Inorganic Chemistry Communications (v.6, #6)

Contents list (iii-v).

A novel ligational mode of pyrimidine-2-thione. Molecular structure of dimethyl-(4-trifluromethyl-6-methylpyrimidine-2-thionate)thallium(III) by Antonio Rodrı́guez; J Arturo Garcı́a-Vázquez; Antonio Sousa-Pedrares; Jaime Romero; Antonio Sousa (619-622).
The reaction between 4-trifluromethyl-6-methylpyrimidine-2-thione (4-CF3-6-CH3pymSH) and dimethylthallium(III) hydroxide in methanol yielded [Me2Tl(4-CF3-6-CH3pymS)]4; this compound exhibits a tetranuclear structure with thionate ligands acting as bridges between two metallic atoms. Vibrational and 1 H , 13 C and 205 Tl NMR spectra of the complex are discussed and related to the structure.
Keywords: Crystal structure; Thallium (III) complex; Pyrimidine-2-thionate complex; Tetranuclear complex;

Photoactivity of cationic phthalocyanine derivative of zinc(II)-loaded natural zeolites by Kuninobu Kasuga; Tomohiro Fukuyama; Tamotsu Sugimori; Makoto Handa (623-625).
Phthalocyaninatozinc(II) with cationic substituents was adsorbed on natural zeolites, clinoptiolite and mordenite, while it was not adsorbed on synthetic zeolites. The complex might be intercalated into a small amount of clay contained in the natural zeolites as an impurity. The complex-loaded zeolites acted as a sensitizer for photooxidation of bilirubin ditaurate in an aqueous solution.
Keywords: Phthalocyanine; Zeolite; Clay; Bilirubin ditaurate; Photosensitizer;

A new family of 3,5-bis(4-n-alkyloxyphenyl)-1-(pyridin-2-yl)-1H-pyrazole ligands (pypzR2) and their complexes of formula c-[PdCl2(pypzR2)] have been synthesised and their mesomorphism was investigated . The effectiveness of the asymmetric molecular design in promoting thermotropic mesophases is greater for complexes than for the related ligands, although the latter exhibit mesophases at lower temperatures. These complexes are the first example of metallomesogens containing N,N -bidentate ligands co-ordinated to PdCl2.
Keywords: Long-chain 3,5-disubstituted-1-(pyridin-2-yl)pyrazoles; Pd(II) complexes; Mesomorphism;

A novel one-dimensional nickel(II) complex incorporating nitroxide radical with the formula {[Ni(NITpPy)2  (TCB)(H 2 O)2]·2H 2 O}n has been synthesized and characterized. Theoretical analysis of the variable-temperature magnetic susceptibility data of the complex reveals that there are two kinds of antiferromagnetic intrachain interactions.A novel one-dimensional nickel(II) complex incorporating a nitroxide radical with the formula {[Ni(NITpPy)2(TCB)(H2O)2]·2H2O} n (NITpPy=2-(4-pyridyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide and TCB=1,4-dicarboxy-2,5-dicarboxylatobenzene dianion) has been synthesized and characterized. Theoretical analysis of the variable-temperature magnetic susceptibility data of the complex reveals that there are two kinds of antiferromagnetic intrachain interactions.
Keywords: Nitroxide radical; Nickel complex; One-dimensional chain; Magnetic properties;

1D and 2D network of ReO4 bonded azoimidazoles by Umasankar Ray; Brojogopal Chand; Anup Kumar Dasmahapatra; Golam Mostafa; Tian-Huey Lu; Chittaranjan Sinha (634-638).
1-Alkyl-2-(arylazo)imidazoles are π-acidic, bidentate chelating molecules. In acid medium imidazole-N centers are protonated and can extract heavy anions. One such example is the binding with ReO4 in acidic medium. 1-Alkyl-2-(arylazo)imidazolium-perrehenate shows hydrogen bonded 1D network. Inclusion of H2O into the molecular frame of 1D increases the dimensionality to 2D network.
Keywords: Imidazolyl azo; Hydrogen bond; π–π stacking; Supramolecular network;

Ferrocenylanthracene polymers: the direct synthesis using “Lawesson’s Reagent” by Ian R Butler; Alfonso G Caballero; Glenn A Kelly (639-642).
A method for polymerizing ferrocenylanthraquinone compounds was investigated, using a methodology developed originally for the polymerization of 9,10-anthracenedithiols. This procedure uses an in situ reaction of “Lawesson’s Reagent” (p-methoxyphenylthionophosphine sulphide dimer), with anthraquinone allowing polymerization to proceed across the 9- and 10-positions of the ferrocenylanthraquinones resulting in polymers with pendant ferrocene groups on the polymer backbone. Monomers used for these reactions were anthraquinone (literature comparison), 2-ferrocenylanthraquinone and 2,6-diferrocenylanthraquinone.
Keywords: Anthraquinone; Ferrocene; Ferrocenylanthraquinone; “Lawesson’s Reagent”; Polymers;

