Inorganic Chemistry Communications (v.7, #2)

Contents list (iii-vi).

On reaction with Ni(OAc)2 and NaX the asymmetric compartmental ligand HL 2 forms a heteropentanuclear nickel(II)–sodium(I) complex in which the core is assembled from two dinuclear [Ni2 L 2 ] units which are each linked to a Na atom by bridging μ3-acetato-groups. If KX or NH4X is used then a homotrinuclear nickel(II) complex is isolated. The crystal structures of [NaNi4(L 2 )2(OAc)6(MeOH)2][ClO4], 1, and [Ni3(L 2 )2(OAc)2(MeOH)(H2O)][BF4]2, 3, are reported [HL 2 is the proligand 2-propyliminomethyl-4-methyl-6-{[methyl-bis(2-pyridin-2-yl-ethyl)-amino]-methyl}-phenol].
Keywords: Crystal structure; Heteropentanuclear nickel(II)–sodium(I) complex; Trinuclear nickel(II) complexes;

Treatment of Pd(d-t-bpy)Cl2 (d-t-bpy=4,4-di-tert-butyl-2,2-bipyridine) with sodium 2-amino-5-mercapto-1,3,4-thiadiazolate (NaSSNH2) or sodium 6-amino-2-mercaptobenzothiazolate (NaSSCNH2) affords two interesting hydrogen-bonded polymers: [Pd(d-t-bpy)(SSNH2)2] (1) and [Pd2(SSCNH2)4] (2). 1 forms a pseudo 3-D zeolite-like framework. Surprisingly, the lantern-typed 2  · 4DMF has been serendipitously isolated in the same reaction condition, and it displays a rare 2-D hydrogen-bonded network composed of a dimetal unit propagated in the crystal lattice.
Keywords: Crystal engineering; Zeolite-like; Supramolecular; Self-assembly; Aurophilic;

Synthesis and crystal structure of decamethyltitanocene hydroxide by Michal Horáček; Róbert Gyepes; Jiřı́ Kubišta; Karel Mach (155-159).
Fully methylated titanocene hydroxide [Ti(OH) (η5-C5Me5)2] (1) was obtained by the reaction of single tucked-in decamethyltitanocene [Ti(η5-C5Me5){η51-C5Me4(CH2)}] (2) with one equivalent of water dissolved in toluene. The X-ray single crystal diffraction of 1 revealed the bent Ti–O–H bonds (112(4)°) where the oxygen atom is only 0.038(4) Å away from the Cg(1), Ti, Cg(2) (Cg – centroid of the cyclopentadienyl ring) plane, and the hydroxyl bond is directed to the cyclopentadienyl ring C(1–5). The Ti–O bond length (1.889(2) Å) and energy of 1a1→b2 transition (6770(50) cm−1) indicate that the π-donation effect of the hydroxyl group is weaker compared to alkoxy groups.
Keywords: Titanium; Titanocene; Pentamethylcyclopentadienyl; Hydroxide; Crystal structure; Electron spin resonance; Electronic absorption spectra;

Nitrosyl ruthenium complex as nitric oxide delivery agent: synthesis, characterization and photochemical properties by Fabiana de Souza Oliveira; Vanessa Togniolo; Thais T Pupo; Antonio Claudio Tedesco; Roberto Santana da Silva (160-164).
In the present study, we report the synthesis, physical chemistry and photochemical properties of trans-[RuCl([15]aneN4)NO]2+ in physiological solution. The nitrosyl ruthenium species undergoes one-electron reduction in aqueous solution producing trans-[RuCl([15]aneN4)H2O]+ and nitric oxide (NO). The NO was also obtained with a laser flash-photolysis at 355 nm of trans-[RuCl([15]aneN4)NO]2+ in aqueous solution. The quantum yield for NO release was determined as 0.61 ± 0.05 mol einstein−1.
Keywords: Ruthenium macrocyclic complex; Nitrosyl complexes; Nitric oxide;

