SmI2-mediated reductive cyclization of ß-arylthio ketones: a facile and diastereoselective synthesis of thiochroman derivatives.

SmI2-mediated reductive cyclization of ß-arylthio ketones to generate thiochroman derivatives is not a generally observed process and the reported examples are limited to geminal disubstitution in the substrates. The results of the current study show that the cyclization also occurs when other substitution patterns are present, affording a general approach to dihydrothiochroman-ols in good yields and high degrees of diastereoselectivity. Besides, the halogen substitution on ß-aryl is tolerated in most cases here although reductive dehalogenation has been reported to predominate in the reductive cyclization process. Dihydrothiochroman-4-ols were readily oxidized to thiochroman-4-ols in almost quantitative yields.

Crystal structure of poly[{µ3-(E)-3-[3-(carboxyl-atometh-oxy)phen-yl]acrylato-κ3O,O':O'':O'''}[µ2-3-(pyridin-4-yl)-1H-pyrazole-κ2N:N']cobalt(II)].

The title compound, [Co(C11H8O5)(C8H7N3)] n , which is based on (E)-3-[3-(carb-oxy-meth-oxy)phen-yl]acrylic acid (H2L) and 3-(pyridin-4-yl)pyrazole (pp) ligands, has been synthesized under solvothermal conditions. The dihedral angle between pyrazole and pyridine rings in the pp ligands is 23.1 (2)°. In the crystal, helical chains formed by pp and L ligands connected to the CoII atom propagate parallel to the c axis. CoII atoms of adjacent chains are bridged by the acrylic acid groups of L ligands into corrugated polymeric sheets in the ac plane.

catena-Poly[[[diaqua-(1,10-phenan-thro-line)manganese]-µ-3-[3-(carboxyl-ato-meth-oxy)phen-yl]acrylato] monohydrate].

The title compound, [Mn(C11H8O5)(C12H8N2)(H2O)2]·H2O, was obtained under hydro-thermal conditions. The coordination environment of the Mn(II) atom is a distorted MnN2O4 octa-hedron defined by two N atoms from 1,10-phenanthroline, two water O atoms and two carboxyl-ate O atoms from two acrylate anions. The bis-monodentate coordination mode of the anion leads to the formation of chains propagating in [010]. Inter-molecular O-H⋯O hydrogen bonds link the chains into a two-dimensional network parallel to (100). In the voids of this arrangement, disordered lattice water mol-ecules are present.

catena-Poly[[[aqua-[3-(3-hy-droxy-phen-yl)prop-2-enoato]samarium(III)]-bis-[µ(2)-3-(3-hy-droxy-phen-yl)prop-2-enoato]] monohydrate].

The title Sm(III) compound, {[Sm(C(9)H(7)O(3))(3)(H(2)O)]·H(2)O}(n), was obtained under hydrothermal conditions. Its structure is isotypic with the analogous Eu complex. The latter was reported incorrectly in space group P1 by Yan et al. [J. Mol. Struct. (2008), 891, 298-304]. This was corrected by Marsh [Acta Cryst. B65, 782-783] to P-1. The Sm(III) ion is nine-coordinated by O atoms from one coordinating water molecule and the remaining ones from the 3-(3-hy-droxy-phen-yl)prop-2-enoatate anions (one bidentate, two bidentate and bridging, two monodentate bridging), leading to a distorted tricapped trigonal-prismatic coordination polyhedron surrounded by solvent water mol-ecules. In the crystal, extensive intermolecular O-H⋯O hydrogen-bonding inter-actions and π-π inter-actions [centroid-centroid separation = 3.9393 (1) Å] lead to the formation of a three-dimensional supra-molecular network.

Tetrakis[µ-3-(3-hy-droxy-phen-yl)propenoato]bis-{aqua-(2,2'-bipyridine)-[3-(3-hy-droxy-phen-yl)propenoato]neodymium(III)} 2,2'-bipyridine disolvate dihydrate.

