Synthesis and X-ray crystal structure of [2-(phosphinomethyl)ferrocenyl]diphenylphosphine

[2-(Phosphinomethyl)ferrocenyl]diphenylphosphine 2, is an air stable primary phosphine bearing a 1,2-disubstituted ferrocene framework, which has been prepared by reduction of the corresponding phosphonate. Confirmation of its structure has been obtained by X-ray single-crystals diffraction analysis. Despite its high stability toward oxidation, phosphine 2 still displays a normal coordinative behaviour toward [(p-cymene)RuCl₂]₂. The expected (p-cymene)RuCl₂(phosphine) complex is formed by coordination of the primary phosphine function, while the conceivably competitive complexation of the PPh₂ group was not observed.     

Characterization and X-ray crystal structure of butanoylsalophencobalt(III)

The synthesis and characterization of the pentacoordinated butanoylsalophencobalt(III) compound, including X-ray analysis, are described. The chemical shift in the ¹³C-n.m.r. of the carbonyl carbon was determined by means of an HMBC experiment. Collision induced dissociation (CID) and high resolution mass spectrometry were used to establish the fragmentation pattern of the CoC₂₄H₂₁N₂O₃ compound. X-ray diffraction analysis shows the presence of two conformations for the acylsalophen ligand system in the same monocrystal, as well as two different OH–C hydrogen bonds with unusual interactions.     

Synthesis and X-ray crystal structure analysis of (−)-1-menthoxygermatrane

A solvate complex of (−)-1-menthoxygermatrane with chloroform ( 1 ) was obtained by reaction of (−)-menthoxytriethylstannane with 1-bromogermatrane in chloroform. The crystal and molecular structure of 1 was established by X-ray analysis.     

Atropisomers of 1-(acyl or aroyl)-2-naphthylindolines. Isolation,X-ray crystal structure and conformational analysis

A series of pairs of stable diastereomeric atropisomers caused by restricted rotation around the Csp3-Csp2 bond of [2-(2-hydroxynaphthalen-1-yl)-3,3-dimethyl-2,3-dihydroindol-1-yl]-(3- or 4-substituted phenyl)-methanone or [2-(2-hydroxynaphthalen-1-yl)-3,3-dimethyl-2,3-dihydroindol-1-yl]-1-alkanone were isolated. The conformational analyses of the atropisomers were performed based on the X-ray crystallographic and (1)H-NMR spectral data. It became clear that rotation about the C2-naphthyl bond is restricted at room temperature, whereas the >NCO-Ar bond rotates freely.     

Synthesis and crystal structure of (S)-pindolol

Racemic 3-(4-indolyloxy)-1,2-propanediol 2 has been effectively resolved into (S)- and (R)-enantiomers by a preferential crystallization procedure. Non-racemic (S)-2 was converted into (S)-4-(2,3-epoxypropoxy)-1H-indole (S)-4 via a Mitsunobu reaction and then into (S)-pindolol (S)-1. The crystalline (S)-1 was studied by single crystal X-ray diffraction. A large number of symmetry independent molecules (Z′ = 6) led to a weakening of the system of strong intermolecular hydrogen bonds, which combined with a loose packing (PI = 64.6%), may be the cause of the abnormally low melting point of (S)-1 as compared with rac-1.     

Synthesis ofo-thiatelluraphenylenezirconocenes. X-ray crystal structure of

o-Thiatelluraphenylenezirconocene complexes were obtained in good yield by reaction of dilithiumo-benzenthiatelluride with zirconocene dichlorides. These compounds represent the first examples of heterodichalcogenaphenylene bent metallocences. They were characterized by spectroscopic methods and the effect on the n.m.r. results of stepwise substitution of one and two Te atoms for S is discussed. X-ray crystal structure analysis was performed for one representative complex. The structure is very similar to that previously reported for a diselenaphenylene complex, but the disorder observed for chalcogen atoms prevents an accurate comparison of the geometrical parameters with other related compounds.     

X-ray crystal structure of racemic bis(ethyl fumarate) (acetonitrile)nickel(0)

The crystal and molecular structure of racemic bis(ethyl fumarate)(acetonitrile) nickel(0) was determined from X-ray diffractometer data. The structure was solved by Patterson and Fourier methods, and refined by least-squares techniques to R = 0.045 for 3034 independent reflections.Crystals are triclinic, space group P$\text{1}$, with Z = 2, in a unit cell of dimensions: a 9.219 (6), b 13.257 (3), c 10.521 (9) », α 92.57 (9)°, β 109.25 (10)°, γ 110.0 (9)°.The coordination around the nickel(0) atom (the four carbon atoms of the HCCH groups, and the N atom of the acetonitrile residue), may be described as planar, with a slightly distorted trigonal symmetry. The conformations of the two ehtyl fumarate residues agree, more or less closely, with the principle of staggered bonds. The torsion angles around the HCCH groups are significantly different from 180°, as observed in other similar complexes. The four asymmetric carbon atoms of a molecule have the same absolute configuration. SSSS and RRRR molecules are present in the unit cell.     