Dehydration kinetic studies of HCO3 catalyzed by three half-sandwich nickel(II) complexes in the presence of inhibitors NO2 , N3 and NCS by Ying-Ji Sun; Lei Z. Zhang; Peng Cheng; Hua-Kuan Lin; Shi-Ping Yan; Dai-Zheng Liao; Zong-Hui Jiang; Pan-Wen Shen (165-168).
This communication reports the dehydration kinetic measurements of HCO3 catalyzed by three inhibitor-containing half-sandwich nickel(II) complexes [TpMe]NiX ([TpMe]=hydrotris(3,5-dimethylpyrazolyl)borate; X2-NO2 (1), N3 (2), NCS (3)) by employing the stopped-flow techniques at pH <7.9. The five- or six-coordinated aqua complexes must be the reactive catalytic species in the catalyzed bicarbonate dehydration reaction and the rate-determining step is the substitution of the labile water molecule by HCO3 . The dehydration rate constants k of the rate-determining step decrease in the order: 1 (186 M−1 s−1) > 2 (169 M−1 s−1) > 3 (120 M−1 s−1), which is correlated with an increase of the activation energy barrier heights, this being the origin of the variation in the inhibition abilities among the different inorganic anions.
Keywords: Catalysis; Dehydration kinetics; Stopped-flow techniques; Nickel; Inhibitor;

Diammonium dibarium hydrogen citrato peroxotitanate(IV), Ba2(NH4)2[Ti4(O2)4(Hcit)2(cit)2] · 10H2O, is obtained directly from H2O2 oxidation of tricitrato titanate, or from the reaction of peroxotitanate with citric acid (H4cit=citric acid), which is decomposed stoichiometrically into BaTi2O5 at the temperature of 800 °C in air.
Keywords: Barium titanate; Citrate; Precursor; Pechini process; Crystal structure;

Novel two-dimensional copper(II) complexes containing tetrachloro-phthalate dianion, dicyanamide or pyrazole by Mao Liang; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan; Peng Cheng (173-175).
Two novel two-dimensional copper(II) complexes, [Cu(tcph)dca] · Hpip (1) (H2tcph=tetrachloro-phthalic acid, dca=dicyanamide anion, pip=piperidine) and [Cu(tcph)(pz)2] (2) (pz=pyrazole), have been synthesized and characterized structurally. The spectroscopic properties have also been discussed.
Keywords: Coordination polymers; Tetrachloro-phthalic acid; Two-dimensional;

Preparation and characterization of ZnO nanofibers by using electrospun PVA/zinc acetate composite fiber as precursor by Xinghua Yang; Changlu Shao; Hongyu Guan; Xiliang Li; Jian Gong (176-178).
Thin PVA/zinc acetate composite fibers were prepared by using sol–gel processing and electrospinning technique. After calcinations of the above precursor fibers, ZnO nanofibers with a diameter of 50–100 nm could be successfully obtained. The fibers were characterized by TG-DTA, SEM, FT-IR, XRD, respectively.

Synthesis of α-tellurium dioxide nanorods from elemental tellurium by laser ablation by Zhi-Yuan Jiang; Zhao-Xiong Xie; Xian-Hua Zhang; Su-Yuan Xie; Rong-Bin Huang; Lan-Sun Zheng (179-181).
Elemental tellurium was evaporated by laser ablation, the vapor of which was condensed and deposited on the surface of the heated glass surface and then formed α-tellurium dioxide nanorods with uniformly size distribution by oxidation in the chamber with hot air atmosphere. TEM images and Electron diffraction (ED) pattern confirm the crystallinity of α-phase tellurium dioxide. The formation process of the nanorods involves a vapor–liquid–solid (VLS) following a chemical oxidation in the hot air atmosphere, in which the low melting point tellurium serves as a liquid-forming reagent.
Keywords: Nanorod; Tellurium dioxide; Laser ablation;

The first polyoxometalate polymer constructed by assembly of the heptamolybdic anion and copper coordination groups by Zhangang Han; Huiyuan Ma; Jun Peng; Yanhui Chen; Enbo Wang; Ninghai Hu (182-185).
The first example of one-dimensional organic–inorganic polymetallic coordination polymer based on heptamolybdate anions, formulated (NH4)[Cu(en)2][Na(en)Cu(en)2(H2O)(Mo7O24)] · 4H2O (en = ethylenediamine) (1) has been hydrothermally synthesized and characterized by element analysis, IR, EPR, CV and single crystal X-ray diffraction. The structure of 1 is fabricated by self-assembly of integrated heptamolybdic anions without collapse of primary structure and copper-ethylenediamine(en) coordination groups into one-dimensional zigzag-shaped chains.
Keywords: Polyoxometalate; Secondary metal-ligand; Heptamolybdic anions; Assembly;

The reaction of 2-nitro-1,4-benzenedicarboxylic acid with Cu(NO3)2 gives rise to a long-waited 3D layered architecture consisting of five-coordinate copper(II) atoms.
Keywords: Layered sheet; Crystal structure; Hydroxide complex; Copper complex; Three-dimensional network;

