Pseudo crystal structures

Fig. 14.12. A molecular decoration a computer-generated pseudo-crystal structure for chloro-corannulene in space group fw3w, with 48 molecules in the unit ceU.

Figure 10.2 Crystal structure of GeF2 (a) projection along the chains, and (b) environment of Ge (pseudo trigonal bipyramidal). The bond to the unshared F is appreciably shorter (179 pm) than those in the chain and there is a weaker interaction (257 pm) linking the chains into a 3D structure.

Conversely, when A-alkyl tryptophan methyl esters were condensed with aldehydes, the trans diastereomers were observed as the major products." X-ray-crystal structures of 1,2,3-trisubstituted tetrahydro-P-carbolines revealed that the Cl substituent preferentially adopted a pseudo-axial position, forcing the C3 substituent into a pseudo-equatorial orientation to give the kinetically and thermodynamically preferred trans isomer." As the steric size of the Cl and N2 substituents increased, the selectivity for the trans isomer became greater. A-alkyl-L-tryptophan methyl ester 42 was condensed with various aliphatic aldehydes in the presence of trifluoroacetic acid to give predominantly the trans isomers. ... 

The crystal structure of 2-bromo-l,4-phenylenediyl bis(tran5-4-n-prop-ylcyclohexanoate) was determined by Hartung and Winter [114]. The molecules exhibit pseudo-centrosymmetry in consequence of a special kind of disorder within the crystal lattice. The peculiarity of the crystal structure is the disorder of the molecules with respect to the position of their bromine atoms which occupy the 2- or 5-position of the phenyl ring in a statistical manner. 

The formation of a 3D lattice does not need any external forces. It is due to van der Waals attraction forces and to repulsive hard-sphere interactions. These forces are isotropic, and the particle arrangement is achieved by increasing the density of the pseudo-crystal, which tends to have a close-packed structure. This imposes the arrangement in a hexagonal network of the monolayer. The growth in 3D could follow either an HC or FCC struc-... 

Examples in organometallic systems are known. Reaction of thiuram disulfides, (R2NCS2)2, with Co(Cp)(CO)2 produces dithiocarbamato pseudo-octahedral cobalt(III) complexes Co(Cp)(dtc)2 with one chelated and one monodentate dtc, also accessible via Co(Cp)I(dtc).1050 Fluxional behavior, including monodentate chelate exchange, was observed for some complexes in temperature-dependent NMR studies. The Co(Cp)I(dtc) complex was defined in a crystal structure. 

Therefore both symmetrical configurations of the hydroxy functions in the host molecule allow the helical tubuland structure. The unsymmetrical epimer anti-2,, syn-7-dihydroxy-2,7-dimethyltricyclo[4.3.1.13-8]undecane (10), the hybrid of 2 and 8, does not possess a molecular twofold axis (or pseudo twofold axis) or the conformation of C—O bonds of Fig. 5, and would not be expected to fit into the helical tubuland structure framework. Its crystal structure is indeed different, with infinite zig-zag sequences of hydrogen bonds constructing a non-including lattice 14). 

The free selenite ion has a pyramidal shape (C3v symmetry) owing to the lone electron pair at the selenium atom. Thus, the Se032- ion can be treated as a pseudo-tetrahedral anion and the lone electron pair often acts as an invisible ligand within the crystal structures of selenites. This observation is called the stereochemical activity of the lone electron pair and it will turn out as one of the... 

Monomeric carbene complexes with 1 1 stoichiometry have now been isolated from the reaction of 4 (R = Bu, adamantyl or 2,4,6-trimethylphenyl R = H) with lithium l,2,4-tris(trimethylsilyl)cyclo-pentadienide (72). The crystal structure of one such complex (R = Bu) revealed that there is a single cr-interaction between the lithium and the carbene center (Li-C(carbene) 1.90 A) with the cyclopentadienyl ring coordinated in an if-fashion to the lithium center. A novel hyper-valent antimonide complex has also been reported (73). Thus, the nucleophilic addition of 4 (R = Mes R = Cl) to Sb(CF3)3 resulted in the isolation of the 1 1 complex with a pseudo-trigonal bipyramidal geometry at the antimony center. 

Most of the chalcogenide studies have involved binary, ternary, and pseudo ternary metal clusters. The ternary Chevrel-phases can be represented by MxMo6X8 (M = transition metal, X = chalcogen atom), where the transition metal fills the cavities in the Mo6X8 crystal structure. The pseudo-ternary (or pseudo-binary) Chevrel-phase clusters can be represented by MxMo6 xX8, where the Mo atoms are substituted by transition metal atoms.185 The crystal structure of ternary and pseudo ternary Chevrel phases are shown in Fig. 4. The carbonyl-chalcogenide clusters189 192 will be discussed in the next section. 

Fig. 4 The crystal structure of Chevrel phase chalcogenides. The atoms are represented by (Mo), O (chalcogen) and A (site of the metal atoms for the ternary Chevrel phases). For pseudo-binary phases, the Mo is partially substituted by the metal atoms. (181 With kind permission of Springer Science and Business Media).

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