X-ray crystal structure of manganese(II) bis(ethylenediphosphinetetraacetato)nickelate(II) hexadecahydrate

X-ray structure analysis of the title compound (diffractometer data, R = 0.061 for 2805 reflections) confirmed the structure proposed on the basis of spectral evidence for the series of isostructural complexes, M₃[NiL₂ (H₂O)₁₆, where H₄L = (HO₂CCH₂)₂PCH₂CH₂P(CH₂CO₂H)₂ and M = Mn, Fe, Co, Ni, Zn or Cd. The compound studied is monoclinic, P2₁/c, a = 9.990(3), b = 28.51(2), c = 14.828(9) Å, β =94.50(5)°, Z = 4. Nickel(II) is coordinated by two P,P-chelating ligand anions in a rather distorted square planar environment. The carboxyl groups of the ligand are not coordinated to nickel; three of them remain free and five are bonded, together with 10 of the total of 16 water molecules, to the manganese(II) ions. The environments of three manganese ions thus formed are all nearly octahedral but differ in the number and bonding mode of the carboxyls (monodentate and/or bridging bidentate). The carboxyl-to-manganese bonds produce a three-dimensional structure of the compound which is further stabilized by hydrogen bonding.     

Synthesis and crystal structure of (S)-(+)-2-[(1,1-dimethylethoxy)carbonyl] amino-2-phenylethanol

The preparation and the crystal structure of the title compound are described. C₆H₅CH[NHCOOC(CH₃)₃]CH₂OH is monoclinic with the following unit-cell dimensions: a = 10.354(2), b = 6.533(3), c = 10.505(1) Å, β = 98.58(1)∘. The space group is P2₁ and Z = 2. The crystal-structure determination was run by using 1481 independent reflexions with a final R value of 0.033 (R_w = 0.043).     

X-ray crystal structure of trimethylsilylmethyllithium

The solid state structure of trimethylsilylmethyllithium has been determined by single crystal X-ray diffraction techniques. The compound crystallizes in the monoclinic system, space group P2₁/n. Cell dimensions were determined as follows: a 10.931(3), b 18.397(6), c 21.490(8) Å, β 96.0(2)°, V 4298(2) ų, Z = 4, and a final R_f 5.1% based on 2203 data with σ(I) ≥ 2.5σ(I). The compound is formed by hexameric units, {LiCH₂Si(CH₃)₃}₆, with two distinct classes of LiLi distances of 2.46 and 3.18 Å. There are also two LiC distances av 2.20 and 2.27 Å. The LiH distances to the methylene H atoms have been determined and are short varying between 2.0 and 2.3 Å to the closest lithium atom. The structure, including possible LiH interactions, is discussed and compared with the other known hexameric aggregates.     

The preparation and X-ray crystal and molecular structure of (α,1,2-η-6-methylbenzyl) bis(triphenylphosphine)rhodium(I)

Reaction of [RhCl(PPh₃)₃] with [o-MeC₆H₄CH₂MgBr] affords high yields of the non-fluxional complex, [Rh(CH₂C₆H₄Me)(PPh₃)₂] which has been shown crystallographically to contain a 1-3-η-benzyl group bound through the phenyl carbon atom that is not substituted with the methyl group. Crystals of this compound are triclinic, space group P$\text{1}$, with a = 10.561(6). b = 17.705(3), c = 10.934(4) Å, α = 80.69(3), β = 116.86(4), γ = 102.30(4)° and Z = 2. The structure was solved via the heavy-atom method and refined to R = 0.032 using 5379 diffractometer data with I > 1.56(I). Attempts to prepare π-bonded xylylene complexes from this compound by reaction with base have been unsuccessful, but protonation followed by recrystallisation from acetone gives [Rh{(CH₃)₂CO}₂(PPh₃)₂]BF₄.     

The crystal and molecular structure of (-)-phaseollin

X-ray analysis has defined the molecular structure of (-)-phaseollin C₂₀H₁₈O₄ a pterocarpan with lipophilic antifungal activity, isolated from Phaseolus vulgaris L. The orthohombic crystals belong to the space group P2₁2₁2₁ with a =6.540(3), b = 12.975(6), c = 19.388(4) Å and Z =4. The structure was solved by direct methods from diffractometer data measured with CuKα radiation, and refined to a final R index of 0.083 for the 992 observed terms. The molecular skeleton(I) has a cis B/C ring junction. Viewed down C(6B)-C(7) the conformation is staggered; ring C is envelope whereas ring B is skewed with C(6B) and C(7) lying respectively above and below the plane of the other ring atoms.     

Preparation,X-ray crystal structure and 13C- and 1H-NMR study of 1-methyl-2-(N-methyl-N-phenylglycyl)-3-(N-methylanilino)indole

Reaction of N-methylaniline with 40% glyoxal yields 1-methyl-2-(N-methyl-N-phenylglycyl)-3-(N-methylanilino)indole ( 1a ) as the main product together with 1-methyl-3-(N-methylanilino)indole ( 1b ). The reaction appears to be general for aromatic secondary amines since N-ethylaniline and N-phenylbenzylamine yield the corresponding indoles. The structure of 1a has been verified by single crystal X-ray diffraction. Compound 1a (C₂₅H₂₅N₃O) crystallized in the triclinic space group Pl? with cell dimensions a = 10.085(3)Å, b = 10.371(3)Å, c = 11.908(5)Å, α = 74.2(3)°, β = 74.7(3)° and γ = 60.7(2)° with Z = 2. The complete ¹H and ¹³C nmr assignment of indoles 1a and 1b was achieved from two-dimensional HETCOR and COSY spectra with the aid of homonuclear and heteronuclear double resonance experiments.