Polymeric crystallization, structural

The geometrical parameters of equilibrium configurations of small fullerenes isolated molecules C , their dimers (Cn)2 and cuban-like clusters(Cn)8 are obtained for n = 20, 24, 28, 32. The Cuban like clusters can be considered as fragments of polymerized crystal structures with simple cubic symmetry. Total energy, heat of formation, energies of HOMO and LUMO orbitals, density of one-electron states (DOS) are determined for equilibrium configurations of all these objects. All the computations are performed by help of pocket PC Gamess in frames of optimized semi-empirical PM3-basis [4-5],... 

Figure 4.3 Polymeric crystal structure of [(Np2Mg)2-(NpMgBr)2] [45]...

Crystal Structure. The crystal stmcture of PVDC is fairly well estabhshed. Several unit cells have been proposed (63). The unit cell contains four monomer units with two monomer units per repeat distance. The calculated density, 1.96 g/cm, is higher than the experimental values, which are 1.80—1.94 g/cm at 25°C, depending on the sample. This is usually the case with crystalline polymers because samples of 100% crystallinity usually cannot be obtained. A dkect calculation of the polymer density from volume changes during polymerization yields a value of 1.97 g/cm (64). If this value is correct, the unit cell densities may be low. 

Colloidal crystals . At the end of Section 2.1.4, there is a brief account of regular, crystal-like structures formed spontaneously by two differently sized populations of hard (polymeric) spheres, typically near 0.5 nm in diameter, depositing out of a colloidal solution. Binary superlattices of composition AB2 and ABn are found. Experiment has allowed phase diagrams to be constructed, showing the crystal structures formed for a fixed radius ratio of the two populations but for variable volume fractions in solution of the two populations, and a computer simulation (Eldridge et al. 1995) has been used to examine how nearly theory and experiment match up. The agreement is not bad, but there are some unexpected differences from which lessons were learned. 

Figure 5.9 Crystal structure of the etherate of polymeric sodium hydridodiethylberyllaie (Et20NaHBeEtj) emphasizing two features of the structure (see text).

In the case of grinding, the cellulose fibers go over a state of fine fibrillation into a more or less powdery substance. This mechanical severance of cellulose may break main valence bonds and will, therefore, decrease its degree of polymerization. In addition, the crystal structure of cellulose fibers is nearly lost [32]. Grinding of the cellulose fibers also, appreciably increases its surface area. 

Ziegler-Natta catalyst A stereospecific catalyst for polymerization reactions, consisting of titanium tetrachloride and triethylaluminum. zinc-blende structure A crystal structure in which the cations occupy half the tetrahedral holes in a nearly close packed cubic lattice of anions also known as sphalerite structure. 

Dithiocarbamate complexes of copper have been sythesized at a high rate. Reports of new complexes include the morpholine-4- (44), thio-morpholine, AT-methylpiperazine-4-, and piperidine- (291) dithiocarba-mates. Novel, polymeric complexes of the type Cu(pipdtc)2 (CuBr) in = 4, or 6) and Cu(pipdtc)2 (CuCl)4 have been prepared by reactions of[Cu(pipdtc)2] with the respective copper halide in CHCla-EtOH (418). The crystal structures of the polymers are known to consist of sheets of individual [Cu(pipdtc)2] molecules linked to polymeric CuBr chains via Cu-S bonds. A series of copper(I) dtc complexes have been the subject of a Cu and Cu NQR-spectral study (440). 

The even-numbered degree of polymerization behaviour of 2 OEt can be interpreted from its crystal structure (Fig. 9), in which the molecule is related to its neighbouring molecules by two different inversion centres to make a plane-to-plane stack (Maekawa et al., 1991a). The ethylenic double... 

A polymeric structure can be generated by intermolecular coordination of a metalloporphyrin equipped with a suitable ligand. Fleischer (18,90) solved the crystal structure of a zinc porphyrin with one 4-pyridyl group attached at the meso position. In the solid state, a coordination polymer is formed (75, Fig. 30). The authors reported that the open polymer persists in solution, but the association constant of 3 x 104 M 1 is rather high, and it seems more likely, in the light of later work on closed macrocycles (see above), that this system forms a cyclic tetramer at 10-3 M concentrations in solution (71,73). 

Smith (91) reported an X-ray crystal structure of a zinc porphyrin polymer (77, Fig. 32) where, unusually, the coordination bond is between a nitro group and the zinc center. The tetranitroporphyrin is highly substituted, and the resulting steric hindrance causes the macrocycle to be noticeably distorted. Adjacent porphyrin planes in the polymer are almost orthogonal. However, there is no evidence of polymerization in solution, and the nitro-zinc interaction is probably too weak to maintain this structure outside the solid state. 

Fig. 5 Scatterplot derived from the CSD reporting the N- I-C angle (deg) vs. the N- I distance (A) for crystal structures containing intermolecular N- I contacts only error-free and non-polymeric structures containing single-bonded iodine atoms and showing no disorder with R < 0.06 are considered. The scatterplot clearly demonstrates the high directionality of the N- I XB...

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