Hydrothermal synthesis and characterization of bimetallic cluster complex [{Mn(phen)(2)}(2)V4O12]center dot 1/2 H2O

A new bimetallic cluster complex with the formula [(Mn(phen)(2))(2)V4O12].1/2 H2O has been synthesized through hydrothermal reaction of vanadate staring material with manganese cation in the presence of nitrogen donor chelating ligand and characterized by single-crystal X-ray diffraction, elemental analysis, IR UV-vis, ESR spectrum and thermal analysis. The compound crystallize in the monoclinic space group P2(1)/c with a = 18.475(4) Angstrom, b = 11.473(2) Angstrom, c = 23.667(5) Angstrom, beta = 97.76(3)degrees, V = 4971(2) Angstrom(3) and Z = 4. The structure of [{Mn(phen)(2)}(2)V4O12].1/2 H2O is composed of a discrete V4O124- cluster covalently attached to two [Mn(phen)(2)](2+) fragments.

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.

Crystal structure and variation in unit cell parameters with crystallization temperatures of poly (ether ketone ether ketone ketone)s containing meta-phenyl links (PEKEKmK)

The X-ray diffraction patterns of the crystalline aromatic ketone polymer PEKEKmK (aryl ether ketone ether ketone ketone polymer containing meta-phenyl links) have been investigated (for the chemical structure, see Formula). An orthorhombic unit cell is proposed to contain two chains with a = 0.772 nm, b = 0.604 nm and c = 2.572 nm. According to the orthorhombic system, the 11 reflections of this polymer were indexed. Meanwhile, variation in unit cell parameters with crystallization temperatures of PEKEKmK was also investigated. [GRAPHICS]

Study on new typical ionic clusters K+ (KNO3)(n) and NO3-(KNO3)(m)

The sample solution of KNO3 is ejected into the gas phase and the ionic dusters of K+(KNO3)(n) and NO3-(KNO3)(m) we formed and observed by electrospray ionization mass spectrometry (ESIMS). The full mass spectra of both the positive ion and the negative ion show that the differences between each peak nearby are all about 101(m/z), which correspond to the molecular weight of KNO3. The general formula of the ionic clusters can be assigned as K+ (KNO3)(n) and NO3--(KNO3)(m).

New typical ionic cluster K+(KNO3)(n) and NO3-(KNO3)(m)

New typical ionic clusters with complex anions could be formed directly from the KNO3 aqueous solution by means of the electrospray ionization mass spectrometry(ESIMS). The difference between the neighboring peaks(m/z), which corresponded to the molecule weight of KNO3 being 101 in the full mass spectrometry of the positive-ion and the negative-ion. The general formula of the ionic clusters belonged to K+(KNO3)(n) and NO3- (KNO3)(m).

Estimation of individual phases from the four-phase structure invariants in the single isomorphous replacement case

The probability distribution of the four-phase invariants in the case of single isomorphous replacement has been developed to estimate some individual phases. An example of its application to obtain the phases having special values of 0, pi or +/-pi /2 is given for a known protein structure in space group P2(1)2(1)2(1). The phasing procedure includes the determination of starting phases and an iterative calculation. The initial values of starting phases, which are required by the formula, can be obtained from the estimate of one-phase seminvariants and by specifying the origin and enantiomorph. In addition, the calculations lead to two sets of possible phases for each type of reflection by assigning arbitrarily an initial phase value. The present method provides a possibility for the multisolution technique to increase greatly the number of known phases while keeping the number of the trials quite small.

Co-Cu-Al mixed oxides derived from hydrotalcite-like compound for NO reduction by CO

Various hydrotalcite based catalysts were prepared for catalytic removal of NO (NO reduction by CO). The general formula of hydrotalcite compounds (HTLc) was Co-Cu-Al-HTLc. Precalcination of these materials at 450 degrees C for NO reduction by CO, was necessary for catalytic activity. All catalysts except Co-A1 and Cu-Al have very good activity at lower temperature for NO reduction by CO. All samples were characterized by XRD and BET. The tentative reaction mechanism was also proposed.

