Crystal and molecular structure of (+)-6,7∶8,9∶10,11-tri-O-isopropylidene-2,3-dideoxy-d-arabino-l-allo-undec-2-enono-1,4-lactone,C20H30O9

The crystal structure of the title lactone, C₂₀H₃₀O₉, a potential precursor of uncommon 11-carbon sugar derivatives, has been determined by single-crystal diffraction methods. The compound crystallizes in the orthorhombic space groupP2₁2₁2₁ witha=15.581(3),b=14.047(2),c=9.888(2) Å, andZ=4. The structure was solved by direct methods and refined by full-matrix least-squares toR=0.054. The absolute configuration of the seven stereogenic carbon atoms was deduced as 4R, 5R, 6R, 7R, 8S, 9R, 10R, being (R)-(+)-glyceraldehyde its progenitor. An intramolecular O-HO hydrogen bond is present. Weak interaction C-HO links the molecules in sheets parallel to the (100) plane.     

Crystal and molecular structure of (−)-1,2-O-isopropylidene-3-O-methyl-7,8-dideoxy-β-l-glycero-d-gluco-non-7-enofuranurono-9,6-lactone,C13H18O7

The crystal structure of the title lactone, C₁₃H₁₈O₇, has been determined by single crystal diffraction methods. The compound crystallizes in the monoclinic space groupP2₁ witha=13.231(2),b=10.248(2),c=5.348(1) Å,=96.66(2)°, andZ=2. A total of 1055 reflection intensities were recorded on a Siemens AED single-crystal diffractometer (CuK radiation) at room temperature. The structure was solved by direct methods and electron density calculations. Full-matrix least-squares refinement gaveR=0.055 for 946 unique reflections above 2(I). The absolute configuration of the six chiral carbon atoms was deduced as 4S, 5R, 6R, 7S, 9R, 10R (crystallographic numbering corresponds to C-6, 5, 4, 3, 2, 1 in the title compound). An intermolecular O-HO hydrogen bond joins the molecules in chains which run along the twofold screw axis.     

Sodium 2‐oxo‐3‐semicarbazono‐2,3‐dihydro‐1H‐indole‐5‐sulfonate dihydrate

The title compound, Na⁺·C₉H₇N₄O₅S⁻·2H₂O, presents a Z configuration around the imine C=N bond and an E configuration around the C(O)NH₂ group, stabilized by two intra­molecular hydrogen bonds. The packing is governed by ionic inter­actions between the Na⁺ cation and the surrounding O atoms. The ionic unit, Na⁺ and 2‐oxo‐3‐semicarbazono‐2,3‐dihydro‐1H‐indole‐5‐sulfonate, forms layers extending in the bc plane. The layers are connected by hydrogen bonds involving the water mol­ecules.     

X-ray crystal and molecular structure of 2,3-dideoxy-4-thio-d-arabino-heptonic acid 1,4-lactone: a key intermediate for syntheses of 2′, 3′-dideoxy-4′-thio-l-nucleosides

The structure of 2,3-dideoxy-4-thio-d-arabino-heptonic acid 1,4-lactone has been determined by X-ray diffraction. Crystals of the compound are orthorhombic, space groupP2₁2₁2₁, with cell dimensionsa=11.555(5),b=10.451(5),c=9.604(5) Å, andZ=4. The diffraction experiment has allowed to assign the absolute configuration (4R, 5R, 6R) to the chiral centers of the molecule.     

X-ray crystal and molecular structure of [3,6-bis(2-pyridyl)pyridazine-N 1,N2]bis(triphenylphosphine) copper(I) hexafluorophosphate

[3,6-bis(2-pyridyl)pyridazine-N ¹,N²]bis(triphenylphosphine) copper(I) hexafluorophosphate crystallizes in space group $P\bar 1$ with cell dimensionaa=14.050(2),b=11.941(2),c=15.200(2) Å, α=71.28(1), β=67.02(1), and γ=84.78(2)^o. In the title compound, the mononuclear cation consists of a tetrahedral copper(I) center involving two nitrogen donors of the 3,6-bis(2-pyridyl)pyridazine (dppn) and two P atoms of the triphenylphosphine molecules. In the dppn ligand the two non-coordinating N atoms (one from pyridine and one from pyridazine) are mutallytrans.     

Isatin 3‐semicarbazone and 1‐methyl­isatin 3‐semicarbazone

The two title semicarbazones, namely 2,3‐dihydro‐1H‐indole‐2,3‐dione 3‐semicarbazone, C₉H₈N₄O₂, (I), and 1‐methyl‐2,3‐dihydro‐1H‐indole‐2,3‐dione 3‐semicarbazone, C₁₀H₁₀N₄O₂, (II), show the same configuration, viz. Z around the imine C=N bond and E around the C(O)—NH₂ bond, stabilized by two intra­molecular hydrogen bonds. The presence of a methyl group on the isatin N atom determines the difference in the packing; in (I), the mol­ecules are linked into chains which lie in the crystallographic (102) plane and run perpendicular to the b axis, while in (II), the mol­ecules are arranged to form helices running parallel to a crystallographic screw axis in the a direction.     

Highly stereocontrolled substitution of phenols with pyruvic esters. A viable route to ortho-hydroxyatrolactic esters of (2R)- and (2S)-configuration

Treatment of phenols with optically active (+)- and (?)-menthyl pyruvate assisted by Al(III)- or Ti(IV)-based promoters leads to the formation of $\text{ortho}$-hydroxyatrolactic esters of (2R)- and (2S)-configuration. The use of suitable menthol-based promoters augments markedly (up to 96% d.e.) the intrinsic stereochemical bias of the chiral pyruvate.     

Synthesis and X-ray structures of dinitrato-bis[2-(2′-thienyl)-1-(2′-thienylmethyl)benzimidazole]copper(II) and dichloro-bis-[2-(2′-thienyl)-benzimidazole]copper(II)-ethanol

Summary The reactions of Cu(NO₃)₂ · 3 H₂O with 2- (2-thienyl)-1-(2-thienylmethyl)benzimidazole (L) and of CuCl₂ · 2H₂O with 2-(2-thienyl)benzimidazole (L) have been carried out. The crystal structure of two isolated complexes,(1) and(2), have been determined by single-crystal x-ray diffraction methods. Crystals of(1) are monoclinic, space groupP2₁ /c, witha=9.884(4),b=9.892(4),c=18.732(8) Å, =114.89(2)°,Z=2;R=0.068 for 1909 observed reflections. Crystals of (2) are orthorhombic, space groupPbcn, witha=14.835(1),b=8.193(1),c=20.493(1) Å,Z=4;R=0.086 for 415 observed reflections. In the complex (1) the copper co-ordination is tetragonal (compressed octahedral) and involves a nitrogen atom of the organic ligand [Cu-N 1.970(6) Å] and two oxygen atoms of the nitrate group [Cu-O 2.318(7) and 2.246(9) Å] which appears to coordinate nearly symmetrically to the metal; however it has unusually large thermal motion which suggests a fluxional behaviour. In the complex (2) the co-ordination is square planar and involves an imidazole nitrogen [Cu-N 1.95(3) Å] and a chlorine atom [Cu-Cl 2.27(1) Å]. A long interaction Cu-S=3.37(2) Å completes the co-ordination polyhedron to a very elongated distorted tetragonal bipyramid. In both compounds a thiophene ring is disordered.