Molecular structure determination conformational analysis

Furthermore, it is often possible to extract from the structural analysis of solid solvates a significant information on solvation patterns and their relation to induced structural polymorphism. An interesting illustration has been provided by crystal structure determinations of solvated 2,4-dichloro-5-carboxy-benzsulfonimide (5)35). This compound contains a large number of polar functions and potential donors and acceptors of hydrogen bonds and appears to have only a few conformational degrees of freedom associated with soft modes of torsional isomerism. It co-crystallizes with a variety of solvents in different structural forms. The observed modes of crystallization and molecular conformation of the host compound were found to be primarily dependent on the nature of the solvent environment. Thus, from protic media such as water and wet acetic acid layered structures were formed which resemble intercalation type compounds. 

Until recently it was not customary to report measurements such as torsion angles and intramolecular non-bonding distances because they are not necessarily characteristic molecular properties. The bond torsion angles, which are of special interest in conformational analysis, are often only reported and discussed when there is a special reason for doing so which is connected with the objectives of the structure determination. Tradition dies hard, and one still finds tables of bond distances and angles in crystal structure papers which are not significantly different from the expected values, whereas torsion angles and other conformational data which are of special interest to the chemist are not reported and have... 

The crystal structure of pentathiepino [6,7- indole has been determined <1994TL5279>. X-Ray crystal structure analysis revealed that 4,5-ethylenedithio-4,5-pentathiotetrathiofulvalene <1999AM758> moiety has a bent structure resembling the molecular structure of neutral bis(ethylenedithio)tetrathiafulvalene and that the pentathio group adopts a chair-formed conformation. The intradimer interplane distance is 3.35 A, which is much shorter than the interdimer one (4.45 A). In a molecule, there are many intermolecular S-S contacts shorter than the sum of the van der Waals radii (3.7 A), and a two-dimensional network of sulfur atoms was developed between the pentathio groups and tetrathiafulvalene moieties. Furthermore, chlorobenzene molecules are beside the anion and occupy the void space as the interstitial solvent. They are also located on the mirror plane and are disordered at two positions with inversion symmetry because of the cavity structure of the void space. 

A combination of the two techniques was shown to be a useful method for the determination of solution structures of weakly coupled dicopper(II) complexes (Fig. 9.4)[119]. The MM-EPR approach involves a conformational analysis of the dimeric structure, the simulation of the EPR spectrum with the geometric parameters resulting from the calculated structures and spin hamiltonian parameters derived from similar complexes, and the refinement of the structure by successive molecular mechanics calculation and EPR simulation cycles. This method was successfully tested with two dinuclear complexes with known X-ray structures and applied to the determination of a copper(II) dimer with unknown structure (Fig. 9.5 and Table 9.9)[119]. 

Thus, the fluorine probe approach has proved useful for the conformational analysis of paclitaxel and taxoids in connection with the determination of possible bioactive conformations.77 The previously unrecognized conformer C might be the molecular structure first recognized by the P-tubulin binding site on microtubules. 

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