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A new cyano-bridged binuclear 4f-3d complex Sm(DMSO)4-(H2O)3Cr(CN)6 was synthesized and characterized by single crystal structure analysis. It crystallizes in monoclinic, space group P21 with a=0.9367(2) nm, b = 1.3917(3) nm, c = 1.1212(2) run, β = 99.88(3)° and Z = 2. In this binuclear complex, Sm atom is eight coordinated and linked to the Cr atom by a cyano bridge. The molecules packs to form 3D structure due to the hydrogen bonds among them. [K3(18-C-6)3(H2O)4]Cr(CN)6·3H2O (18-C-6 represents 18-crown-6-ether) that was synthesized as a byproduct in the preparation of a Gd—Cr complex is also structurally characterized. Crystal data: triclinic, space group P-l with a = 1.0496(7) nm, b= 1.1567(14) nm, c = 1.3530(13) nm, a = 94.15(9)°, β = 96.04(8)°, γ = 95.25(9)° and Z = l. [K3(18-C-6)3(H2O)4]-Cr(CN)6·3H2O consists of ionic [K3(18-C-6)3(H2O)4]3+ and [Cr(CN)6]3- pairs, of which the [K3(18-C-6)3(H2O)4]3+ ion is a trinuclear duster connected by water, and K atoms are eight coordinated by eight oxygen atoms of one 18-C-6 and two water molecules.

A novel inorganic-organic hybrid material, Fe2O(OH)(C5H4-NCOO)SO4 was synthesized via solvothermal route using a reaction of FeCl3 ·6H2O, KCNS, and 4-cyanopyridne in aqueous solution of H2O2 and ethanol at 130 °C for 3 d. The compound crystallized in monoclinic space group P21, with cell parameters a=0.73850(15) nm, b = 0.65100(13) mn, c = 1.0546(2) nm, β = 90.36(3)°, V = 0.50700(18) nm3 and Z = 2. The structure is constructed with inorganic layered [Fe2O(OH) SO4]+ cations linked by organic (C5H4NCOO)− anions. The compound is thermally stable up to approximately 240 °C.

The complex Eu(btfa)3 (phen) (btfa=4,4,4-trifluoro-1-phenyl-1, 3-butanedione, phen = 1,10-phenanthroline) has been prepared and characterized by elemental analysis, IR and UV spectroscopies. The crystal and molecular structures of the complex have been determined by X-ray diffraction analysis. It belongs to the monoclinic crystal system, space group P21/c with a = 0.9700(2) nm, b = 3.7450(5) nm, c = 1.0917(3) nm, β = 92.51(2)°, V = 3.962(1) nm5, Z = 4, Dc = 1.639 g/cm3, μ = 1.676 mm−1, F(000) = 1936, R1, = 0.0388, wR2 = 0.0775. Structure analysis shows that the europium(III) ion is coordinated to six oxygen atoms of β-diketonate anions and two nitrogen atoms of phenanthroline molecule. The coordination polyhedron is an approximate square antiprism.

The strong π-acid ligand Ph2PN(iBu)PPh2 reacts with Co2(CO)S (1:1) to give Co2[μ-Ph2PN(iBu)PPh2] (μ-CO)2(CO)4 (1); however, when the ratio is 2:1 a novel species [Co{Ph2PN(iBu)PPh2-P,P′}2(CO)][Co(CO)4] (2) has been obtained. Crystal data for 2: Mr = 1140.83; triclinic, space group P 1 , a = 12.330(2), b = 13.340(2), c = 18.122(3) A, α = 86.63(1), β = 80.75(1), γ = 84.24(1)°, V = 2924 A3, Z = 2; R = 0.060 for 3711 reflections having I ⩾ 3σ(I). The results of X-ray diffraction, ESR, variable-temperature magnetic susceptibility, conductivity, and XPS analysis support that the species 2 is a d9-d9 cage molecule-pair. The mechanism for the formation of the species 2 has been investigated initially by 31P NMR.

η-CH3C(O)C5H4(CO)2Mo(μ-C6H5C2C6H5)Co(CO)3 (1a),η5-CH3C(O)C5H4(CO)2Mo(μ-p-CH3C6H4C2C6H5)Co(CO)3 (1b), η5-CH3O2CC5H4(CO)2Mo(μ-C6H5C2C6H5)Co(CO)3 (1c), η5-CH3C(O)C5H4(CO)2W(μ-C6H5C2C6H5)Co(CO)3 (1d) and η5-CH3O2CC5H4(CO)2W(μ-C6H5C2C6H5)Co(CO)3 (1e) were prepared by reactions of the corresponding sodium salts of functionally substituted cyclopentadienyl carbonyl molybdenum (tungsten) anions with (CO)3Co(μ-C6H5C2C6H5)Co(CO)3 or (CO)3Co(μ-p-CH3C6H5C2C6H5)Co(CO)3, respectively. The compounds 1a-1e were characterized by elemental analysis, IR, 1H NMR and mass spectroscopy, while the structure of 1c was further established by X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P21/n with a = 8.503(1), b = 26.721(7), c = 11.033(2) A; β = 106.09(2)°; V = 2408 A3; and Z = 4.

