The determination of the crystal structures of diferrocenyl ketone, anti-8-tricycle [3,2,1,O2,4] octyl p-bromobenzenesulphonate, anti-7-norbornenyl p-bromobenzoate and ochotensine methiodide
Creators: name: Macdonald, Alaistair Cumming
Publisher: name: University of British Columbia
Year: 2011

description: The crystal structure of diferrocenyl ketone has been analyzed using Fe(Kα) X-radiation. The molecule is symmetrical about a 2-fold axis passing through the carbonyl bond. Coordinates of the iron atom were determined from two Patterson-Harker sections and coordinates of the remaining atoms were derived from subsequent three dimensional Fourier summations. Structure refinement was carried out using (block-diagonal) least squares with allowances for anisotropic temperature vibration. The R value derived from the final coordinates is 0.09. The cyclopentadienyl rings not bonded to the keto group are vibrating more than those which are; when this is taken into account the iron atom lies midway between the cyclopentadienyl rings which are planar and 3.30 Å apart. The carbon bond lengths in these rings are all the same length (1.45 Å) and the conformation of one ring with respect to the other is almost eclipsed. The intermolecular contacts are all of normal length. The molecular dimensions of anti-8-tricyclo [3,2,1,0²˒⁴] octyl p-bromobenzenesulphonate and anti-7-norborneny1 p-bromo-benzoate have been measured to assist in the interpretation of the solvolytic reactivity in norbornane derivatives. Data were collected (Cu(Kα) radiation) by counter methods in both cases; the structures were determined using the heavy atom-Patterson method and refinements were carried out using differential syntheses and (block-diagonal) least squares. The discrepancy factors derived from the final coordinates are 0.09 and 0.18 respectively. The norbornane and norbornene skeletons have symmetry m and the bond lengths are normal. The bond angles at the methylene bridge are 97° and 96° respectively, the other angles are all less than the tetrahedral angle. The angles between the planes formed by different parts of the skeleton are identical in both cases. Bond lengths and angles in the remainders of both molecules are of normal dimensions. The configuration of the cyclopropyl methylene group in anti-8- tricycle [3,2,1,0²˒⁴] octyl p-bromobenzenesulphonate is exo to the norbornane skeleton. The results indicate that there is insufficient variation in the methylene bridge bond angles to account for the difference in solvolytic reactivity. The crystal and molecular structure of ochotensine methiodide has been investigated in order to determine the chemical structure of the molecule. The data were recorded photographically using Cu(Kα) radiation and a Weissenberg equi-inclination camera; estimation of the intensities was carried out by visual methods and interfilm scales were derived from corresponding symmetry related structure amplitudes. 845 independent reflections were measured in this way. The position of the iodine atom was determined from a three dimensional Patterson function and the positions of the remaining atoms from three subsequent three-dimensional Fourier maps. Refinement of the temperature and atomic parameters was carried out by (block diagonal) least squares; the final R value was 0.11. The analysis has shown that the structure of ochotensine is similar to that postulated for ochotensimine and the position of the phenolic group on ring A has been determined. A difference synthesis was carried out to verify the positions of the atoms. The bond lengths and angles are normal but several short intermolecular contacts were observed. The planes of the two benzene rings are inclined at an angle of 94°.