Mass spectrometric and FTIR spectroscopic identification of FeF4 molecules in gaseous phase by Juliet V Rau; Stella Nunziante Cesaro; Norbert S Chilingarov; Miroslav S Leskiv; Giovanni Balducci; Lev N Sidorov (643-645).
The existence of a new compound – gaseous FeF4 – was assumed based on the results of Knudsen effusion mass spectrometry and FTIR spectroscopy. Hyperfluorination was achieved by applying excessive amount of CeF4(s) fluorinating agent in reaction with FeF3(s) at high temperatures (T=930–1050 K). The 758.5 cm−1 vibrational frequency was attributed to the Fe–F stretching mode of argon isolated FeF4 molecules.
Keywords: Gaseous iron tetrafluoride; Knudsen effusion mass spectrometry; FTIR spectroscopy;

Preparation and crystal structure determination of adducts of copper(II) chloride with 3-aryl-1-(imino-pyridin-2-yl-methyl)-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-pyrazoles by Helio G. Bonacorso; Ernesto S. Lang; Hilário Lewandowski; Marcos A.P. Martins; Clovis Peppe; Nilo Zanatta (646-649).
1,1,1-Trifluoro-4-methoxy-4-aryl-but-3-en-2-ones react with 2-pyridylcarboxamidrazone to produce the corresponding 1,1,1-trifluoro-4-aryl-4-(N1-pyridine-2-carboxamidrazone)-3-buten-2-ones. The butenones react with copper(II) chloride to give 1:1 adducts, in which the donor molecules were shown to isomerize to their cyclic pyrazolic forms. The crystal structure of the 4-fluoro-phenyl derivative, dichloro-[3-(4-fluorophenyl)-1-(imino-pyridin-2-yl-methyl)-5-hydroxy-5-trifluoromethyl-4,5-dihydro-1H-pyrazole]-copper(II), was solved by X-ray crystallography. The structural results are compared with those of other copper(II) chloride adducts of similar ligands containing the amidrazone pharmacophore, which have been tested as anticancer drugs.
Keywords: Amidrazone pharmacophore; Dihydropyrazoles; Copper complex; Crystal structure determination;

DFT investigation of copper–peptide complexes related to the octarepeat domain of the prion protein by Elena Franzini; Luca De Gioia; Piercarlo Fantucci; Giuseppe Zampella; Vlasta Bonačić-Koutecký (650-653).
Recently, it has been demonstrated that the prion protein binds Cu(II) ions by the N-terminal domain [Chem. Eur. J. 6 (2000) 4195; Biochemistry 38 (1999) 11560], which is composed of four or more repeats of the eight-residue sequence PHGGGWGQ (octarepeat). X-ray diffraction experiments [Biochemistry 41 (2002) 3991] have shown that the peptide HGGGW embraces the fundamental Cu2+ binding unit and EPR and circular dichroism (CD) experiments, carried out on the Cu(HGGG) complex, show subtle differences in the local coordination geometry with respect to the Cu(HGGGW) species. In this contribution we have investigated Ac–HGGG–NH2/Cu2+ model complexes by means of DFT calculations, showing that the relative stabilities of four- and five-coordinated species are affected by the extent of the H-bond network and by peptide strain. However, when these contributions are not significant, square-planar coordination of Cu is definitely preferred. These observations fit well with the data from EPR experiments [Biochem. J. 344 (1999) 1; Trends Neurosci. 24 (2001) 85; Curr. Opin. Chem. Biol. 4 (2000) 184] that pointed out how a modification in the coordination environment of Cu can take place by going from Cu(HGGGW) to Cu(HGGG).