Synthesis of nanocrystalline Ni2B via a solvo-thermal route by Xin Feng; Yu-Jun Bai; Bo Lü; Yong-Rui Zhao; Jie Yang; Jie-Ru Chi (189-191).
Nickel boride (Ni2B) nanocrystals were successfully synthesized via the reaction of NiCl2 and NaBH4 at 420 °C with benzene as solvent. The yield is about 60%. The crystals were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectra (XPS). Highly crystallized Ni2B with an average size of 20 nm was obtained.
Keywords: Nickel boride; Solvo-thermal route; X-ray powder diffraction; Transmission electron microscopy; X-ray photoelectron spectra;

A convenient solid-state reaction route to nanocrystalline TiB2 by Liang Shi; Yunle Gu; Luyang Chen; Zeheng Yang; Jianhua Ma; Yitai Qian (192-194).
Nanocrystalline titanium diboride (TiB2) powders were successfully synthesized at 650 °C by using TiCl4, Mg and MgB2 as the reactants. Transmission electron microscopy images show that typical TiB2 crystallites are composed of uniform particles with the average grain size of about 40 nm.
Keywords: Chemical synthesis; X-ray powder diffraction; Titanium diboride; Nanocrystals;

The reaction of 1,4,8,11-tetrakis(3-hydroxy-6-methyl-2-pyridylmethyl)-1,4,8,11- tetraazacyclotetradecane with nickel and cobalt nitrate in methanol at 1:1 molar ratio afforded two new crystals. Both of them are isotructural analogues. Nickel complex crystallized in triclinic space group P-1 with a=10.050(3), b=12.599(4), c=18.267(6) Å, α=109.595(3)°, β=103.829(7)°, γ=93.376(6)°, V=2091.2(12) Å 3, and Z=2. The Ni(II) ions are five-coordinated by four nitrogen atoms and one phenolic oxygen atom. Their coordination geometry can be described as square pyramid, with short Ni–O distance.(1.984(3) A ̊ ) Cobalt complex crystallized in triclinic space group P-1 with a=9.9479(9), b=12.4441(11), c=18.2620(16) Å, α=108.0730(10)°, β=104.5780(10)°, γ=93.2030(10)°, V=2057.8(3) Å3, and Z=4. The Co(II) ions are also five-coordinated by similar atoms as found in copper complex.
Keywords: Macrocyclic ligand; Phenol group; Crystal structure; Nickel; Cobalt;

The preparation and complexation of 5,10-bis(diphenylphosphino)phenazine by Mireia Rodriguez i Zubiri; Heather L. Milton; David J. Cole-Hamilton; Alexandra M.Z. Slawin; J.Derek Woollins (201-203).
The new phosphine based on phenazine forms a stable platinum complex with a severely distorted (non-planar) C12N2 backbone.
Keywords: X-ray crystallography; Synthesis; Structure;

Conformational isomers of cis-chloro(nitrosyl)(1,4,7,10-tetraazacyclododecene)ruthenium(II), cis-[RuIICl(imcyclen)(NO+)]2+. Oxidation of the coordinated 1,4,7,10-tetraazacyclododecane (cyclen) ligand by Kleber Queiroz Ferreira; Flavia Gouveia Santos; Zênis Novais da Rocha; Thais Guaratini; Roberto Santana da Silva; Elia Tfouni (204-208).
The reaction of cis-dichloro(1,4,7,10-tetraazacyclododecane)ruthenium(III), cis-[RuIIICl2(cyclen)]+, in acidic aqueous solution, in the presence of nitric oxide, results in cis-[RuIICl(imcyclen)(NO+)]2+. The cis nitrosyl complex is precipitated as a mixture of two conformational isomers, which are separated by high performance liquid chromatography. Electrochemical, infrared spectroeletrochemistry, and infrared, UV–Vis, 1H NMR, and EPR spectra results indicate the presence of coordinated nitric oxide in the form of nitrosonium (NO+), and that the macrocyclic ligand (cyclen) is in the oxidized form in the complexes.
Keywords: Nitrosyl ruthenium cyclen conformational isomers; Nitric oxide; Nitrosyl ruthenium imcyclen conformational isomers;

