Determination of degree of crystallinity of Nylon 1212 by wide-angle X-ray diffraction

Based on the X-ray scattering intensity theory and using the approximate expression for the atomic scattering factor, the correction factors for three crystalline peaks and an amorphous peak of Nylon 1212 were calculated and the formula of degree of crystallinity of Nylon 1212 was derived by a graphic multipeak resolution method. The degree of crystallinity calculated from the WARD method is compatible with those obtained by density and calorimetry methods.

Self-immobilized titanium and zirconium catalysts with phenoxy-imine ligands for ethylene polymerization. X-ray crystal structure of bis(N-(3-tert-butylsalicylidene)-4 '-allyloxyanilinato) zirconium(IV) dichloride

Four self-immobilized FI catalysts with allyl substituted phenoxy-imine ligands [{4-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2) MCl2] (1: M = Ti: 2: M = Zr), [{3-(CH2=CHCH2O)C6H5N=CH-C6H3(3-tert-C4H9)O}(2)MCl2] (3: M = Zr), [{4-(CH2=CHCH2-2,6-(iso-C3H7)(2))C6H5N=CH-C6H3(3,5-(NO2)(2))O}(2)MCl2] (4: M = Zr) have been synthesized and characterized. The molecular structure of 2 has been determined by X-ray crystallographic analysis. The results of ethylene polymerization showed that the self-immobilized titanium (IV) and zirconium (IV) catalysts 1-3 kept high activity for ethylene polymerization and 4 showed no activity. SEM showed the immobilization effect could greatly improve the morphology of polymer particles to afford micron-granula polyolefin as supported catalysts.

Self-immobilized metallocene catalysts bearing an allyl group for ethylene polymerization, X-ray crystal structure of [(CH2=CHCH2)CH3Si(C13H8)(2)]ZrCl2

A series of ansa-metallocene complexes with an allyl substituted silane bridge [(CH =CHCH2)CH3Si(C5H4)(2)]TiCl2 (1), [(CH2=CHCH2)CH3Si(C9H6)(2)]MCl2 [M = Ti (2), Zr (3), Hf (4)] and [(CH2=CHCH2)CH3Si(C13H8)(2)]ZrCl2 (6) have been synthesized and characterized. The molecular structure of 6 has been determined by X-ray crystallographic analysis. Complexes 1-4, 6 bearing allyl groups have been investigated as self-immobilized catalysts for ethylene polymerization in the presence of MMAO. The results showed that the self-immobilized catalysts 1-4, 6 kept high ethylene polymerization activities of ca. 10(6) g PE mol(-1) M h(-1) and high molecular weight (M-w approximate to 10(5)) of polyethylene.

Photochemical synthesis, characterization and X-ray crystal structure of dodecamolybdophosphate tetrabutylammonium heteropoly blue (Bu4N)(4)[PMo12O40]center dot 2DMF center dot H2O

In this paper, we will report the preparation of a mixed-valence polyoxometalate compound (Bu4N)(4)[PMo12O40].2DMF.H2O (TBA = tetrabutylammonium; DMF = N,N-dimethyl formamide). The title compound has been photochemically synthesized and characterized by using elemental analysis, IR, solid diffusion reflectance electronic spectra, ESR spectra, XPS, CV and X-ray single-crystal analysis. The crystal lographic data are as follows: monoclinic, P2(1)/c, a = 14.124(3), b = 17.481(4), c = 22.744(5) Angstrom, beta = 101.66(3)degrees, V = 5500(2) Angstrom(3), C70H160Mo12N6O43P, M-r = 2956.29, Z = 2, D-c = 1.785 g/cm(3), F(000) = 2970 and mu(MoKalpha) = 1.412 mm(-1). The structure has been refined to R = 0.0638 and wR = 0.1975 by full-matrix least-squares methods. The title compound is composed of four tetrabutylammonium cations, one [(PMoMo11O40)-Mo-V](4-) heteropoly anion, two N,N-dimethyl formamide and one H2O molecule.

In situ study of nanostructure and morphological development during the crystal-mesophase transition of poly(di-n-hexylsilane) and poly(di-n-butylsilane) by X-ray and hot-stage AFM

Nanostructure and morphology and their development of poly(di-n-hexylsilane) (PDHS) and poly(di-n-butylsilane) (PDBS) during the crystal-mesophase transition are investigated using small angle X-ray scattering (SAXS), wide angle X-ray diffraction and hot-stage atomic force microscopy. At room temperature, PDHS consists of stacks of lamellae separated by mesophase layers, which can be well accounted using an ideal two-phase model. During the crystal-mesophase transition, obvious morphological changes are observed due to the marked changes in main chain conformation and intermolecular distances between crystalline phase and mesophase. In contrast to PDHS, the lamellae in PDBS barely show anisotropy in dimensions at room temperature. The nonperiodic structure and rather small electronic density fluctuation in PDBS lead to the much weak SAXS. The nonperiodic structure is preserved during the crystal-mesophase transition because of the similarity of main chain conformation and intermolecular distances between crystalline phase and mesophase.