The first carboranyl bis(adenosine diphosphate) (CBADP): a synthetic investigation by Kamesh Vyakaranam; Geeta Rana; Shannon Delaney; Sarah Ledger; Narayan S. Hosmane (654-657).
The synthesis of the first carboranyl bis(adenosine diphosphate) (CBADP) (5) was achieved in three steps. The first step involved the reaction of o-carborane dianion, 1, with methyl dichlorophosphate to yield 2. Reagent 4 was synthesized by the reaction of bis-benzoyl-protected adenosine with phosphoryl chloride, followed by the protection of the free hydroxyl group in the product, 3, with methyl triflate. The final step converged both 2 and 4 into the title compound, CBADP (5).
Keywords: Boron neutron capture therapy; Nucleosides; Lithiation; Phosphorylation; Dianion; Carborane; Adenosine diphosphate;

A novel cyano-bridged Sr(II)–Fe(III) polymer containing alternating octanuclear and tetranuclear cores by Amitabha Datta; G.M. Golzar Hossain; Nirmal Kumar Karan; K.M. Abdul Malik; Samiran Mitra (658-661).
A novel cyano-bridged Sr(II)–Fe(III) polymeric complex ([Sr3(phen)6(H2O)6{Fe(CN)6}2]·phen·6.5H2O) n (1) has been synthesized and structurally characterized. The complex contains alternating octanuclear 24-membered and tetranuclear 12-membered metallocycles, which are repeated to form a polymeric chain. The Sr(II) centres are eight coordinated with distorted bicapped trigonal prismatic geometry while the Fe(III) centres have six coordinate octahedral geometry.
Keywords: Heterometallic macrocycle; Strontium–iron; Cyano-bridged; Phenanthroline; Crystal structure;

A novel ruthenium complex with 2-(2-pyridyl)-4-methylcarbonylquinoline ligand has been prepared and characterized: the first crystal structure of such complex along with its physical and chemical properties are also described.
Keywords: Ruthenium(II) complex; Structure; Electrochemistry; 2-(2-pyridyl)-4-methylcarbonylquinoline;

The zinc(II) complex, of the dimeric {Zn[3-(Ac-Phe)-5-methyl-pyrazole]2}2(ClO4)4 (5) was obtained by the reaction of the amino acid–pyrazole conjugate, 3-(Ac-Phe)-5-methyl-pyrazole (4) and Zn(ClO4)2. An acetone solvate of this complex was analyzed by single crystal X-ray crystallography, which establishes the dimeric nature of the complex with a large Zn–Zn separation of 5.551(6) Å and exbihiting coordination to the distorted trigonal bipyramidal zinc centers through the amino acid CO and the pyrazole N.
Keywords: Pyrazole; Bioconjugate; Amino acid; Zinc complex; Bioinorganic;

The synthesis and characterization of Pb5S2I6 whiskers and tubules by Qing Yang; Kaibin Tang; Chunrui Wang; Jian Zuo; Yitai Qian (670-674).
Pb5S2I6 whiskers and tubules were synthesized from the reaction among lead chloride, thiourea, and excess sodium iodide under hydrothermal conditions at 200 °C for 20–40 h. XRD, SEM, XPS, ICP-AES, and TEM characterized the final products. Most products are whiskers with structure of 3–4 mm in length, 0.5–2.0 μm in diameter for a singular one. Meanwhile, about 10% tubules are produced in the process. The tubules are 3–6 mm in length, 8–20 μm in diameter, and 1–3 μm in thickness. Nanowhiskers were also produced in the route at 180–200 °C for 8–10 h. Raman spectra show that the Pb5S2I6 crystals have complex vibrational modes of PbS and PbI2.
Keywords: Chalcogenide halides; Crystals; Hydrothermal reaction; X-ray photoelectron spectroscopy; Raman spectroscopy;

Two tetrasubstituted tetranuclear ruthenium clusters containing dimethylphenylphosphine [H4Ru4(CO)8(PMe2Ph)4] and [H2Ru4(CO)9(PMe2Ph)4] were prepared and characterized spectroscopically as well as by X-ray crystallography. Both compounds show a structure based on the usual 60-electron tetrahedral framework with each ruthenium atom being bonded to one phosphine ligand. In the case of the nonacarbonyl derivative, one of the ruthenium atoms has one terminal carbonyl group and is also bonded to two semibridging carbonyl groups; two other metal–metal bonds are bridged by the hydride groups. In the case of the octacarbonyl compound all the ruthenium atoms are bonded to two terminal carbonyls and to two bridging hydrides. NMR spectroscopical information of [H4Ru4(CO)8(PMe2Ph)4] suggests the presence of two isomers in solution which we propose to have D2d and Cs symmetries. The observation of the NMR properties gives some observations about conditions that favour coupling between substituents in different ruthenium atoms.
Keywords: Tetraruthenium clusters; Dimethylphenylphosphine; NMR characterization; Crystal structures;

