The Crystal Structures of Several Organic Compounds. I. α-Keto-1, 1'-Trimethyleneferrocene. II. The Chloranil-Hexamethylbenzene Complex, a Refinement. III. Two Phenazine Derivatives from Pseudomonas aureofaciens

Citation

Jones, Noel Duane (1964) The Crystal Structures of Several Organic Compounds. I. α-Keto-1, 1'-Trimethyleneferrocene. II. The Chloranil-Hexamethylbenzene Complex, a Refinement. III. Two Phenazine Derivatives from Pseudomonas aureofaciens. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/TMB9-4198. https://resolver.caltech.edu/CaltechETD:etd-09252002-115411

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. I. The three-dimensional crystal structure of a [alpha]-keto-1,1'-trimethyleneferrocene has been determined by X-ray diffraction analysis. This compound crystallizes in the centrosymmetric monoclinic space group [...]. The unit cell contains four molecules and has the dimensions a = [...] and b = [...] and [?]. The structure was solved from the locations of the iron-iron vectors in the (001) Patterson projection and was refined in both two and three-dimensions by the method of least-squares. The final reliability factor, R, was 0. 067. The dihedral angle between the best planes through the two nearly planar cyclopentadienyl rings is about 9. 8?. The average ring carbon-carbon bond is [...] and the average iron-ring bond is [...]. The principal thermal motion is a vibration of the entire molecule in a direction roughly parallel to the [...] axis. II. The crystal structure of the chloranil-hexamethylbenzene complex, as first reported by Harding and Wallwork [Acta Cryst., 8, 787 (1955)], has been refined in order to show that their data are consistent with a more reasonable structure than that proposed by them. The molecular dimensions of the refined structure show no significant deviations from the expected values. In addition, the molecules are nearly planar. III. The crystal structures of two phenazine derivatives from extracts of Pseudomonas aureofaciens have been determined. The first of these, 1-phenazinecarboxylic acid, has been solved and refined in two dimensions. The molecular structure of the other derivative, 2-hydroxy-1-phenazinecarboxylic acid, was unknown at the time this work was begun. It has been solved in three dimensions and partially refined by the method of least-squares. 1-Phenazinecarboxylic acid crystallizes in the space group [...] with four molecules in the monoclinic unit cell. The lattice constants are [...] and [...]. The structure was solved from the weighted hk0 reciprocal lattice net and from the (001) Patterson map. The molecule is tilted 20-25[degrees] with respect to the (001) plane and is internally hydrogen bonded. The principal thermal vibration is a torsion motion about an axis which passes through the center ring of the phenazine nucleus. 2-Hydroxy-1-phenazinecarboxylic acid also crystallizes in the space group [...] with four molecules in a unit cell which has the dimensions [...] and [...]. This structure was solved from the weighted [...] reciprocal lattice net and from the (010) Patterson vector map. The average ring carbon-carbon bond length, calculated from the partially refined positional parameters, is [...] and the average carbon-nitrogen bond length is [...]. The molecules lie parallel and coplanar in "ribbons" which are stacked normal to the [...] axis and very nearly parallel to the (012) plane. The hydroxyl hydrogen atom is internally bonded to the carboxyl group and the carboxyl hydrogen atom possibly forms a "bifurcated" bond, being bonded both intra- and intermolecularly.

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