SYNTHESIS, STRUCTURE AND SPECTRA PROPERTIES OF THE NEODYMIUM MOLYBDOGERMANATE HETEROPOLY COMPLEX

K7H6[Nd(GeMo11O39)2].18H2O was first synthesized and the crystal structure was determined. Crystal structure data are as follows: monolinic, space group P2(1)/n, a = 1.7095(4), b = 2.6895(3), c = 2.1214(5) nm, beta = 103.11 (2)-degrees, V = 9.4994(3) nm3, Z = 4, D(m) = 3.14g/cm3, D(c) = 3.05g/cm3, mu(MoK-alpha) = 43.7 cm-1. Experimental evidence and theoretical foundation of the method inferring the molecule structure of heteropoly compounds using their IR spectra were gaved by studying IR spectra properties of the complex with results of structural analysis. Electronic spectra prove that 4f-obital of Nd3+ take part in bonding in the complex.

SYNTHESIS AND CRYSTAL-STRUCTURE OF THE TRIS(CYCLOPENTADIENYL)PHENYL COMPLEX OF NEODYMIUM, (LI-BULLET-3DME)[(ETA-5-C5H5)3NDC6H5]

(Li.3DME)[eta(5)-C5H5)3NdC6H5], 1 was synthesized by the reaction of NdCl3.2LiCl, 2 equivalents of cyclopentadienylsodium and one equivalent of phenyllithium in THF at -78-degrees-C, and crystallized from THF and DME. The crystal structure of 1 was determined by X-ray diffraction method at -80-degrees-C. The crystal of 1 is triclinic, space group P1BAR with a = 15.752(6), b = 16.232(3), c = 23.038(7) angstrom, alpha = 108.81(2), beta = 93.31(3), gamma = 108.38(2)-degrees, Z = 6 and D = 1.33 g/cm3. Least-squares refinement (5732 observed reflections) led to a final R of 0.053. The complex consists of disconnected ion pairs of (Li.3DME)+ and [(eta(5)-C5H5)3NdC6H5]-. The neodymium atom was connected to three eta(5)-bonded cyclopentadienyls and one sigma-bonded phenyl in a distorted tetrahedral arrangement with Nd-C(sigma-) 2.593(17), 2.613(13) and 2.601(13) angstrom.

STRUCTURE OF 1,10-DIAMINODECANE TETRACHLOROZINCATE

[NH3(CH2)10NH3][ZnCl4], M(r) = 381.51, triclinic, P1BAR, a = 7.296 (1), b = 10.110 (3), c = 12.814 (4) angstrom, alpha = 90.84 (2), beta = 101.17 (2), gamma = 92.52 (2)-degrees, V = 926.13 angstrom 3, Z = 2, D(x) = 1.37 Mg m-3, lambda(Mo K-alpha) = 0.71073 angstrom, mu = 1.925 mm-1, F(000) = 396, T = 298 K, final R = 0.070 for 1237 unique reflections [I > 3-sigma(I)]. The structure is characterized by layers of inorganic ions sandwiched between layers formed by the paraffinic chains.

STRUCTURE OF 1,3-PROPANEDIAMMONIUM TETRACHLOROCOBALTATE(II)

[CoCl4(C3H12N2)], M(r) = 276.87, monoclinic, P2(1)/n, a = 10.703 (2), b = 10.653 (1), c = 10.852 (2) angstrom, beta = 118.46 (1)-degrees, V = 1087.8 angstrom 3, Z = 4, D(x) = 1.69 g cm-3, lambda(Mo K-alpha) = 0.71073 angstrom, mu = 22.60 cm-1, F(000) = 556, T = 298 K, final R = 0.059 for 1068 unique reflections [I > 3-sigma(I)]. The Co(II) ion is coordinated by four Cl atoms in a tetrahedral geometry. The paraffinic chains which bridge the tetrahedra have a nearly planar zigzag configuration.

CRYSTAL STRUCTURE AND THERMAL ANALYSIS OF ERBIUM COMPLEX WITH BENZENE ACETIC ACID

The crystal structure of erbium (III) complex of benzene acetic acid is reported. The complex crystallizes in the monoclinic space group P2(1)/a with a = 0,9008(3)nm, b=1.4242(5) nm, c=1.8437(7) nm, beta=98.80(3)degrees, V = 2.337(1) nm(3), Z = 4. The mechanism of thermal decomposition of complex has been studied by TG-DTG-DTA. The activation energy for dehydration reaction has been calculated by Freeman Carroll method. The enthalpy change for dehydration and phase change process has been determined.