Reaction of the symmetrical α-diimine ligand L with either PtCl2 or PdCl2(C6H5CN)2 affords the square planar d8 complexes 1 and 2, respectively. Both complexes were characterized by NMR spectroscopy and elemental analysis. The solid-state structure of 1, which crystallized in the triclinic space group P 1 ̄ with unit cell parameters a=8.688(2)  A ̊ , b=13.840(2)  A ̊ , c=14.136(2)  A ̊ , α=111.346(14)°, β=103.82(2)°, and γ=102.69(2)°, was established by X-ray crystallography.
Keywords: Diazabutadiene ligands; Platinum(II) complex; Palladium(II) complex;

Synthesis and structural characterisation of unprecedented dinuclear zinc(II) complex with H-bonded bridging phthalate ions by Svetlana G Baca; Yurii A Simonov; Maria Gdaniec; Nicolae Gerbeleu; Irina G Filippova; Grigore A Timco (685-689).
An extremely unusual dimer [(bpy)2Zn(Pht)H(Pht)Zn(bpy)2)](HPht)(H2Pht)·2H2O (1) (where Pht2−=dianion of o-phthalic acid, bpy=2,2-bipyridine) in which [Zn(bpy)2] metal cores are connected through Pht⋯H⋯Pht bridge has been synthesised and its structure determined by X-ray crystallography.
Keywords: Zinc(II) carboxylate; Phthalate complex; Crystal structure; Hydrogen bonding;

A unique three-dimensional coordination polymer constructed from 4,4-biphenyldicarboxylate and zinc(II) by La-Sheng Long; Yan-Ping Ren; Li-Hua Ma; Yun-Bao Jiang; Rong-Bin Huang; Lan-Sun Zheng (690-693).
Zinc(II) coordination polymer [Zn(bpdc)] n (bpdc=4,4-biphenyldicarboxylate) (1) with a unique entanglement PtS structure was synthesized by hydrothermal reaction of zinc nitrate and 4,4-biphenyldicarboxylic acid in aqueous sodium hydroxide solution.
Keywords: Zinc(II); 4,4-biphenyldicarboxylic acid; Coordination polymer; Entanglement PtS structure;

Single crystal structure of a heterometallic one-dimensional polymer: [{Cu(1,10-phen)}2(V2O4)(O3PCH2CH2CH2CH2PO3H)2(H2O)] n by Rui-Biao Fu; Xin-Tao Wu; Sheng-Min Hu; Wen-Xin Du; Jian-Jun Zhang; Zhi-Youg Fu (694-697).
A heterometallic one-dimensional polymer [{Cu(1,10-phen)}2(V2O4)(O3PCH2CH2CH2CH2PO3H)2(H2O)] n 1 (1,10-phen=1,10-phenanthroline) has been synthesized under hydrothermal conditions. The structure of 1 shows a stepped chain with two parallel 1,4-butylenediphosphonate ligands as linking units.
Keywords: Single crystal; Polymer; 1,4-Butylenediphosphonate ligands;

A binary copper(II) complex [CuL2] (1), where HL is the Schiff base N-salicylidene-2-methoxyaniline, was prepared and structurally characterized. The complex which crystallizes in cubic space group Ia-3d with an unit cell dimension of 31.2451(17) Å, V=30503(3)  A ̊ 3 , Z=48, and refined to R-value of 0.0379 for 1700 data with I>2σ(I), shows a distorted four coordinate structure with a CuN2O2 chromophore. The complex self-assembles into a supramolecular architecture by non-covalent C–H⋯O interactions forming open and closed channels.
Keywords: Copper(II) complex; Schiff base; X-ray structure; Supramolecular architecture; Lattice channels;

A novel 1D ladder-like organic–inorganic hybrid compound [(Cu(bIz)2)]2[{Cu(bIz)2}2Mo8O26] (bIz=benzimidazole) by Junhua Luo; Maochun Hong; Ruihu Wang; Qian Shi; Rong Cao; Jiabao Weng; Ruiqing Sun; Hanhui Zhang (702-705).
A novel organic–inorganic hybrid compound [(Cu(bIz)2)]2[{Cu(bIz)2}2Mo8O26] (1) has been synthesized from solvothermal reaction of benzimidazole, NaMoO4 and MoO3 with CuCl2·2H2O in H2O/CH3OH solution and characterized by single-crystal X-ray diffraction analysis. Crystallographic data for 1: monoclinic, space group C2/c, a=23.6823(2) Å, b=20.2669(5) Å, c=16.0220(3) Å, β=109.030(1), Z=8, V=7269.8(2)  A ̊ 3 . The compound consists of a centrosymmetric β-octamolybdate-supported complex anion [{Cu(bIz)2}2Mo8O26]2−, and two bis-bIz coordinated Cu(I) cations. The hydrogen bonds between [{Cu(bIz)2}2Mo8O26]2− anions generate a interesting 1D ladder. TG analysis, UV–Vis spectra and fluorescent spectroscopy of the compound were also studied.
Keywords: Crystal structure; Copper-molybdate complex; Fluorescence; Solvothermal reaction;