The most hindered hydrotris(pyrazolyl)borate ligand, X-ray structure of chlorocopper(II) complex: [Cu(Cl){HB(3-Ad-5-Pr i pz)3}] as compared with [Cu(Cl){HB(3-Bu t -5-Pr i pz)3}] by Kiyoshi Fujisawa; Naoki Tada; Yoko Ishikawa; Hideyuki Higashimura; Yoshitaro Miyashita; Ken-ichi Okamoto (209-212).
Admantyl substituted hydrotris(pyrazolyl)borate ligand, which is the most hindered in all the hydrotris(pyrazolyl)borate ligands, is newly synthesized. Two chlorocopper(II) complexes with [HB(3-Ad-5-Pr i pz)3] and [HB(3-Bu t -5-Pr i pz)3] were characterized by X-ray diffraction and some spectroscopic techniques.
Keywords: Copper(II); Hydrotris(pyrazolyl)borate; Mononuclear complex; Crystal structure;

Violet emission of Ce doped sol–gel Al2O3–SiO2 glasses without any deoxidizing heat-treatment by Chun Feng Song; Meng Kai Lü; Shu Feng Wang; Dong Xu; Duo Rong Yuan (213-215).
Ce doped sol–gel SiO2, Al2O3–SiO2 glasses have been fabricated by heat-treatment in air atmosphere and their photoluminescence properties have been studied. A characteristic violet emission from Ce3+ is observed in Ce doped sol–gel Al2O3–SiO2 glasses. The results show that characteristic Ce3+ emission can be obtained by incorporating Al3+ into sol–gel SiO2 glasses without any deoxidizing heat-treatment.
Keywords: Photoluminescence; Sol–gel; Glasses; Heat-treatment; Doped;

A novel cerium–adipate coordination polymer [Ce2(ad)3(H2O)2] n (1) has been hydrothermally synthesized and structurally characterized, which possesses three-dimensional network structure constructed from infinite chains of edge-sharing CeO8(H2O) polyhedron and long carbon chains. Each cerium cation binds to nine oxygen atoms belonging to six adipates and one water molecule, the adjacent cerium atoms are linked together through chelating-bridging and bidentate bridging carboxylates to form infinite polyhedron chains along [1 0 0] direction. The starlike distribution of six μ4-adipates around the central cerium generates a complicated network, which is thermally stable without any collapse even though no any guest molecules reside in the large channels.
Keywords: Cerium; Adipate; Hydrothermal synthesis; Crystal structure; Polyhedron chain;

N,N -bis(α-picolinoyl)hydrazine H2L is a potentially bis-tridentate conjugated ligand in its doubly deprotonated form L2−. The digold(III) complex (μ-L)[AuCl2]2 was obtained from KAuCl4 either by using H2L/NaOH or through a ring-opening/hydrolysis reaction of 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine (bptz), as similarly observed recently with CuII. The crystal structure of (μ-L)[AuCl2]2 exhibits bis(N,N )-coordination; two perpendicular molecular halves with uncoordinated carbonyl functions are present which explains the relatively short Au–Au distance of 3.974 Å.
Keywords: Crystal structure; Dinuclear Complex; Gold compound; Hydrazido ligand; Tetrazine ring;

New porous crystals of Cu(I) complexes with Schiff-base-containing triazole ligands by Krzysztof Drabent; Agata Białońska; Zbigniew Ciunik (224-227).
The new route of syntheses, crystal structure and properties of two new copper(I) complexes, (CuL 1 2)2(BF4)2  · 0.5THF (1) and (CuL 2 2)2(BF4)2 (2) where L 1 =N-[(E)-(4-chlorophenyl)methylidene]-4H-1,2,4-triazol-4-amine and L 2 =N-[(E)-(3,5-dimethoxyphenyl)methylidene]-4H-1,2,4-triazol-4-amine are described. The planar dimeric molecules of 1 and 2 have a great ability toward building the porous structures of the crystals. The size of formed channels depends on the type of substituents on phenyl group of ligands.
Keywords: Metal complexes; Nitrogen heterocycles; Schiff bases; N ligands; Copper;

Structures and properties of two novel one-dimensional complexes bridged by 4,4-methylenebis(3,5-dimethylpyrazole) by Wei Han; Ling Li; Wen Gu; Zhan-Quan Liu; Shi-Ping Yan; Dai-Zheng Liao; Zong-Hui Jiang; Pan-Wen Shen (228-231).
Two novel one-dimensional Co(II) and Zn(II) complexes {[Co(H2mbdpz)2](ClO4)2} n (1) and {[Zn(H2mbdpz)(NCS)2](DMF)2} n (2) (H2mbdpz=4,4-methylenebis(3,5-dimethylpyrazole)) have been synthesized and structurally characterized. In complex 1, the strict alternation of the double-bridging [Co(H2mbdpz)2]2+ ring units formed an infinite chain with the neighboring ring planes being close to 90°; the replacement of H2mbdpz with thiocyanate ions leading to a single-bridging zigzag chain, was found in complex 2. The magnetic susceptibility indicated that complex 1 was almost no magnetic interactions between the cobalt(II) ions and the corresponding J value was −0.08 cm−1 and g=2.27.
Keywords: Cobalt; Zinc; Crystal structure; One-dimension; Magnetic property;

