(2)py) (12) in which the NPP ligand has been cleaved. This in turn reacts with O(2) to form trans-NiCl(2)(Ph(2)P(O)CH(2)py)(2) (13). The methine proton of NPP is transferred to the metal on reaction with Pt(C(2)H(4))(PPh(3))(2) and [Ir(COD)(NPP)]BF(4) to form the hydride complexes Pt(H)(PPh(3))(NPP-H) (14) and [Ir(H)(NPP)(NPP-H)]BF(4) (15). In 15 the intact NPP ligand is tridentate. The structures of 1 - 7 and 12 - 15 have been determined.

An intermediate for chloroquine analogs: (E)-2-(4,7-dichloro-2-quinolinyl)-3-(dimethylamino)-2-propenal.

The title compound C14H12C12N2O, has been shown to have an E configuration about the double bond in the propenal moiety. Significant delocalization of the lone pair on the N atom of the dimethylamino group into the pi system of this moiety is indicated by the planarity about this N atom.