Molecular conformation, crystal

Klebe, G., Graser, F., Hadicke, E. and Berndt, J. (1989). Crystallochromy as a solid state effect correlation of molecular conformation, crystal packing and colour in perylene-3,4 9,10-bis(carboximide) pigments. Acta Crystallogr. B, 45, 69-77. [263, 264]... 

Diphenyl-2,5-cyclohexadienone 3 exists as four polymorphs, labeled A-D, whose crystallographic details are summarized in Table 3-2 [14]. Polymorphs A-D are conformational polymorphs since they have different molecular conformers in their crystal structures. They are also concomitant polymorphs because they crystallized simultaneously from the same flask and under identical crystal nucleation and growth conditions. Forms B-D with multiple molecules in the asymmetric unit Z > ) may also be classified as conformational isomorphs. Such polymorph clusters with different molecular conformations, crystal packing and C—H - O... 

Form Crystal system Space group, lattice constants and number of chains per unit cell Molecular conformation Crystal density (g/cm )... 

It may be desirable to predict which crystal structure is most stable in order to predict the products formed under thermodynamic conditions. This is a very difficult task. As of yet, no completely automated way to try all possible crystal structures formed from a particular collection of elements (analogous to a molecular conformation search) has been devised. Even if such an effort were attempted, the amount of computer power necessary would be enormous. Such studies usually test a collection of likely structures, which is by no means infal-... 

In 1990, Baumeister et al. [127] described the crystal and molecular structure of 4-ethoxy-3 -(4-ethoxyphenyliminomethyl)-4 -(4-methoxy-benzoy-loxy)azobenzene. The molecules have a bifurcated shape. The phenyliminom-ethyl branch is bent markedly from the nearly linear three ring fragment, but is almost coplanar with the azobenzene moiety. They found that the molecular conformation is affected by an intramolecular interaction of the carboxylic and azomethine groups. The crystal packing was described in terms of a sheet structure with interdigitating rows of molecules. 

Perez et al. [128] investigated the crystal structure of 4-(4 -ethoxybezoy-loxy)-2-butoxy-4 -(4-butoxysalicylaldimine)azobenzene. This compound contains four rings in the main core and a lateral alkoxy branch on one of the inner rings. The lateral butoxy chain is nearly perpendicular to the long axis of the main core. This molecular conformation induces the molecules to make a very complex network in the solid. The crystal cohesion is due to van der Waals interactions. The change of the lateral chain conformation in the solid and nematic phases is discussed. 

Keywords Smectic liquid crystals, Molecular conformations, polar and steric frustrations, Polyphilic and perfluorinated mesogens. X-ray diffraction... 

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. 

The isolation of crystalline products having mixed polymorphic compositions (often referred to as concomitant polymorphism) remains a topic of interest, even though the phase rule predicts that a system at equilibrium consisting two components (solvent + solute) and three phases (solution + Form I + Form II) is uni variant. Hence, for crystallizations performed at a fixed pressure (typically atmospheric) the system becomes nonvariant and genuine equilibrium can exist at only one temperature. Therefore, concomitant products must be obtained under nonequilibrium conditions. Flexibility in molecular conformation was attributed to the concomitant polymorphs of a spirobicyclic dione [34] and of 3-acetylcoumarin [35],... 

At the end of the process, one obtains a large amount of information regarding the solid-state structure of a compound. Its three-dimensional structure and molecular conformation become known, as do the patterns of molecular packings that enable the assembly of the crystal. In addition, one obtains complete summaries of bond angles and bond lengths for the molecules in the crystal as well as detailed atomic coordinates for all of the atoms present in the solid. One generally finds... 

Crystal interactions may lead to a number of readily observable consequences. The molecular geometries may be different in different polymorphic forms of a given compound or, as in the case above, in symmetry-independent sites in a given crystal a change of molecular substituents remote from the torsionally flexible bonds may change the molecular conformation, as a result of modification... 

The complexity that may arise even for a relatively simple molecule is illustrated by iminodiacetic acid, H02CCH2NHCH2C02H. This acid has three crystal forms. The bond angles and lengths are essentially the same in all the forms, but the torsional angles differ, providing three different molecular conformations (19). In addition, one of the forms has two symmetry-independent molecules, of slightly different conformations, in its asymmetric unit. 

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