An asymmetric trihydrido-bridged arene ruthenium complex by Ludovic Vieille-Petit; Bruno Therrien; Georg Süss-Fink (232-234).
Reaction of [Ru(η6-indane)(H2O)3]2+ and [Ru(η6-C6Me6)(H2O)3]2+ with NaBH4 in water gives a mixture of three triple hydrido-bridged arene ruthenium cations [(η6-arene)Ru(μ-H)3Ru(η6-arene)]+ (arene=indane and hexamethylbenzene; arene=indane and hexamethylbenzene). After treatment with NaBF4, the three complexes are separated by column chromatography and the asymmetrical [(η6-indane)Ru(μ-H)3Ru(η6-C6Me6)][BF4] (cation 1a) can be isolated in moderate yield. 1a decomposes in solution to give the corresponding hydroxo-bridged complex [(η6-indane)Ru(μ-OH)3Ru(η6-C6Me6)]+ (2) with retention of the asymmetrical geometry as shown by single-crystal X-ray structure analysis. The indane ligand adopts an envelope conformation toward the ruthenium atom.
Keywords: Arene ligands; Bridging ligands; Dinuclear complexes; Hydrido; Hydroxo; Ruthenium;

A 4-acyl-5-pyrazolone ligand (HQ) in N-unidentate coordination mode in a Rh(CO)2Cl(HQ)-type complex by Augusto Cingolani; Fabio Marchetti; Claudio Pettinari; Riccardo Pettinari; Brian W. Skelton; Allan H. White (235-237).
A new rhodium(I) dicarbonyl compound containing a neutral 4-acylpyrazolone bonded in N-unidentate fashion has been synthesized and structurally characterized.
Keywords: Rhodium; β-Diketonate; X-ray; Carbonyl complexes; Tautomerism;

The first polymeric Cu(I) dppe complexes have been synthesized and their structures in solution and solid state have been studied.
Keywords: Cu(I) dppe polymer; Cu(I) nitrate complex; Solvent dependant product; Copper(I); Phosphine complex;

Complex compounds of platinum(IV) and O,O-dialkyl-ethylenediamine-N,N -di-3-propanoate ligands. A structural evidence for geometry of hydrolytic product of some esters by Tibor J Sabo; Goran N Kaluđerović; Sanja R Grgurić-Šipka; Frank W Heinemann; Srecko R Trifunović (241-244).
Depending on the ester alkyl group, the reaction of O,O-dialkylethylenediamine-N,N -di-3-propanoate ligands (R2eddp) with potassium hexachloroplatinate(IV) afforded trans-dichloro(ethylenediamine-N,N -di-3-propanoato)platinum(IV) and tetrachloro(O,O-dialkyl-ethylenediamine-N,N -di-3-propanoato)platinum(IV) complexes. The complexes were characterized by elemental analysis, electronic absorption, infrared, 1H and 13C NMR spectroscopy. The trans configuration of [Pt(eddp)Cl2] complex was confirmed by X-ray crystallography.
Keywords: Platinum(IV); Tetradentate ligands; Bidentate ligands; Eddp;

A half cleaved zirconacyclopentadiene by Matthias Zeller (245-248).
When the sterically strained bicyclic zirconacyclopentadiene 2 is reacted with two equivalents of iodine in the presence of copper(I) chloride, the diiodinated product 4 forms in the range of 10 h. However, when reacted only for 2 h, the monoiodinated zirconium complex 3 is isolated. 3 shows an unexpected stability towards hydrolysis and oxidation. The molecular structure of complex 3 has been determined by X-ray structural analysis.
Keywords: Zirconacyclopentadienes; Half Cleavage; Alkenylzirconocenes; Alkenyliodides;

One-pot synthesis and self-assembly of double stranded helical metal complexes by Zhikun Wu; Guoqiang Yang; Qingqi Chen; Jingang Liu; Shiyong Yang; Jin Shi Ma (249-252).
A convenient and highly efficient method to synthesize the bis(pyrrol-2-yl-methyleneamine) zinc(II) complexes has been developed. Their double helical dinuclear structures are confirmed by X-ray analysis.
Keywords: One-pot synthesis; Self-assembly; Supramolecules; Helicates; Schiff base;

