X-ray crystallographic studies on the self-condensation products of o-aminobenzaldehyde and anthranilic acid and of the metal complexes of some related tetra-azamacrocycles.
type: CreativeWork
description: This Thesis describes X-ray crystallographic investigations on twelve compounds. The first three are the products of the acid condensation of ortho-aminobenzaldehyde, OAB, the so-called TAAB salts, based on the tetra-anhydro tetramer of OAB. Although known since 1926, their structures have remained controversial. Of the three salts, TAABH2(X)2, investigated, that of X = picrate was found to be ordered, whilst those of X = HSO4 and BF4 were disordered. The structure of the TAABH2 cation is saddle-shaped and based on a fused heptacyclic framework. In all the three salts the anion appears to be doubly hydrogen bonded to the cation, through hydrogen donors NH and CH. The results enable a controversy in the literature regarding the structures of these compounds to be resolved. The self-condensation products of anthranilic acid, AA, also somewhat controversial in nature, have been investigated. The formation of a trimeric, and minor yields of a tetrameric derivative, is confirmed. The crystal structures of the tetramer and of two solvates of the trimer (CHCI3 and CH3CN.H2O) were determined. These two compounds, also, have a fused heptacyclic double saddle-shape overall structure. Their structures are compared with those of the TAAB salts. Related types of hydrogen bonding are surveyed, and the results found in this Thesis are put in a wider context. The structure of the copper complex Cu(TAABH2 ) of reduced TAAB derivative TAABH4, a 16-membered tetra-azamacrocycle has been investigated. It, too, has an overall saddle-shape, but this is considerably flatter than those of the TAAB salts and AA derivatives. Two metal complexes (CuII and Felll) of a 14-membered tribenzotetra-azamacrocycle were investigated. In the case of the iron compound. X-ray crystallography showed that an unexpected, novel oxygenation reaction of the ethylene bridge had taken place to give an a,B-diketo group. The purpose-made copper diketo-analogue was examined for comparative purposes. This derivative,…
abstract: This Thesis describes X-ray crystallographic investigations on twelve compounds. The first three are the products of the acid condensation of ortho-aminobenzaldehyde, OAB, the so-called TAAB salts, based on the tetra-anhydro tetramer of OAB. Although known since 1926, their structures have remained controversial. Of the three salts, TAABH2(X)2, investigated, that of X = picrate was found to be ordered, whilst those of X = HSO4 and BF4 were disordered. The structure of the TAABH2 cation is saddle-shaped and based on a fused heptacyclic framework. In all the three salts the anion appears to be doubly hydrogen bonded to the cation, through hydrogen donors NH and CH. The results enable a controversy in the literature regarding the structures of these compounds to be resolved. The self-condensation products of anthranilic acid, AA, also somewhat controversial in nature, have been investigated. The formation of a trimeric, and minor yields of a tetrameric derivative, is confirmed. The crystal structures of the tetramer and of two solvates of the trimer (CHCI3 and CH3CN.H2O) were determined. These two compounds, also, have a fused heptacyclic double saddle-shape overall structure. Their structures are compared with those of the TAAB salts. Related types of hydrogen bonding are surveyed, and the results found in this Thesis are put in a wider context. The structure of the copper complex Cu(TAABH2 ) of reduced TAAB derivative TAABH4, a 16-membered tetra-azamacrocycle has been investigated. It, too, has an overall saddle-shape, but this is considerably flatter than those of the TAAB salts and AA derivatives. Two metal complexes (CuII and Felll) of a 14-membered tribenzotetra-azamacrocycle were investigated. In the case of the iron compound. X-ray crystallography showed that an unexpected, novel oxygenation reaction of the ethylene bridge had taken place to give an a,B-diketo group. The purpose-made copper diketo-analogue was examined for comparative purposes. This derivative,…
author: Shaw, Leyla Suheyla
keywords: 540 Chemistry & allied sciences
date published: 1982-05
date modified: 2026-07-24T02:54:27Z
provider: London Metropolitan University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: Polytechnic of North London