The dinuclear title compound, [Nd(2)(C(9)H(7)O(3))(6)(C(10)H(8)N(2))(2)]·2C(10)H(8)N(2)·2H(2)O, was synthesized under hydro-thermal conditions. The centrosymmetric complex consists of two nine-coordinated Nd(3+) cations, six 3-hy-droxy-cinnamate anions and two chelating 2,2'-bipyridine mol-ecules. The coordination geometry around the cations can be best described as distorted tricapped trigonal-prismatic. The carboxyl-ate groups show different coordination and bridging modes. Two of them chelate to one Nd(3+) cation, two bridge the two cations in a bis-monodentate fashion, and two chelate to one and bridge monodentately to the symmetry-related Nd(3+) cation. The dinuclear mol-ecule is surrounded by two 2,2'-bipyridine solvent and two water mol-ecules. Extensive O-H⋯O and O-H⋯N hydrogen-bonding inter-actions between the components lead to the formation of a three-dimensional network.

Bis(2,2'-bipyridine-κN,N')bis-[3-(3-hy-droxyphenyl)propenoato-κO,O]cadmium.

The title compound, [Cd(C(9)H(7)O(3))(2)(C(10)H(8)N(2))(2)], was synthesized under mild hydro-thermal conditions. The structure of the complex mol-ecule consists of four approximately planar fragments: two 3-(3-hy-droxyphenyl)propenoate residues and two 2,2'-bipyridine ligands [largest deviation from the least-squares planes is 0.240 (1) Šfor one of 3-(3-hy-droxy-phenyl)propenoate residues]. The dihedral angles formed by the least-squares planes of the 2,2'-bipyridine ligands and the opposite 3-(3-hy-droxyphenyl)propenoate residues are 22.68 (7) and 26.47 (6)°. The CdN(4)O(4) coordination polyhedron can be described as distorted dodecahedral. Inter-molecular O-H⋯O hydrogen bonds between carboxyl-ate O atoms and hy-droxy groups lead to the formation of chains along the a-axis direction.

Bis(2-amino-3H-benzothia-zolium) bis-(7-oxabicyclo-[2.2.1]heptane-2,3-di-carbox-yl-ato)manganate(II) hexa-hydrate.

In the crystal structure of the title salt, (C(7)H(7)N(2)S)(2)[Mn(C(8)H(8)O(5))(2)]·6H(2)O, the heterocyclic N atom of the 2-amino-benzothia-zole mol-ecule is protonated. The Mn(II) atom (site symmetry ) has a slightly distorted octa-hedral MnO(6) coordination defined by the bridging O atoms of the bicyclo-heptane unit and four carboxyl-ate O atoms of two symmetry-related and fully deprotonated ligands. The crystal packing is stabilized by N-H⋯O hydrogen bonds between the cations and anions and by O-H⋯O hydrogen bonds including the crystal water mol-ecules.

Bis(µ-naphthalene-1,8-dicarboxyl-ato-κO:O)bis-[aqua-bis-(N,N'-dimethyl-formamide-κO)copper(II)].

In the centrosymmetric dinuclear title complex, [Cu(2)(C(12)H(6)O(4))(2)(C(3)H(7)NO)(4)(H(2)O)(2)], the coordination environment of each Cu(II) atom displays a distorted CuO(5) square-pyramidal geometry, which is formed by two carboxyl-ate O atoms of two µ-1,8-nap ligands (1,8-nap is naphthalene-1,8-dicarboxyl-ate), two O atoms of two DMF (DMF is N,N'-dimethyl-formamide) and one coordinated water mol-ecule. The Cu-O distances involving the four O atoms in the square plane are in the range 1.9501 (11)-1.9677 (11) Å, with the Cu atom lying nearly in the plane [deviation = 0.0726 (2) Å]. The axial O atom occupies the peak position with a Cu-O distance of 2.885 (12) Å, which is significantly longer than the rest of the Cu-O distances. Each 1,8-nap ligand acts as bridge, linking two Cu(II) atoms into a dinuclear structure. Inter-molecular O-H⋯O and C-H⋯O hydrogen-bonding inter-actions consolidate the structure.

2-[4-(Carb-oxy-meth-yl)phen-oxy]acetic acid.