INFRARED SPECTRA AND CRYSTAL STRUCTURE OF BIS-(DIMETHOXYLPHOSPHATO) COPPER

The title complex has beep synthesized by the reaction of CaCl2, with trimethyl phosphate. Its Infrared spectra from 4000 to 100 cm(-1) measured. The assignment of acme absorption bands was discussed. It is found that the stretching vibrations of bridge groups O-P-O are divided into two groups according to their bond length. The crystal structure of the complex boa been determined from single crystal K-ray diffraction data. The crystals belong to monoclinic system, space group P2(1)/c with cell parameteras, a = 1,0704(4), b = 0.5093(2), c = 1.9737(6)nm, beta = 96.23(3)degrees, V = 1.0696(6)nm(2), Z = 4, final R = 0.044. Copper ion is coordinated to five Rimester oxygen atoms to form a distorted square pyramid. The adjacent copper ions are connected by symmetric and non-symmetric bridge groups of O-P-O, forming an infinite one-dimensional chain coordination polymer.

C-13 AND H-1 NMR STUDIES OF SOLUTION STRUCTURE OF LANTHANIDE COMPLEX WITH GLYCYL-GLYCINE

C-13 and H-1 NMR technique was used to study the interaction of Gly-Gly with heavy lanthanide cations Dy3+, Ho3+, Er3+, Tm3+ and Yb3+ in aqueous solution. The stability constants for the 1:1 and 1:2 complexes of Gly-Gly with Ho3+ and Yb3+ were determined from the titration curves of chemical shift versus concentration ratio of lanthanide to Gly-Gly. The solution structure of the Ln-Gly-Gly complex was analyzed based upon the C-13 and H-1 lanthanide induced shifts and the results show that in the complex Gly Gly is coordinated to the lanthanide ion through the carboxyl oxygens with the backbone of the ligand in an extended state.

PREPARATION AND MOLECULAR-STRUCTURE OF METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)NEODYMIUM AND METHYLBIS(TERT-BUTYLCYCLOPENTADIENYL)GADOLINIUM

Bis(t-butylcyclopentadienyl)lanthanide chloride (Ln = Nd or Gd) reacts with one equivalent of methyllithium in ether/tetrahydrofuran to give the complex [(C5H4tBu)2LnCH3]2 (Ln = Nd or Gd). The structure of [(C5H4tBu)2NdCH3]2 has been determined by X-ray analysis. The crystals are monoclinic of space group Cm with a = 9.538(2), b = 23.298(4), c = 9.505(3) angstrom, beta = 119.53(2)-degrees, V = 1828.0(7) angstrom 3, D(calc.) = 1.458 g/cm3 and Z = 2 for the dimer. The two (C5H4tBu)2Nd units in the dimer are connected by asymmetrical methyl bridges with independent Nd-C bond lengths of 2.70(2) and 2.53(2) angstrom and Nd-C-Nd angles of 94.7(9) and 87.3(6)-degrees.

STRUCTURE OF CIS-DIAQUABIS(1,10-PHENANTHROLINE)ZINC SULFATE HEXAHYDRATE

[Zn(C12H8N2)2(H2O)2]SO4.6H2O, M(r) = 665.98, triclinic, P1BAR, a = 10.070 (4), b = 12.280 (3), c = 13.358 (2) angstrom, alpha = 109.12 (2), beta = 92.58 (2), gamma = 110.85 (2)-degrees, V = 1433.9 (7) angstrom 3, Z = 2, D(x) = 1.54 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 10.1 cm-1, F(000) = 692, T = 293 K, R = 0.044 for 3985 observed reflections. The Zn atom is coordinated in a distorted octahedral geometry by four N atoms from two 1,10-phenanthroline (phen) ligands and two water molecules. The intermolecular ring-stacking interactions between the phen ligands occur in two forms: infinite chains and discrete dimers. Hydrogen bonds further stabilize the structure.

SYNTHESIS AND CRYSTAL-STRUCTURE OF K4H2[PMO9V3O40].10H2O

The crystal structure of the title compound was determined from single crystal X-ray diffraction at -90-degrees-C. The complex crystallizes in the tetragonal P4/mnc, Z = 2, a = 12.515(3), c = 17.636(7) angstrom. The structure was solved by Patterson and Fourier techniques and refined by least-squares to R = 0.061 for 788 reflections. The central PO4 is disordered, P-O = 1.54 angstrom, M(M = Mo or V) is 6-coordinate, M-O = 1.62-2.48 angstrom, K is 7-coordinate, K-O = 2.84-3.10 angstrom.

A NOVEL METAL THIAMINE COMPLEX WITH A CYCLIC DIMER FORMED BY METAL-BRIDGED 2 THIAMINE LIGANDS - CRYSTAL-STRUCTURE OF [MN(THIAMINE)CL2(H2O)]2[THIAMINE]2CL4.2H2O