Synthesis, properties and X-ray crystal structure of a new heteropolyacid supermolecular charge-transfer complex [(VB1)(2)DMFHPMo12O40 center dot 5DMF]

The title complex [(VB1)(2)DMFHPMo12O40.5DMF, VB1 = vitamin B-1 (thiamine chloride), DMF = N,N-dimethylformamide] has been synthesized and characterized by elemental analysis, IR, UV-Vis, electron spin resonance, X-ray photoelectron spectroscopy and cyclic voltammetry methods. The X-ray crystal structure revealed that there is one independent molecule in the unit cell of the title complex that contains one mixed-valence heteropolyanion, two VB1+ cations and six DMF molecules. The title complex possesses a centrosymmetrical arrangement in the unit cell, with the P atom at the symmetry center of the heteropolyanion and with eight O atoms surrounding the central P atom, such that two sets of PO4 tetrahedra are formed. The PO4 tetrahedra and MoO66-(7-) octahedra are disordered in the heteropolyanion. The bond distances of P-O-a and Mo=O-d are in the ranges 1.57 (4)-1.70 (4) Angstrom and 1.61 (2)-1.67 (2) Angstrom, respectively.

High-temperature X-ray diffraction studies on polyamide6/clay nanocomposites upon annealing

The influence of nanodispersed clay on the alpha crystalline structure of polyamide 6 (PA6) was examined in-situ with X-ray diffraction (XRD) between room temperature and melting. In pure PA6 upon annealing the alpha crystalline phase was substituted by an unstable pseudohexagonal phase at 150degreesC, then it transformed into a new stable crystalline structure - high temperature alpha' phase above the transition temperature. However, in PA6/clay nanocomposite (PA6CN), the alpha phase did not present crystalline phase transition on heating. The increase in the annealing temperature only led to continuous intensity variation. The different behaviors were caused by the confined spaces formed by silicate layers, which constrained the mobility of the polymer chains in-between.

Hydrothermal synthesis and X-ray single crystal structure of bimetallic cluster complex [{Co(phen)(2)}(2)V4O12]center dot H2O

A new bimetallic cluster complex with the formula [{Co(phen)(2)}(2)V4O12](H2O)-H-. was synthesized from the hydrothermal reaction of V2O5, H2C2O4, Co(NO3)(2), 1,10-phenanthroline (phen), (C4H9)(4)NOH and water. The compound crystallizes in an orthorhombic system with space group Pbcn and unit cell parameters a = 19.106(3) Angstrom, b = 15.250(3) Angstrom, c = 16.321(2) Angstrom, V = 4755.4(13) Angstrom(3), Z = 4 and R = 0.0318. The bimetallic cluster complex [{Co(phen)(2)}(2)V4O12](H2O)-H-. is composed of a discrete V4O124- cluster eovalently attached to two [Co(phen)(2)](2+) fragments and the discrete hexanuclear bimetallic clusters of [{Co(phen)(2)}(V4O12)-V-2](H2O)-H-. are further extended into interesting three-dimensional supermolecular arrays via pi-pi stacking interactions of phen groups. Other characterizations by elemental analysis, IR, and thermal analysis are also described.

Photochemical synthesis, properties and X-ray crystal structure of tetrabutylammonium dodecamolybdophosphate heteropoly blue

The title heteropoly blue, (Bu4N)(6)H-10 [(PMo11MoO40)-Mo-VI-O-V](4) . H2O has been photochemically synthesized and characterized with elemental analysis, solid diffusion reflectance electronic spectra, CV, ESR, XPS, IR spectra, conductivity measurement and X-ray single crystal analysis. The crystallographic data for C96H218Mo48N6O169P4 are as follows: M-r = 8889.76, triclinic, P (1) over bar, a = 1.4142 (3) nm, b = 2.6027 (5) nm, c = 2.6403(5) nm, alpha = 113.96(3)degrees, beta = 90.05(3)degrees, gamma = 105.71(3)degrees, V = 8.481 (3) nm(3), Z = 1, D-c = 1.741 g/cm(3), F (000) = 4264, mu = 1.798 mm(-1). The X-ray crystal structure analysis reveals that there Is one independent molecule in the unit cell of the title heteropoly blue which contains four mixed-valence heteropoly anions, six tetrabutylammonium cations and one water molecule. Its molecular structure possesses a centrosymmetrical arrangement in the unit cell. The phosphorus atom is In the crystallographic inversion center of the heteropoly anion and the eight oxygen atoms surrounding central phosphorus atom comprise of a distorted hexahedron. Heteropolyanion has two equal sets of PO4 tetrahedron. The PO4 tetrahedron and the MoO6 octahedron in the polyanion are greatly distorted.