The title compound, C(10)H(10)O(5), was obtained by the reaction of 4-hy-droxy-phenyl-acetic acid with chloro-acetic acid. In the crystal, the mol-ecules form a three-dimensional network by way of inter-molecular O-H⋯O hydrogen bonding.

Bis[µ-3-(2-hy-droxy-phen-yl)propenoato]bis-{aqua-(4,4'-bipyridine)-bis-[3-(2-hydroxy-phen-yl)propenoato]yttrium(III)} 4,4'-bipyridine disolvate.

The title compound, [Y(2)(C(9)H(7)O(3))(6)(C(10)H(8)N(2))(2)(H(2)O)(2)]·2C(10)H(8)N(2), contains two eight-coordinated Y(III) ions, which are linked by two carboxyl-ate groups from two 2-hy-droxy-cinnamate anions, leading to a centrosymmetric dinuclear structure surrounded by solvent 4,4'-bipyridine mol-ecules. It forms a three-dimensional framework connected by extensive O-H⋯O and O-H⋯N hydrogen-bonding inter-actions.

Poly[[tetraaqua-bis(µ(3)-1H-benzimidazole-5,6-dicarboxyl-ato)dicobalt(II)] trihydrate].

The title complex, {[Co(2)(C(9)H(4)N(2)O(4))(2)(H(2)O)(4)]·3H(2)O}(n), was synthesized hydro-thermally. The unique Co(II) ion is coordin-ated in a distorted octa-hedral coordination environment by two water mol-ecules and three symmetry-related 1H-benzimid-azole-5,6-dicarboxyl-ate (Hbidc) ligands. The Hbidc ligands coordinate via a bis-chelating and mono-chelating carboxyl-ate group and by an imidazole group N atom, bridging the Co(II) ions and forming an extended two-dimensional structure in the ab plane. In the crystal structure, inter-molecular N-H⋯O and O-H⋯O hydrogen bonds connect complex and solvent water mol-ecules, forming a three-dimensional supermolecular network. One of the solvent water mol-ecules lies on a twofold rotation axis.

catena-Poly[[[tetra-aqua-manganese(II)]-µ-4,4'-bipyridine] bis-(3-hydroxy-cinnamate) dihydrate].

The title compound, {[Mn(C(10)H(8)N(2))(H(2)O)(4)](C(9)H(7)O(3))(2)·2H(2)O}(n), was obtained by the hydro-thermal reaction of manganese chloride with mixed 3-hydroxy-lcinnamic acid (H(2)L) and 4,4'-bipyridine (4,4'-bipy) ligands. The structure contains [Mn(C(10)H(8)N(2))(H(2)O)(4)](2+) cations with the Mn(II) atoms lying on a centres of inversion and bridged into a linear chain along the a axis by 4,4'-bipy ligands, surrounded by HL(-) anions and uncoordinated water mol-ecules. Extensive O-H⋯O hydrogen-bonding and weak π-π inter-actions [centroid-centroid distance = 3.7572  (3) Å] between the constituents lead to the formation of a three-dimensional supra-molecular network.

Bis(µ-naphthalene-1,8-dicarboxyl-ato)bis-[aqua-(2,2'-bipyridine)zinc(II)] tetra-hydrate.

The title complex, [Zn(2)(C(12)H(6)O(4))(2)(C(10)H(8)N(2))(2)(H(2)O)(2)]·4H(2)O, is a binuclear complex with two independent Zn(II) ions in a slightly disorted trigonal bipyramidal environment, coordinated by one aqua ligand, two naphthalene-1,8-dicarboxyl-ate ligands and one 2,2'-bipyridine ligand. π-π Inter-actions [centroid-centroid distance of 3.8489 (5) Å] and O-H⋯O hydrogen bonds connect the mol-ecules, forming a three-dimensional structure.

Poly[mu-aqua-mu4-naphthalene-1,8-dicarboxylato-zinc(II)].