The crystal structure of [Mn(thiamine)Cl2(H2O)]2[thiamine]2Cl4.2H2O has been determined by X-ray diffraction methods. The compound contains a cyclic dimer of a complex cation with two thiamine ligands bridged by two Mn(II) ions across a crystallographic center of symmetry. Each Mn(II) is coordinated by two chloride atoms, a water molecule, a N(1') atom of the pyrimidine from a thiamine and an O(53) atom of the hydroxyethyl side chain from another thiamine. There are two free-base thiamine molecules related by a center of symmetry in the unit cell, which form a base-pair through the hydrogen bonds. Both the independent thiamine molecules in the asymmetric unit assume the common F conformation with phi-T = 10.0(9) and 3.6(10) and phi-P = 85.6(7) and 79.6(7), respectively. The compound provides a possible model for a metal-bridged enzyme-coenzyme complex in thiamine catalysis. Crystallographic data: triclinic, space group P1BAR, a = 12.441(4), b = 13.572(4), c = 11.267(3) angstrom, alpha = 103.15(2), beta 89.03(3), gamma = 115.64(2)-degrees, Z = 1, D(calc) = 1.524 g cm-3, and R = 0.050 for 3019 observed reflections with I > 3-sigma(I).

STRUCTURE OF HEXAMETHYLENETETRATELLURAFULVALENE DIIODIDE

C12H12I2Te4, M(r) = 920.44, monoclinic, P2(1)/n, a = 10.942 (2), b = 14.924 (2), c = 11.415 (2) angstrom, beta = 104.32 (1)-degrees, V = 1806.0 (5) angstrom 3, Z = 4, D(x) = 3.38 g cm-3, lambda(Mo K-alpha) = 0.71069 angstrom, mu = 100.7 cm-1, F(000) = 1592, T = 294 K, R = 0.033 for 1828 observed reflections. One of the Te atoms is bonded to the two I atoms, which are on either side of the molecular plane. The Te-I distances are 2.963 (1) and 2.961 (1) angstrom, which means oxidation at the Te atom instead of at the C = C bonds.

SYNTHESIS AND STRUCTURE OF (ETA-5-C5H5)2YB.DME

(eta-5-C5H5)2YbCl.THF reacts with an equivalent molecular quantity of K(2,4-C7H11) (2,4-dimethyl pentadienyl potassium), and treatment of the product with DME yields (eta-5-C5H5)2Yb.DME. The crystal of (eta-5-C5H5)2Yb.DME belongs to the orthorhombic space group Fdd2 with a = 13.678(4) angstrom, b = 23.255(6) angstrom, c = 9.192(2) angstrom and Z = 8. The crystal parameters are found to differ from previously reported data.

SYNTHESIS AND CRYSTAL-STRUCTURE OF HETEROPOLY MOLYBDOSILICIC LANTHANIDE K10H3[PR(SIMO11O39)2].18H2O

The intensity data of the title complex were collected at a low temperature of -90-degrees-C. The compound crystallizes in the monoclinic space group P2(1)/n, a = 17.504(2), b = 27.323 (5), c = 21.616(4) angstrom, beta = 104.49 (2)degrees, Z = 4. The structure was solved by Patterson and Fourier techniques and refined by least-squares to an R = 0.088 for 8320 independent reflections. The central Pr ion is bonded to eight oxygen atoms from two molybdosilicic heteropoly ligands to form a square antiprism. The Pr-O average distance is 2.44 (2) angstrom. Both molybdosilicic heteropoly ligands are of a defective alpha-Keggin structure.

SYNTHESIS AND X-RAY CRYSTAL-STRUCTURE OF A MONOPENTAMETHYLCYCLOPENTADIENYL DERIVATIVE OF GADOLINIUM (NA(MU-2-THF)[(C5ME5)GD(THF)]2(MU-2-CL)3(MU-3-CL)2)2.6THF

The reaction of GdCl3 with 1 equiv of NaC5Me5 generates a neutral complex C5Me5GdCl2(THF)3 and a novel complex {Na(mu-2-THF)[(C5Me5)Gd(THF)]2(mu-2-Cl)3(mu-3-Cl)2}2.6THF whixh recrystallizes from THF in triclinic, the space group P1BAR with unit cell dimentions of a 12.183(4), b 13.638(6), c 17.883(7) angstrom, alpha-110.38(3), beta-94.04(3), gamma-99.44(3)-degrees, V 2721.20 angstrom-3 and D(calc) 1.43 g cm-3 for Z = 1. Least-squares refinement of 2170 observed reflections led to a final R value of 0.047. The title complex consists of two Na(mu-2-THF)[(C5Me5)Gd(THF)]2(mu-3-Cl)3(mu-3-Cl)2 units bridged together via two mu-2-THF to Na coordination. Each Gd ion is surrounded by one C5Me5 ligand, two mu-3-Cl, two mu-2-Cl and one THF in a distorted octahedral arrangement with average Gd-C(ring) 2.686(33), Gd-mu-2-Cl 2.724(7), Gd-mu-3-Cl 2.832(8) and Gd-O 2.407(11) angstrom. The sodium ion coordinates to two bridging THF, two mu-2-Cl and two mu-3-Cl to form a distorted octahedron with average Na-mu-2-O, Na-mu-2-Cl and Na-mu-3-Cl of 2.411(21), 2.807(15) and 2.845(12) angstrom, respectively.