Molecular chains: two new isomorphous coordination polymers of oxydiacetate by Chao Jiang; Xiang Zhu; Zhao-Peng Yu; Zhi-Yong Wang (706-709).
Two new isomorphous coordination polymers: [M2(μ-H2O)(oda)2(H2O)2] n (where M=Mn(II), 1, and M=Cd(II), 2) have been synthesized under hydro(solvo)thermal reaction conditions, which are characterized by single crystal X-ray determination, IR and thermogravimetric analysis (TGA). Both 1 and 2 have a covalently linked one-dimensional chain structure and are self-assembled from the building units M(oda). Magnetic measurement of 1 indicates weak antiferromagnetic interactions along the carboxylate-bridged Mn(II)–Mn(II) chains. Crystallographic data for 1, C8H14Mn2O13, monoclinic, space group C2/c (no. 15), a=14.831(3) Å, b=7.5388(12) Å, c=13.068(2) Å, β=96.009(2)°, Z=4, V=1453.1(4) A ̊ 3 . Crystallographic data for 2, C8H14Cd2O13, monoclinic, space group C2/c (no. 15), a=15.0139(3) Å, b=7.5531(3) Å, c=13.3505(5) Å, β=94.333(2)°, Z=4, V=1509.64(9) A ̊ 3 .
Keywords: Coordination polymer; One-dimensional structure; Metal oxydiacetate; Hydro(solvo)thermal synthesis; Magnetic-properties;

Microwave synthesis of AgBiS2 dendrites in aqueous solution by Di Chen; Guozhen Shen; Kaibin Tang; Xuan Jiang; Liying Huang; Ying Jin; Yitai Qian (710-712).
The microwave-assisted synthesis is generally much faster, cleaner, and more economical than the conventional methods. Here, dendritic crystals of AgBiS2 were synthesized in aqueous solution under microwave irradiation for 30 min. Powder X-ray diffraction (XRD) pattern indicates that the product is in the pure cubic phase. The product is also characterized by the techniques of transmission electron microscopy (TEM) and selected area electron diffraction (SAED).
Keywords: Microwave synthesis; Dendritic crystals; α-AgBiS2; X-ray diffraction;

Treatment of [Os3(CO)11(MeCN)] with 1 equivalent of 9-anthraldehyde oxime in refluxing chloroform afforded a new triosmium cluster [Os3(CO)11(C14H9CN)] 1 in moderate yield. Dehydration of oxime and the formation of metal-bound nitrile were observed. Crystal structure analysis revealed that cluster 1 consists of a triangular metal skeleton, with the anthracenecarbonitrile ligand terminally bonded to an osmium atom. Molecular orbital calculations were carried out to gain further insight into the electronic structure of 1. Cluster 1 was also obtained in a higher yield by the reaction of [Os3(CO)11(MeCN)] with 9-anthracenecarbonitrile.
Keywords: Triosmium carbonyl cluster; Oxime ligand; 9-Anthraldehyde oxime; X-ray crystallography;

Tetrakis(trimethylsilyl)cyclodisilthiane and -selenane by U. Herzog; H. Borrmann (718-720).
Reactions of 2,2-dichlorohexamethyltrisilane (1) with lithium sulfide or selenide furnishes (Me3Si)2Si(E)2Si(SiMe3)2 (E=S (2), Se (3)). Both compounds were characterized by multinuclear NMR spectroscopy ( 1 H , 13 C , 29 Si , 77 Se ). The molecular structure of 2 is reported. 2 crystallizes in monoclinic space group P21/n (Z=2). The four membered ring Si2S2 is planar with an angle Si–S–Si of 83.32° resulting in a transannular Si–Si distance of 2.886 Å.

