Shortening, crystal structure

X-r crystal structure determinations have been completed on two salts containing bicyclo[2.2.1]heptyl cations (Fig. 5.12). Both are more stable than the 2-norbomyl cation itself 18 is tertiary whereas 19 contains a stabilizing methoxy group. The crystal structure of 18 shows an extremely long (1.74 A) C—C bond between C-1 and C-6. The C(1)—C(2) bond is shortened to 1.44 A. The distance between C-2 and C-6 is shortened from 2.5 A in norbomane to 2.09 AThese structural changes can be depicted as a partially bridged structure. 

In a comparison of fluorescence spectra between the ester and thioester derivative crystals of PDA, the ester crystal shows a strong emission whereas the thioester crystal fluoresces much more weakly. For example, the intensity of a PDA methyl thioester crystal is about one-thousandth of that of a PDA methyl ester crystal. Furthermore, the fluorescence lifetime of mixed crystals which consist of a large amount of PDA methyl ester and a small amount of the corresponding thioester moiety is much shortened, compared to the lifetime of pure PDA methyl ester crystals. In quenching experiments in solutions of PDA ester, the fluorescence of the PDA ester is dramatically quenched by thioacetate. Similar behaviour has been obtained with several types of diolefin derivatives having a thioester moiety, where crystal structures are isomorphous with the corresponding ester derivatives. 

The free t-butyl cation [7" ] in the gas phase is nothing more than a species detectable by the electron impact method (Yeo and Williams, 1970). However, it is not only an observable species by nmr studies in SbFs/FSOsH (Olah et al., 1964), but can be isolated from the solution in the form of its SbF or Sb2Ffi salt (Olah and Lukas, 1967a,b Olah et al., 1973 Yannoni et al., 1989). The crystal structure shows that this ion is planar and its carbon-carbon bonds are shortened to 144.2 pm (Hollenstein and Laube, 1993). Its particular electronic stabilization among aliphatic carbocations is attributed by physical organic chemists to the operation of both inductive and hyperconjugative effects in the cr bond system. 

The minimum amount of information needed to specify a crystal structure is the unit cell type, that is, cubic, tetragonal, and so on, the unit cell parameters, and the positions of all of the atoms in the unit cell. The atomic contents of the unit cell are a simple multiple, Z, of the composition of the material. The value of Z is equal to the number of formula units of the solid in the unit cell. Atom positions are expressed in terms of three coordinates, x, y, and z. These are taken as fractions of a, b, and c, the unit cell sides, say and j. The x, y, and z coordinates are plotted with respect to the unit cell axes, not to a Cartesian set of axes. The space group describes the symmetry of the unit cell, and although it is not mandatory when specifying a structure, its use considerably shortens the list of atomic positions that must be specified in order to built the structure. 

P450 2C9 crystal structure information also served in docking and molecule dynamics operations to simulate the simultaneous binding of a heteroactivator and a substrate [ 17]. N SAID substrates were thereby positioned nearer to the heme than the heteroactivator. For the latter, limited conformational freedom was discovered because of the reduced active-site volume. The presence of an activator shortened the substrate-heme iron distances leading to an increase in the number of catalytic... 

P—S bond is elongated to 196.5 pm and the P—0(H) bond shortened to 148 pm.164 The structures of the m-vinyl carbonate (136)165 and the cyclic phosphonic anhydride (96)123 have been determined, and for the latter compound the ring was found to be almost planar. A -Ray diffraction data of deoxyuridine phosphate,166 phospholipid multilayers,167 nucleotides,168 and skeletal muscle169 have been analysed. The crystal structure of the phosphazene (137) has been established.170... 

The dependence of Tc on pressure is studied for a variety of reasons. In a chemical sense, bond lengths are shortened, and orbital interactions are increased. The volume decrease leads in principle to a rise in carrier density. In reality, however, not only do vibrational frequencies change, but crystal structure and symmetry are often affected by high pressure. Numerous materials undergo semiconductor to metal phase transitions as a function of pressure. Increasing pressure can often be considered analogous to a decrease in temperature. 

Single crystal structural analyses of K2[ZnF4] and K3[Zn2F7] have been reported.1043 Although the [ZnF4]2 ion is perfectly tetrahedral, the [Zn2F7]3 ion shows a shortening of the terminal Zn—F bonds. 

The crystal structure is a composite of different possible linkages, in which some chains are shortened (principally at the middle sulfurs of the chains), whereby sulfur absences are responsible for the PdSM composition. 

In many instances, TGs exist in polymorphic forms. Crystal structure is very important to the properties of margarines, shortenings, and specialty fats. The very unstable a form is readily transformed to the more stable ft form, which in some TGs has a higher melting point (more stable) than the /3 form. In single-acid TGs, the order is a — f3 — a, but some mixed TGs show a lower-melting (less stable) (3 form. This is further complicated by the existence of multiple / and /3 forms, depending upon the detailed TG structures at hand. 

The crystal structure can be rationalized by considering the influence of interactions with the neighboring chains. For I, II, and V, the bifurcated structure leaves the second amino hydrogen more available for interactions with a neighboring chain than the more energetically favored head-on dimer. The shortening of the hydrogen bond to the ortho substituent (in C vs. B-type structures) that is often apparent may also serve to bet-... 

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