3-Cyclopropyl-1,2-dimethyldiaziridine: synthesis and study of molecular structure by gas electron diffraction method

The molecular structure and conformational behavior of 3-cyclopropyl-1,2-dimethyldiaziridine have been for the first time experimentally studied by gas-phase electron diffraction and quantum chemical calculations. The two most stable conformers at 298 K possess anti and gauche mutual ring orientation (with prevalence of the anti conformer) whereas only one anti conformer is observed in solution. The determined structural parameters of gaseous 3-cyclopropyl-1,2-dimethyldiaziridine have been compared with those for 3,3-bidiaziridine structural analogues in the crystal phase. The simple and convenient procedure for the synthesis of 3-cyclopropyl-1,2-dimethyldiaziridine comprising cyclopropane and diaziridine rings in one molecule was developed. The standard enthalpy of formation of 3-cyclopropyl-1,2-dimethyldiaziridine in the gas phase was calculated using Gaussian-4 theory, yielding value of 281.9?±?5.0 kJ/mol.     

An electron diffraction study of the molecular structure of 1,2-difluoroethane

The molecular structure of 1,2-difluoroethane in the gas phase has been determined by electron diffraction at room temperature. Only the gauche conformation was found, the dihedral angle F-C-C-F is 74.5°. The bond lengths r_g(1) are: r(C-C) = 1.535 Å, r(C-F) = 1.394 Å, r(C-H) = 1.13 Å. The valency angles are: α(C-C-F) = 108.3, α(C-C-H) = 108.3. The dihedral angle between the C-C-F and C-C-H planes is 113.6°.     

The molecular structure of cis- and trans-1,2-difluoro-ethene: An electron diffraction study

The molecular structure of cis- and trans-1,2-difluoroethene was studied in the gas phase by electron diffraction, using the sector-microphotometer technique. The molecules are planar. For trans-difluoroethene the geometrical parameters are: C-F bond: 1.338(0.003) Å; CC bond: 1.320(0.009) Å; C-H bond: 1.088(0.004) Å, ∠CCF 119.8°(0.2°); ∠CCH: 125° (1.2°). For cis-difluoroethene: C-F bond: 1.332(0.003) Å; CC bond: 1.311(0.008) Å; C-H bond: 1.100(0.003) Å; ∠CCF: 122.5°(0.2°); ∠CCH:127.0 °(2.3°).     

An electron diffraction study of deposited docosanoic acid monolayers

Docosanoic acid monolayers deposited on thin polymer films under different water surface conditions have been investigated using transmission electron diffraction at normal and tilted incidence. Diffraction patterns obtained from the L₂ and L₂' phase are quite similar, but distinctly different to samples coated from the CS phase. The former were consistent with molecules perpendicular to the substrate, arranged in a texture of grains with unusual orthorhombic packing. There is evidence for a phase transition from a liquid crystalline phase on the water surface.     

An electron diffraction study of the molecular structure of hexamethyldisiloxane

An electron diffraction determination of the molecular geometry of hexamethyldisiloxane has removed much of the uncertainty concerning this structure. The length of the SiO bond and the SiOSi bond angle were determined to be 1.631 ± 0.003 Å and 148 ± 3°, respectively. The experimental data are consistent with a staggered conformation (C_2v symmetry) while a model with twist angles around the SiO bonds of about 30° cannot be excluded. The molecule is probably performing large amplitude intramolecular motion.     

An electron diffraction study of the molecular structure of meta-difluorobenzene

The molecular structure of meta-difluorobenzene in the gas phase has been determined by electron diffraction at room temperature. The carbon ring deviates slightly from D_6h symmetry. The four C-C distances adjacent to the F atoms are 1.384 Å, the two other C-C distances are slightly longer, i.e. 1.405 Å. The C-F and C-H distances are 1.324 and 1.107 Å. The C-C-F valency angle is 119.5°.     

An electron diffraction study of the molecular geometry of dimethyl sulphone

The present electron diffraction study of dimethyl sulphone eliminates the discrepancy between the values of the parameter ∠O-S-O obtained by microwave spectroscopy and electron diffraction. The following geometrical parameters (r_a values) have been obtained: r(C-H) = 1.114±0.003 Å, r(S-O) = 1.435±0.003 Å, r(S-C) = 1.771±0.004 Å, ∠C-S-C = 102.6±0.9°, ∠O-S-O = 119.7±1.1° and ∠S-C-H = 108.5±0.8°. Comparison of sulphone molecular geometries shows a trend toward longer S-O bonds and smaller O-S-O bond angles as ligand electronegativity decreases. The constancy of the O?O interatomic distance indicates the importance of non-bonded interactions.     

An electron diffraction study of the molecular structure of gaseous cyclobutylgermane

The molecular structure and conformation of cyclobutylgermane have been determined by gas-phase electron diffraction. Like its counterpart cyclobutylsilane (CBS) it possesses quasi-equatorial and quasi-axial conformers. The most interesting aspect of the structure of CBG is the influence of the germyl group on the ratio of equatorial to axial conformers. The predominance of the quasi-equatorial conformer (ΔG = 3.1(1) kJ mol⁻¹), the near equality of the skeleton C---C bond lengths (C---C = 1.557(3)A) (r_a value) and the values of the puckering angles for the equatorial angles form and the axial one of 25.3(3.1)° and −20.4(3.6)° respectively, all support the predictions made by Jonvik and Boggs concerning the correlation between electronegativity and structural parameters in four-membered rings. From a consideration of these predictions, a comparison of the most prominent structural factors in CBG and cyclobutylsilane indicates that the germanium atom is more electronegative than silicon. This result could be considered as the first structural evidence for the previously postulated inversion of the electronegativity order within group IV.     

An electron diffraction study of the molecular structure of gaseous allyl silane

The molecular structure of allyl silane has been studied by gas-phase electron diffraction. The experimental radial distribution curve has only four prominent peaks, resulting in serious resolution problems in the structure determination. A single conformer whose dimensions resemble those of related molecules fits the diffraction data. The torsion angle φ_siccc is102 ± 1°, measured from the conformation having Si-C and CC eclipsed.