Synthesis, physicochemical properties and crystal structure of isothiocianato [2-(diphenylphosphino)benzaldehyde selenosemicarbazonato(1)] nickel(II) by Ilija D. Brčeski; Vukadin M. Leovac; Goran A. Bogdanović; Sofija P. Sovilj; Mihail Revenco (253-256).
The syntheses of a new ligand 2-(diphenylphosphino)benzaldehyde selenosemicarbazone (HL) and the corresponding complex with Ni(II) of the formula [Ni(L)(NCS)] are reported. The complex was characterized by single crystal X-ray analysis. The compound complex is diamagnetic and has a markedly deformed square-planar structure with PNSe set of donor atoms of the ligand, the Schiff base monoanion, and the N atom of the coordinated NCS group. The phosphorus atom deviates even by 0.494(3) Å from the mean plane defined by the other coordination atoms (NSeN) and the metal atom.
Keywords: Nickel(II) complex; 2-(Diphenylphosphino)benzaldehyde selenosemicarbazone; Crystal structure; IR spectra; Deformed coordination geometry;

A rational redox route for the synthesis of tellurium nanotubes by Xin-yuan Liu; Mao-song Mo; Xiang-ying Chen; Yi-tai Qian (257-259).
Tellurium nanotubes have been synthesized via a hydrothermal redox route starting from Na2TeO3 and Na2SO3. X-ray diffraction reveals that the product is a pure trigonal phase and transmission electron microscope indicates the widths of the nanotubes are in the range of 100–400 nm.
Keywords: Nanotube; Tellurium; Hydrothermal;

A novel strong fluorescent three-dimensional supramolecular coordination polymer based on bridging terephthalate by Hong-Bin Xu; Zhong-Min Su; Kui-Zhan Shao; Ya-Hui Zhao; Yan Xing; Yu-Cang Liang; Heng-Jun Zhang; Dong-Xia Zhu (260-263).
A novel coordination polymer [Cd(bpy)(tp)(H2O)] n (1) has been prepared through hydrothermal reaction and structurally characterized, and the compound gives strong fluorescent emission. The structure of the compound consists of CdN2O4 octahedron linked through bridging terephthalate (tp) into 1D structure, and then a 3D supramolecular structure is formed adopting herringbone packing in the solid state through π–π stacking and hydrogen bonding interactions.
Keywords: Crystal structure; Strong fluorescence; Hydrogen bonds; π–π stacking; Herringbone network;

The novel polyoxovanadate containing antimony [(C2N2H10)2β-{SbIII 8VIV 14O42(H2O)}](C2N2H8) · 4H2O has been synthesized from a mixture of VOSO4, Sb2O3, en and H2O under hydrothermal conditions. The spherical [β-{SbIII8VIV 14O42(H2O)}]4−clusters form a one-dimensional double-chain structure with non-bonding Sb ⋯ O contacts.The novel polyoxovanadate containing antimony [(C2N2H10)2β-{SbIII8VIV 14O42(H2O)}](C2N2H8) · 4H2O has been synthesized from a mixture of VOSO4, Sb2O3, en and H2O under hydrothermal conditions. The spherical [β-{SbIII8VIV 14O42(H2O)}]4− clusters form a one-dimensional double-chain structure with non-bonding Sb ⋯ O contacts.
Keywords: Polyoxometalate; Antimony; Crystal structure; Hydrothermal synthesis;

Photoluminescence of Pb2+ ions in sol–gel derived Zn2SiO4 by Ping Yang; Meng Kai Lü; Chun Feng Song; Su Wen Liu; Feng Gu; Shu Feng Wang (268-270).
The luminescence of sol–gel derived Zn2SiO4 powder samples doped with Pb2+ ions has been reported. The emission spectra of Pb2+-doped Zn2SiO4 can be adjusted by changing the excitation wavelength. The blue, green, yellow and red emission peaks have all been observed from Pb2+-doped Zn2SiO4 powder samples.
Keywords: Zn2SiO4:Pb; Luminescence;

A tri-layer cadmium(II) benzenetricarboxylate coordination polymer: crystal structure and photoluminescent property by Sheng-Qing Xia; Sheng-Min Hu; Jian-Jun Zhang; Xin-Tao Wu; Jing-Cao Dai; Zhi-Yong Fu; Wen-Xin Du (271-273).
A cadmium benzenetricarboxylate coordination polymer has been synthesized by hydrothermal reaction. It presents an interesting tri-layer structure motif featuring tri-nuclear units and exhibits intense photoluminescence as well.
Keywords: Coordinate polymer; Cadmium; Tri-layer; Octahedron;