Synthesis, molecular, crystal and electronic structure of [RuCl2(PPh3)2(C3N2H4)2] by J.G. Małecki; J.O. Dziȩgielewski; R. Kruszynski; T.J. Bartczak (721-724).
The reaction of [RuCl2(PPh3)3] complex with pyrazole has been examined. A new ruthenium complex – [RuCl2(PPh3)2(C3N2H4)2] has been obtained and characterised by IR and UV–Vis measurements. Crystal and molecular structure of the complex has been determined.
Keywords: Ruthenium; Pyrazole; X-ray structure; Tertiary phosphine complexes;

A novel complex [Cu(CH3COO)(bpe)(H2O)] n ·n/2[Cu2(nta)2(bpe)] ·6nH2O) (bpe=trans-1,2-bis(4-pyridyl)ethylene) was synthesized and characterized. The molecule structure shows that it is composed of the ladder-like double chain cations [Cu(CH3COO)(bpe)(H2O)] n n+ and the dimeric anions [Cu2(nta)2(bpe)]2−. Through bridging oxygen atom of the acetate, the Cu2 (μ-O)2 core is formed. The ladder-like chain cation is the narrowest ladder [3.422(3) Å]. Two-dimensional undulating network is constructed by the cations and the dimeric anions through hydrogen-bonding interactions.
Keywords: Ladder; Crystal structure; Two-dimensional network; Hydrogen-bonding;

A new organic–inorganic hybrid compound {[Co(H2O)2][Co2(phen)2(btc)2]} n 1 has been hydrothermally synthesized and characterized by elemental analyses, IR spectrum, TG analysis and single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1 ̄ , a=7.7709(16) Å, b=10.572(2) Å, c=12.178(2) Å, α=88.49(3)°, β=77.97(3)°, γ=69.84(3)°, V=917.5(3) Å3, Z=1, R1=0.0571. The compound 1 exhibits a novel two-dimensional network with unusual (4,6)-lattice-type network constructed by [Co2(phen)2(btc)2]2− dimers and the [Co(H2O)2]2+ fragments.
Keywords: Coordination polymer; Metal-organic network; Hydrothermal synthesis; Crystal structure;

The hexanuclear osmium–rhodium carbonyl carbide cluster [Os 5 Rh(μ 5 -C)(μ 3 -CO)(CO)13 Cp ] 3 has been synthesized in 66% yield by the ionic coupling reaction of [N(PPh3)2]2[Os5C(CO)14] 1 with [Rh 2(Cp )2][BF 4]2 2. An X-ray analysis on 3 showed a square based pyramidal metal skeleton with a μ3-CO bridging a RhOs2 triangular face.
Keywords: Osmium; Rhodium; Carbide; X-ray crystallography;

Microwave-assisted synthesis of tube-like HgS nanoparticles in aqueous solution under ambient condition by Mingwang Shao; Lingfen Kong; Qing Li; Weichao Yu; Yitai Qian (737-739).
Tube-like HgS nanoparticles with face center cubic structure were synthesized via employing TM01-type microwave irradiation as template. In this process, HgCl2 and Na2S were used as mercury and sulfur sources, respectively, which changed to HgS through chemical reaction in aqueous solution and under ambient condition. The products were investigated with X-ray diffraction and transmission electron microscope.
Keywords: Nanomaterials; HgS; Microwave;

A coordination polymer [Cu(phen)(H2O)2(SO4)] n (1) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, thermogravimetric analysis, and single crystal X-ray diffraction. This compound displays a novel double chains structure, in which each one-dimensional chain is constituted by the distorted octahedral complex of copper(II) bridged through bidentate sulfate ligands. Magnetic susceptibility measurement of 1 has been performed down to 2 K. Although paramagnetic behavior is dominantly manifested, compound 1 shows a weak antiferromagnetic interaction on cooling from room temperature to 2 K.
Keywords: Hydrothermal syntheses; Copper(II); Coordination polymer; One-dimensional chain; Magnetic properties;

A simple method for the preparation of octanuclear tin (IV) oxosulfide cluster and the conversion of it to decanuclear cluster by Jian-Jun Zhang; Sheng-Min Hu; Xin-Tao Wu; Wen-Xin Du; Rui-Biao Fu; Long-Sheng Wang (744-747).
An octanuclear tin (IV) complex [(n-C4H9)4N]4 [Sn84-O)22-OH)2S12Cl6] 1 was synthesized simply by the reaction of Na2S·7H2O and SnCl4·5H2O in DMF. The yield is high and this may provide a new strategy for the preparation of other octanuclear tin (IV) oxosulfide cluster. When 1 was heated under hydrothermal conditions, a decanuclear cluster [(n-C4H9)4N]4 [Sn104-O)43-S)42-S)12Cl4]·(4,4-bipy) 2 may be obtained. The two clusters were all characterized by X-ray structure analysis.
Keywords: Octanuclear; Decanuclear; Tin (IV) oxosulfide cluster; Crystal structure;