Single-crystal X-ray structure and properties of K-10[Ni-4(H2O)(2)(AsW9O34)(2)]center dot 4H(2)O

The rational synthesis and the structural and magnetic characterization of a nickel cluster are presented. The compound comprises a rhomblike Ni4O16 group encapsulated between two-heptadentate tungstoarsenate ligands [AsW9O34](9-). The crystal structure of K-10[Ni-4(H2O)(2)(AsW9O34)(2)](.)4H(2)O was solved in monoclinic, P2(1)/n symmetry, with a = 12.258(3) Angstrom, b = 21.232(4) Angstrom, c = 15.837(3) Angstrom, beta = 92.05(3)degrees, V = 4119.1(14) Angstrom(3), Z = 2, and R = 0.0862. The crystal structure of the Ni(II) derivative was compared with that of the Cu(II), Zn(II), Co(II) and Mn(II) derivatives. The Ni4O14(H2O)(2) unit in the compound shows no Jahn-Teller distortion. On the other hand, the Ni(II) derivative shows ferromagnetic exchange interactions within the Ni4O16 group (J = 7.8 cm(-1), J' = 13.7 cm(-1)) and an S = 4 ground state, the highest spin state reported in a heteropoly complex. Its redox electrochemistry has been studied in acid buffer solutions using cyclic voltammetry. It exhibited two steps of one-electron redox waves attributed to redox processes of the tungsten-oxo framework. The new catalyst showed an electrocatalytic effect on the reduction of NO2-.

1,1 '-di(tert-butyl)metallocenium cations. The x-ray crystal structures of [M((C5H4Bu)-Bu-t)(2)]PF6 (M = Fe, Co) and [Co((C5H4Bu)-Bu-t)(2)](2)CoCl4

The hexafluorophosphate salts [Fe((C5H4Bu)-Bu-t)(2)]PF6 (1) and [Co((C5H4Bu)-Bu-t)(2)]PF6 (2) crystallize in isotypic structures with centrosymmetric cations which have a staggered (transoid) conformation of the exactly parallel ring Ligands (conformational angle tau = 180 degrees). The tetrachlorocobaltate salt, [CO((C5H4Bu)-Bu-t)(2)](2)CoCl4 (3), contains one almost eclipsed (tau = 140.4 degrees) and one almost staggered (tau = 101.4 degrees) cobaltocenium cation; in both cases, the cyclopentadienyl ring planes are slightly inclined (by alpha = 5.4 degrees and 4.1 degrees, respectively) to give more room to the tert-butyl substituents which are bent away from the metal in all three complexes 1 - 3.

X-ray crystal structure and molecular mechanics calculations of (2,6-iso-dipropyl-phenylamide) dimethyl (tetra-methylcyclopenta-dienyl) silane titanium dichloride

Crystal and molecular structure of (2.6-dipropylphenylamide) dimethyl (tetra-methyl cyclopentadienyl) silane titanium dichloride (I) was fully characterized by X-ray diffraction. The crystal is obtained from a mixture of ether/hexane as orthorhombic. with a = 12.658 (3) Angstrom. b = 16.62 (3) Angstrom. c = 11.760 (2) Angstrom. V = 2474.2 (9) Angstrom(3). Z = 4, space group Pnma. R = 0.0399; Componud I compose of the pi-bounded ring with its dimethylsilyl-dipropyl phenyl amido group and the two terminal chloride atoms coordinated to central metal to form a so-called constrained geometry catalyst (CGC) structure. The result of molecular mechanics (MM) calculations on compound I shows that bond lengths and bond angles from the MM calculation are comparable to the data obtained from the X-ray diffraction study. The relation of the structure of CGCs and their catalytic activity by MM calculations is also discussed.

Local similarity in organic crystals and the non-uniqueness of X-ray powder patterns

Two new concepts for molecular solids, 'local similarity' and 'boundary-preserving isometry', are defined mathematically and a theorem which relates these concepts is formulated. 'Locally similar' solids possess an identical short-range structure and a 'boundary-preserving isometry' is a new mathematical operation on a finite region of a solid that transforms mathematically a given solid to a locally similar one. It is shown further that the existence of such a 'boundary-preserving isometry' in a given solid has infinitely many 'locally similar' solids as a consequence. Chemical implications, referring to the similarity of X-ray powder patterns and patent registration, are discussed as well. These theoretical concepts, which are first introduced in a schematic manner, are proved to exist in nature by the elucidation of the crystal structure of some diketopyrrolopyrrole (DPP) derivatives with surprisingly similar powder patterns. Although the available powder patterns were not indexable, the underlying crystals could be elucidated by using the new technique of ab initio prediction of possible polymorphs and a subsequent Rietveld refinement. Further ab initio packing calculations on other molecules reveal that 'local crystal similarity' is not restricted to DPP derivatives and should also be exhibited by other molecules such as quinacridones. The 'boundary-preserving isometry' is presented as a predictive tool for crystal engineering purposes and attempts to detect it in crystals of the Cambridge Structural Database (CSD) are reported.