Twelve low spin ruthenium(III) Schiff base complexes of the type [RuX(EPh3) (LL)] (where X=Cl or Br; E=P or As; LL=dibasic tetradentate Schiff base) were synthesized and characterized. These complexes catalyze oxidation of primary alcohol with up to 87.9% in the presence of N-methylmorpholine-N-oxide (NMO).
Keywords: Ruthenium(III) Schiff base complexes; Characterization; Redox properties; Catalytic oxidation;

A three-dimensional framework is formed by polymeric aqua (nitrilotriacetato)-lanthanum, [La(C6H6NO6)H2O] n , in which the nitrilotriacetate (NTA) ligand adopts for the first the eight-coordinated mode that has not been previously observed.
Keywords: Lanthanide compound; Nitrilotriacetate (NTA); Coordination mode; Three-dimensional framework;

Salalen: a hybrid Salan/Salen tetradentate [ONNO]-type ligand and its coordination behavior with group IV metals by Adi Yeori; Shimrit Gendler; Stanislav Groysman; Israel Goldberg; Moshe Kol (280-282).
A straightforward synthesis of Salalens, tetradentate [ONNO]-type ligands comprised of an amine-phenolate and an imine-phenolate subunits is introduced. The Salalen ligand precursor reacted with titanium(IV) ethoxide and with tetrakis(dimethylamido)zirconium to yield the corresponding [(Salalen)MX2]-type C1-symmetric complexes in a single isomeric form, indicating that Salalen is a genuine hybrid of its parent Salan and Salen ligands.
Keywords: Salen; Salan; Salalen; Titanium; Zirconium;

Fabrication, structure and magnetic properties of fluoroperovskite KMnF3 nanostructures by Qun Tang; Jianmin Shen; Wenjia Zhou; Jianwei Liu; Zhaoping Liu; Yitai Qian (283-285).
Cubic fluoroperovskite KMnF3 nanostructures including acicular nanocrystals and ultrafine nanoparticles were solvothermally synthesized.
Keywords: Perovskite structure; Nanostructures; Magnetic properties;

Octahedral hexanuclear silver(I) and copper(I) ferrocenylacetylide complexes by Qiao-Hua Wei; Li-Yi Zhang; Lin-Xi Shi; Zhong-Ning Chen (286-288).
Octahedral hexanuclear ferrocenylacetylide complexes [Ag6(μ-dppm)231-CCFc)4(CH3OH)2](BF4)2 (1) and [Cu6(μ-dppm)231-CCFc)4(ClO4)2] (2) (dppm=Ph2PCH2PPh2, Fc=ferrocenyl) are synthesised and characterized structurally.
Keywords: Copper(I); Crystal structure; Ethynylferrocene; Silver(I);

Treatment of the labile precursor complexes cis- or trans-[PtCl(dmf)(NH3)2]OTf (dmf=N,N-dimethylformamide; OTf=trifluoromethanesulfonate) with the monodentate 1-aminoalkyl-1,2-carborane ligands NH2(CH2) n C2B10H11 (n=1,3) afforded the moderately-stable species cis- or trans-[PtCl(NH3)2{NH2(CH2) n C2B10H11}]OTf, respectively. The novel complexes are the first examples of platinum(II)-amine derivatives containing a 1,2-dicarba-closo-dodecaborane(12) (closo-1,2-carborane) ligand.
Keywords: Platinum(II) complex; closo-1,2-Carborane; NMR spectroscopy; Electrospray ionisation mass spectrometry;

Discernible apical coordination in μ3-oxo-bridged mixed metal trinuclear carboxylate [Fe2MnO(CHCl2COO)6(THF)2H2O] by Sergiu Shova; Denis Prodius; Valeriu Mereacre; Yurii A. Simonov; Janusz Lipkowski; Constantin Turta (292-295).
Novel μ3-oxo-bridged heterotrinuclear iron(III)-manganese(II) carboxylate of the composition [Fe2MnO(CHCl2COO)6(THF)2H2O] has been synthesized and characterized by X-ray crystallography, IR and TG. The positional parameters of the various metal ions within trinuclear [Fe2MnO]6+ core were determined unambiguously due to their different coordination environment and hydrogen bonds forming between two H2O molecules coordinated to Mn ions in different clusters.
Keywords: Iron(III) manganese(II) heterocluster; Crystal structure; Hydrogen bonding;