Trimethoprim cations forming self complementary hydrogen-bonded DADA arrays interact with the copper–phthalate supramolecular frameworks through extensive hydrogen bonding.
Keywords: Copper(II) complex; Crystal structure; Extensive hydrogenbond;

Palladium mediated activation of a C–F bond in pentafluoropyridine: synthesis, structure and reactivity of a pyridyloxy complex by Thomas Braun; Sascha Rothfeld; Verena Schorlemer; Anja Stammler; Hans-Georg Stammler (752-755).
[PdMe2(tmeda)] (1) reacts with pentafluoropyridine in the presence of water and triethylamine to give the aryloxy compound [PdMe(OC5NF4)(tmeda)] (2). The structure of 2 has been determined by X-ray crystallography. The palladium oxygen distance to the aryloxy ligand is 2.0368(14) Å. Treatment of 2 with Me3SiCl effects the cleavage of the palladium oxygen bond and the silane 4-C5NF4(OSiMe3) (3) is formed.
Keywords: Palladium complex; Fluorinated pyridines; Aryloxy silanes;

A novel metal-organic complex of analytical Rh(COD)(2-pymo) formulation (COD=1,5-cyclooctadiene, 2-Hpymo=2-hydroxypyrimidine) has been prepared by reacting [Rh(COD)Cl]2 with 2-Hpymo. While direct syntheses in a variety of solvents (acetone, toluene or methanol) typically afforded amorphous powders, recrystallization from methanol allowed to perform a single crystal data collection on the CH3OH solvate. The crystal structure of the latter [tetragonal, P-42c, a=13.9780(2), c=14.4980(10)  A ̊ , V=2832.7(6)  A ̊ 3 ] contains cyclic [Rh(COD)(2-pymo)]4 tetramers, in which distorted square planar metal atoms are bridged by η 1-μ 2-N,N -exo-bidentate 2-pymo ligands in 1,3-alternate disposition. Upon dissolving both the amorphous and the crystalline (solvated) species in CD2Cl2, variable temperature NMR spectra confirmed the presence of identical (tetrameric) species, thus excluding the existence of other oligomers of different nuclearity in the amorphous powders.
Keywords: 2-Pyrimidinolate; Rhodium; Tetramer;

Ferrocene-based ligands in ruthenium alkylidene chemistry by Ian R Butler; Simon J Coles; Michael B Hursthouse; Dilwyn J Roberts; Naho Fujimoto (760-762).

Synthesis of novel copper (II) benzoate pyrazine and its phase transition induced by CO2 adsorption by Satoshi Takamizawa; Ei-ichi Nakata; Haruhiko Yokoyama (763-765).
A novel crystalline solid, [Cu(II)2(O2CPh)4(pyz)] n , was synthesized and characterized by single-crystal X-ray diffraction analysis; the compound demonstrates thermal phase transition that is correlated with CO2 adsorption.
Keywords: Phase transition; CO2 adsorption; DSC measurement; Dinuclear Cu complex; One-dimensional polymer;

Synthesis and spectroscopic RNA binding studies of [Ru(phen)2MHPIP]2+ by Hong Xu; Hong Deng; Qian-Ling Zhang; Yi Huang; Jian-Zhong Liu; Liang-Nian Ji (766-768).
A new ruthenium(II) polypyridyl complex, [Ru(phen)2MHPIP]2+ (phen = 1,10-phenanthroline, MHPIP=2-(3-methoxy-4-hydroxyphenyl)imidazo[4,5-f]1,10-phenanthroline), has been synthesized and characterized. The binding of this complex with yeast tRNA has been investigated by UV, fluorescence and CD spectroscopy systematically. The experimental results suggest that the complex can bind to yeast tRNA enantioselectively, and that spectroscopic method is effective on studying the interaction of metal complexes with RNA.
Keywords: Ruthenium(II) complexes; RNA; Interaction; Enantioselectivity;

A unique polymeric coordination system that exhibits supramolecular isomerism within two dimensions by Ishtvan Boldog; Joachim Sieler; Konstantin V. Domasevitch (769-772).
Cadmium nitrate and bitopic conformationally flexible linker 3,3,5,5-tetramethyl-4,4-bipyrazole readily form two-dimensional layer polymers [Cd(Me4bpz)2(NO3)2]. Depending on conditions for crystallization the complex could afford two different net topologies that are based on combinations of metal-ligand quadrangles (44 net) and triangles/hexagons (3262 net) and provides a first example for supramolecular isomerism of flat 2D coordination polymers.
Keywords: Coordination polymers; Supramolecular isomerism; Coordination networks; Pyrazole ligands; Bitopic tectons;