Twenty new compounds of the form Ph3GeCHArCH2COOSnR3 (R = n-Bu, cyclohexyl; Ar = substituted phenyl) have been synthesized. Their structures were characterized by IR and 119Sn and 1H NMR spectroscopy. The compounds are five-coordinated carboxylate bridged polymers when R = n– Bu; when R = cyclohexyl (Cy) they are four-coordinate. 119Sn NMR measurements of chemical shift for the two series of compounds have shown that there is a good linear relationship for the chemical shift of 119Sn NMR between the tributyltin and tricyclohexyltin propionates, viz. δ119Sn(Bu3Sn) = 1.0474 δ 119Sn(Cy3Sn) + 95.8076, n = 5, r = 0.993. The structure of one compound was determined by X-ray diffraction. It exists as a monomeric four-coordinated species in a distorted tetrahedronal geometry.

Reaction of [OsVI(N)Cl4]− with bis(diphenylarsino)ethane (AsAs) in acetone gave [OsVI(N)Cl3(AsAs)] isolated as an orange solid. The complex (space group P 1 (No.2), a=11.512(2), b=14.389(2), c=19.138(4) A, α=102.97(1), β=94.84(2), γ=110.24(1)°, V=2852.6(9) A3, Z=4; R=0.062 for 5216 observed Mo Kα data) is a distorted octahedral with three chlorine atoms in a meridional configuration. The measured OsN distances of the two crystallographically independent [OsVI(N)Cl3(AsAs)] molecules are 1.70(1) and 1.66(2) A. The photoluminescent properties of the osmium complex are discussed.

Crystalline [Dy(NCS)3(dibenzo-30-crown-10)(H2O)2]·H2O·MeCN can be obtained by slowly evaporating a reaction mixture of Dy(NCS)3·nH2O with dibenzo-30-crown-10 in a solution of acetonitrile. The material crystallizes in the monoclinic space groupP21/n, the cell parameters area=11.450(5),b=23.284(4),c=18.424(6)A, β=106.28(4)°,V=4715A3,M=968.47,D x=1.36 g cm−1, μ=17.80 cm−1,F(000)=1972,Z=4.2740 independently observed [I≥3σI] reflections were used in the final least-squares refinement leading to an agreement index ofR=0.085. The Dy(III) ion coordination geometry approximates a square antiprism, involving two water oxygens and three dibenzo-30-crown-10 oxygen atoms and three isthiocyanate nitrogens. Hydrogen bonds are formed between the two water molecules and four uncoordinated crown ether oxygen atoms.

The preparation, crystal structure and vibrational spectra of the new uranium (IV) compound UCl(H2PO2)3·2H2O are reported. The uranium atom is surrounded by six hypophosphito and two aqua oxygen atoms at the corners of a square antiprism. Hypophosphite groups serve as bridges between uranium atoms in the polymeric structure. The bands in the IR spectrum which correspond to hypophosphite modes of vibration are very similar to those of the isostructural bromo analogue UBr(H2PO2)3·2H2O, whereas features involving aqua ligand modes show stronger halide—water hydrogen bonding for the chloro compound.

The title compound has been synthesized and its crystal structure determined by X-ray crystallographic method. The crystal is monoclinic, space group C2/c, with unit cell dimensions a=19.260 (3), b=11.217 (1), c=15.997 (1) A; β=92.08 (2)° and Z=8. This is the first crystal structure determined in the series of bicyclo[10.3.0]pentadec-1(12)-en-13-one derivatives. The structure and the conformation of the cis-cyclododecene moiety in this compound is demonstrated to be closely similar to the lowest energy conformer [lene 2333].

The title complex has been prepared and characterized by IR spectroscopy and X-ray crystallography. The crystals are monoclinic, space group P21, with a = 9.2010(9), b = 13.044(3), c = 9.888(4) A, β = 109.35(2)° and Z = 2. The structure has been refined to RF = 0.038 for 288 variables and 3385 observed Mo Kα reflections. The crystal consists of an assembly of [C(NH2)3]+ cations, [TiO(CO3)3]4− anions, and water molecules which are interlinked by hydrogen bonds to form a three-dimensional network. The coordination geometry about the titanium atom may be described as a distorted pentagonal bipyramid, the axial positions being occupied by the oxo ligand and an oxygen atom of one of the chelating bidentate carbonato ligands.

The isomorphous cadmium(II) oxalate trihydrate (I) and lead(II) oxalate trihydrate (II) crystals belong to space groupP¯1 withZ=2. The crystallographic parameters for compoundI are:a=6.006(1),b=6.663(1),c=8.497(1)A,a=74.76(1),β=74.39(1), γ=80.94(1)°, andR=0.028 for 2643 observed MoKα reflections; forII:a=6.008(1),b=6.671(1),c=8.493(1)A,a=74.70(1),β=74.33(1), γ=80.98(1)°, andR=0.065 for 4536 reflections. In the crystal structure, the metal atom is surrounded by seven oxygen atoms (including two aqua ligands) in the form of a distorted pentagonal bipyramid. The coordination polyhedra are interconnected through bridging oxalate groups to form a “thick layer” matching the (020) plane. Adjacent layers are further linked by hydrogen bonds involving both ligand and lattice water molecules to generate a three-dimensional network.

The X-ray crystal structure of the complex [Ni2(TPHA)(bpy)4](ClO4)2 (TPHA = terephthalato, bpy = 2,2′-bipyridine) has been determined. Its structure consists of a terephthalato bridged nickel(II) binuclear cation and non-coordinated perchlorate anions. In the complex the TPHA bridges are in a bis bidentate configuration. The environment of the nickel(II) ion is distorted octahedral.