Bond covalencies in R2BaCuO5 (R = Sm, Gd, Dy, Ho, Y, Er, Tm, Yb, Lu)

Bond covalencies in R2BaCuO5 (R = Sm, Gd, Dy, Ho, Y, Er, Tm, Yb, Lu) were calculated by means of a semiempirical method. This method is the generalization of the dielectric description theory of Phillips-Van Vechten-Levine-Tanaka scheme. The present paper presents the formula concerning the decomposing of complex crystals which are usually anisotropic systems into the sum of binary crystals which are isotropic systems. It can be seen that although the bond covalency is related to many physical quantities, it is mainly influenced by bond valence or bond charge, and a higher bond valence will produce higher bond covalency.

Synthesis, characterisation and catalytic activity of propionamide complexes of rare earth chlorides

Propionamide complexes of rare earth chlorides were synthesized, Formula of the complexes is LnCl(3). 3BA. The ligand is shown to behave as a normal amide donor With the oxygen of the carbonyl group coordinated to the metal ions. Binary system composed Elf propionamide and aluminum alkyl shows higher activity and stereospecificity for butadiene polymerization. The cis-1,4 content of polybutadiene is more than 98%.

Preliminary study on the charge transfer and bond ionicity of binary crystals

Charge transfer and bond ionicity of some monovalent, divalent, and trivalent binary crystals of A(N)B(8-N) type have been investigated using the self-consistent method. The method divides the binary crystal systems into two subsystems which contain only one kind of element each in physical space. The charge transfer values are obtained by adjusting the charge in a self-consistent way. Based on the obtained charge transfer values, an empirical formula for bond ionicity has been proposed. It has been shown that the present results for bond ionicity are in good agreement with the previous theoretical study delivered by Levine and Pauling. The results also indicate that a large magnitude of charge transfer (or less excess charge in the bonding region) gives rise to high bond ionicity (or low bond covalency); this agrees well with the viewpoint that the excess charge in the bonding region is the origin of the formation of bond covalency. (C) 1998 American Institute of Physics. [S0021-9606(98)00837-X].

Bulk modulus of ternary chalcopyrite A(I)B(III)C(2)(VI) and A(II)B(IV)C(2)(V) semiconductors

Based on the complex crystal chemical bond theory, the formula of Liu and Cohen's, which is only suitable for one type of bond, has been extended to calculate the bulk modulus of ternary chalcopyrite A(I)B(III)C(2)(VI) and A(II)B(IV)C(2)(V) which contains two types of bonds. The calculated results are in fair agreement with the previous theoretical values reported and experimental values. (C) 1998 Elsevier Science Ltd. All rights reserved.

Structure, electric and magnetic properties of new compounds CdYMWO7 (M = Cr and Mn)

Two new compounds with the formula of CdYMWO7 (M = Cr, Mn) were prepared by solid state reaction. They crystallized with orthorhombic structure with the cell parameters of a = 11.7200 Angstrom, b = 7.1779 Angstrom, c = 6.9805 Angstrom (CdYCrWO7), and a = 11.7960 Angstrom, b = 6.1737 Angstrom, c = 7.6530 Angstrom (CdYMnWO7). These compounds are insulators with high resistivities at room temperature. The temperature dependence of the magnetic susceptibility of CdYMWO7 (M = Cr and Mn) show Curie-Weiss Law's behaviors from 80 to 300 K. The magnetic moments at room temperature fit very well with those corresponding to Cr3+ and Mn3+ ions. This suggests that both Cr and Mn ions exist in + 3 oxidation state in CdYMWO7 compounds. (C) 1998 Elsevier Science Ltd. All rights reserved.

Variation of crystallographic parameters in PEEKK with heat treatment temperature

Using the wide-angle X-ray diffraction method, the variation of crystallographic parameters of poly(aryl ether ether ketone ketone) (PEEKK) has been studied in different heat treatment temperatures. All the reflections and their intensities as well as their Miller indices are presented in detail according to an orthorhombic system. The investigation indicates that the unit cell parameters a, b, c and the unit cell volume V systematically decrease with increasing heat treatment temperature. This variation is interpreted by the change of conformation of polymer molecular chains during thermal treatment. The results calculated from the formula of degree of crystallinity (W-c,W-x) for PEEKK, which was derived based on X-ray scattering intensity theory and the graphic multipeak resolution method, are compatible with the density measurement (W-c,W-d) and calorimetry (W-c,W-h) values. (C) 1997 Elesevier Science Ltd.