In the title complex, [Zn(C(12)H(6)O(4))(H(2)O)](n), a Zn(II) polymer based on naphthalene-1,8-dicarboxylate (1,8-nap), the Zn(II) atoms adopt an elongated octahedral coordination geometry. A zigzag chain is formed by mu(2)-aqua ligands and mu(2)-carboxylate groups of the 1,8-nap ligands. Adjacent parallel chains are further linked by 1,8-nap ligands, forming a twisted two-dimensional layer structure along the (100) plane.

Poly[(mu2-1,3-di-4-pyridylpropane-kappa2N:N')(mu3-glutarato-kappa3O:O':O'')dizinc(II)].

The title compound, [Zn2(C5H6O4)2(C13H14N2)]n or [Zn2(glu)2(bpp)]n, is a novel zinc polymer based on mixed flexible glutarate (glu) and 1,3-di-4-pyridylpropane (bpp) ligands. The Zn(II) center has a distorted tetrahedral geometry and the central atom of the bpp ligand is located at a special site with a C2 axis passing through it. A layer is formed by Zn-glu bonding. Such layers are pillared by bpp ligands, forming a three-dimensional framework with large channels. The inverted interpenetration of two three-dimensional frameworks completes the molecular structure.

catena-Poly[[tetraaquamanganese(II)]-mu-4-(carboxylatomethylsulfanyl)phenoxyacetato].

The title compound, [Mn(C10H8O5S)(H2O)4]n, a one-dimensional manganese(II) complex comprising helical chains bridged by 4-(carboxylatomethylsulfanyl)phenoxyacetate ligands has been characterized by single-crystal X-ray diffraction analysis. Hydrogen-bonding interactions between adjacent chains extend the complex into a three-dimensional supramolecular architecture.

A 3-D noninterpenetrating diamondoid network of a decanuclear copper(I) complex.

The solvothermal reaction of CuCl(2).2H(2)O with pyridine-4-thiol and ethanol yielded a novel photoluminescent 3-D polymeric complex with an interesting decorated diamondoid network that is constructed of decanuclear copper(I) cluster units and mu(4)-Cl ligands. The in situ generation of CuSO(4).5H(2)O implies the spontaneous occurrence of desulfurization and redox reactions in the present system.

4,4'-Thiodipyridinium tetrachlorocopper(II).

The title compound, (C(10)H(10)N(2)S)[CuCl(4)], was obtained by the reaction of cupric chloride with pyridine-4-thiol in a mixture of acetonitrile and tetrahydrofuran, suggesting that the desulfurization and coupling reactions of pyridine-4-thiol occurred in the presence of the Cu(2+) ion. X-ray diffraction analysis reveals the presence of one 4,4'-thiodipyridinium cation, H(2)bps(2+), and one [CuCl(4)](2-) anion. The cations interact with the anions via N-H...Cl hydrogen-bonding interactions to form a closed 'chair' conformation.

Poly[aquaneodymium(III)-mu5-2-oxido-5-sulfonatobenzoato].

The title compound, [Nd(C(7)H(3)O(6)S)(H(2)O)](n) or [Nd(SSA)(H(2)O)](n) (H(3)SSA is 5-sulfosalicylic acid), was synthesized by the hydrothermal reaction of Nd(2)O(3) with H(3)SSA in water. The compound forms a three-dimensional network in which the asymmetric unit contains one Nd(III) atom, one SSA ligand and one coordinated water molecule. The central Nd(III) ion is eight-coordinate, bonded to seven O atoms from five different SSA ligands [Nd-O = 2.405 (4)-2.612 (4) angstroms] and one aqua O atom [Nd-OW = 2.441 (4) angstroms].

Interweaving 3D network with double helical tubes filled by 1D coordination polymer chains.

The hydrothermal reaction of mellitic acid, 4,4'-bipydine, and Cu(CH(3)COO)(2).H(2)O gave rise to a novel 3D supramolecular architecture interpenetrated by three types of coordination polymer motifs. Two independent [[Cu(2)(mellitate)(4,4'-bpy)(H(2)O)(2)](2)(-)] 3D polymers incorporating helical substructures were interwoven into a 3D network with double-stranded helical tubes that host 1D linear polymers [Cu(4,4'-bpy)(H(2)O)(4)](2+)](n).