Enantiopreferential DNA-binding of a novel dinuclear complex [(bpy)2Ru(bdptb)Ru(bpy)2]4+ by Cai-Wu Jiang; Hui Chao; Xian-Lan Hong; Hong Li; Wen-Jie Mei; Liang-Nian Ji (773-775).
A novel dinuclear ruthenium(II) complex [(bpy)2Ru(bdptb)Ru(bpy)2]4+ (bpy=2,2-bipyridyl; bdptb=2,2-bis(5,6-diphenyl-1,2,4-triazin-3-yl)-4,4-bipyridine) has been synthesized and characterized. The DNA-binding behaviors of this complex have been studied by viscosity, absorption and circular dichroism (CD) spectra. It has firstly been found that the dinuclear ruthenium(II) complex display the enantiopreferential DNA-binding after equilibrium dialysis.
Keywords: Ruthenium complexes; Polypyridine ligands; DNA; Enantiopreference;

Hydrothermal synthesis and structural characterization of an organically-templated zincophosphite: [C4N2H12]0.5·[Zn3(HPO3)4]·H3O by Wenjun Dong; Guanghua Li; Zhan Shi; Wensheng Fu; Dong Zhang; Xiaobo Chen; Zhimin Dai; Lei Wang; Shouhua Feng (776-780).
A new three-dimensional organically templated [C4N2H12]0.5·[Zn3(HPO3)4]·H3O was hydrothermally synthesized and characterized by single crystal X-ray diffraction. The three-dimensional framework is built up from two-dimensional layers with 4.8-membered rings and one-dimensional chains of 4-membered rings. The structure has strictly alternating ZnO4 tetrahedra and HPO3 pseudo pyramids which are linked through their vertices giving rise to the three-dimensional architecture with 8,12-membered ring channels. The protonated water molecules and diprotonated piperazine are located in the 8-membered and 12-membered channels, respectively. The compound crystallizes in monoclinic system, space group P21/n with cell parameters, a=9.6739(16)  A ̊ , b=8.4528(13)  A ̊ , c=20.257(4)  A ̊ , β=97.966(5)°, Z=4, R=0.023, and R w=0.060. It was characterized by the powder X-ray diffraction, differential thermal-thermogravimetric analyses, IR spectroscopy and proton-decoupled 31P MAS NMR solid-state spectroscopy.
Keywords: Hydrothermal synthesis; Organically templated; Zincophosphite; Crystal structure;

Synthesis of bismuth with various morphologies by electrodeposition by Shan Jiang; Yun-Hui Huang; Feng Luo; Nan Du; Chun-Hua Yan (781-785).
Metal bismuth with various morphologies, with particle size from nanometer to micrometer, has been successfully prepared by electrodeposition onto Pt, Au, Al and ITO electrodes at room temperature. The size and morphology of the deposits are strongly dependent on preparation conditions, such as deposition potential, current density, electrode and electrolyte. As observed by scanning and transmission electron microscopes, the deposited Bi particles exhibit plentiful appearances, such as prickly rod, banch, skeleton and strip-like shapes. A significant positive magnetoresistence effect is observed even at room temperature.
Keywords: Bismuth particles; Electrodeposition; Morphologies; Magnetoresistance;

The [ReOCl3(dppe)] complex reacts with acetonitrile in the presence of excess of triphenylphosphine to give a new monomeric nitrile rhenium(III) complex – [ReCl3(MeCN)(dppe)] (1). This paper presents spectroscopic characterization, magnetochemical measurements, crystal and molecular structure for 1.
Keywords: Rhenium; Acetonitrile; Nitrile complexes; X-ray structure;

Two novel Zn(II) helical chain polymers containing both bridging and terminal carboxylato groups by Chirantan Roy Choudhury; Amitabha Datta; Volker Gramlich; G.M. Golzar Hossain; K.M. Abdul Malik; Samiran Mitra (790-793).
Two novel carboxylato-bridged Zn(II) polymeric complexes [Zn(L)(CCl3COO)] n and [Zn(L)(CF3COO)] n , where [L=2-N-(2-pyridylimine)benzoic acid] have been synthesized and structurally characterized. The structures of the two complexes are similar with the Zn(L)(Cl3CCO2) or Zn(L)(F3CCO2) units being repeated to form infinite helical chains. In each structure, the neighbouring Zn atoms are bridged sequentially by syn–anti carboxylate groups of the Schiff base.
Keywords: Zinc; Carboxylate; Crystal structure; Helical chain; Schiff base;