General expression for probabilistic estimation of multiphase structure invariants in the case of a native protein and multiple derivatives. Application to estimates of the three-phase structure invariants

Concise probabilistic formulae with definite crystallographic implications are obtained from the distribution for eight three-phase structure invariants (3PSIs) in the case of a native protein and a heavy-atom derivative [Hauptman (1982). Acta Cryst. A38, 289-294] and from the distribution for 27 3PSIs in the case of a native and two derivatives [Fortier, Weeks & Hauptman (1984). Acta Cryst. A40, 646-651]. The main results of the probabilistic formulae for the four-phase structure invariants are presented and compared with those for the 3PSIs. The analysis directly leads to a general formula of probabilistic estimation for the n-phase structure invariants in the case of a native and m derivatives. The factors affecting the estimated accuracy of the 3PSIs are examined using the diffraction data from a moderate-sized protein. A method to estimate a set of the large-modulus invariants, each corresponding to one of the eight 3PSIs, that has the largest \Delta\ values and relatively large structure-factor moduli between the native and derivative is suggested, which remarkably improves the accuracy, and thus a phasing procedure making full use of all eight 3PSIs is proposed.

Synthesis of lanthanide-alkylaluminium bimetallic complexes and studies on their catalytic activities for polymerization of some polar monomers

Three new lanthanide (Ln)-alkylaluminium (Al) bimetallic complexes with the formula [(mu-CF3CO2)(2)Ln(mu-CF3CHO2)AIR(2) . 2THF](2) (Ln = Nd, Y, R=i-C4H9 (i-Bu); Ln=Eu, R=C2H5(Et); THF=tetrahydrofuran) were synthesized by the reaction of Ln(CF,CO,), (Ln=Nd, Y) with HAI (i-Bu)(2) and of Eu(CF3CO2)(3) with AlEt(3), respectively. Their crystal structures were determined by X-ray diffraction at 233 K. [(mu-CF3CO2)(2)Nd (mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Nd-Al) and [(mu-CF3CO2)(2)Y(mu-CF3CHO2)Al(i-Bu)(2) . 2THF](2) (Y-Al) are isomorphous and crystallize in space group with a=12.441(3) Angstrom [12.347(5) Angstrom for Y-Al], b=12.832(3) Angstrom [12.832(4) Angstrom], c=11.334(3) Angstrom [11.292(8) Angstrom], alpha=104.93 (2)degrees [104.45(4)degrees], beta=98.47(2)degrees [98.81(4)degrees], gamma=64.60(2)degrees [64.30(3)degrees], R=0.519 [0.113], R(w)=0.0532 [0.110], Z=1 and [(mu-CF3CO2)(2)Eu(CF3CHO2)AlEt(2) . 2THF](2)(Eu-Al) in space group P2(1)/n with a=11.913(6) Angstrom, b=14.051(9) Angstrom, c=17.920(9) Angstrom, alpha=101.88(11)degrees, beta=gamma=90 degrees, R=0.0509, R(w)=0.0471 and Z=2. The six CF3CO2- (including CF3CHO2-) of each complex, among which pairs are equivalent, coordinated to Ln and Al in three patterns: (A) the two oxygen atoms in one of the three CF3CO2- type coordinated to two different Ln; (B) the two oxygen atoms in the second of CF3CO2- type coordinated to Ln and Al, respectively; (C) one of the two oxygen atoms in the third CF3CO2- type bidentately coordinated to two Ln and another oxygen coordinated to Al and one of the two Ln, respectively. Unlike types A and B, in type C the carboxyl carbon with a hydrogen atom bonded to it was found to appear as an sp(3)-hybridized configuration rather than an sp(2)-one. 1D and 2D NMR results further confirmed the existence of such a disproportionated CF3CHO2- ligand. Methyl methacrylate (MMA) and epichlorohydrin (ECH) could be polymerized by Y-Al or Eu-Al as a single-component catalyst and highly syndiotactic poly(MMA) was obtained. THF could also be polymerized by Y-Al in the presence of a small amount of ECH.