[(TMEDA)Ni(acac)2] was synthesized by the coordination of TMEDA to Ni(acac)2. Its crystal structure shows a slightly distorted octahedral geometry with Ni–N bond lengths of 2.152(2) and 2.1655(17) Å and Ni–O bond distances between 2.0219(14) and 2.0383(16), respectively. Density functional theory calculations (Becke3LYP/6-31G(d)) confirm that the ground state of this octahedral coordinated Ni(II) is a triplet favored by 22.6 kcal/mol over the singlet electron configuration. The thermochemistry of the coordination reaction is exergonic and shows an overall free energy difference of −10.6 kcal/mol. According to our computational results the reaction can be considered a two step process. First TMEDA coordinates to the Ni(acac)2 via one nitrogen atom yielding a five-coordinate intermediate (during this step the electron configuration changes from singlet to the triplet state), followed by the formation of the octahedral complex. Comparisons to related X-ray structures are given.
Keywords: Nickel; β-Diketonates; DFT calculations; Crystal structure; Singlet–triplet gap;

Photoluminescence of Ce3+ in haloapatites Ca5(PO4)3X by Ping Yang; Guang-Qing Yao; Jian-Hua Lin (302-304).
The luminescence properties of Ce3+ ions in calcium halophosphates Ca5(PO4)3X (X=F, Cl) has been studied. The excitation bands of Ca5−2x Ce x Na x (PO4)3Cl are shifted to lower energies comparing with Ca5−2x Ce x Na x (PO4)3F. Codoping with Na+ ions results in a remarkably increase of the luminescence intensity of Ce3+-doped Ca5(PO4)3X apatites due to the charge compensation.
Keywords: Ce3+; Photoluminescence; Haloapatites; Charge compensation;

Synthesis and characterization of β-diketiminate terbium complex by Zhen-Qin Zhang; Qi Shen; Yong Zhang; Ying-Ming Yao; Jun Lin (305-307).
The terbium complex supported by β-diketiminate was synthesized and structurally characterized. Due to an efficient energy transfer from the ligand to the central Tb3+, this complex shows a strong emission corresponding to Tb3+ 5D47F J (J=6,5,4,3) transitions, with 5D47F5 (550 nm) green emission as the most prominent group. The decay behavior of Tb3+ luminescence depends strongly on the excitation wavelengths.
Keywords: β-diketiminate complex; Terbium complex; Crystal structure; Luminescence;

Synthesis of nanostructured spinel LiMnO by hydrothermal method at 70 °C by Zhanqiang Liu; Wen-lou Wang; Xianming Liu; Minchang Wu; Zhen Zeng; Dan Li (308-310).
Nanostructured spherical spinel LiMnO was synthesized at the temperature as low as 70 °C using CTAMnO4 as manganese source under the hydrothermal conditions.
Keywords: Spinel LiMnO; Nanostructure; Hydrothermal synthesis; Low temperature;

A di-μ-phenoxo bridged zinc dimer with unfamiliar spatial arrangement by Jesùs Sanmartı́n Matalobos; Ana M. Garcı́a-Deibe; Matilde Fondo; Débora Navarro; Manuel R. Bermejo (311-314).
A curious dimeric complex, Zn2(H2SB)2  · 3H2O · Me2CO [H4SB: N,N -bis(2,5-dihydroxybencylidene)-1,4-diaminobutane], was synthesised by self-assembly reaction between H2SB2− and Zn2+ ions electrochemically generated. Interestingly, the zinc ions reside in chemically identical N2O3 coordination environments, but adopting two different geometries: trigonal bipyramidal and square based pyramidal. This peculiar molecule is non-centrosymmetric, but owns a pseudo twofold axis normal to the centre of the Zn2O2 metallacycle. This unfamiliar arrangement of the dimer leads to keep both tetra-methylene spacers at the same side of the plane formed by the metallacycle, resulting in a cavity where both zinc ions appear uncovered.
Keywords: Crystal structure; Self-assembly; Zinc dimer; Schiff base;

In the first CuI coordination polymer containing an angular bipyridine-type ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (bpo), {[Cu(bpo)2(CH3CN)]ClO4  · CH3CN · (H2O)1.5} n (1), the bpo molecules exhibit different monodendate and bidendate bridging modes in binding to the CuI center, forming a novel 1-D infinite comb-like polymeric chain with the monodendate ligands on one side. The most striking feature of this structure is the formation of a 3-D porous network with large rectangular channels through two distinct types of inter-chain π–π stacking interactions, which was further stabilized by weak hydrogen-bonding interactions.
Keywords: Crystal structure; Coordination polymer; Copper(I); Aromatic stacking interactions; Supramolecular assembly;