Inorganic Chemistry Communications (v.10, #11)

Contents List (iii-xii).

1,1′-Ferrocene dicarboxylic acid pyridin-4-yl ester reacts with the hydroxo-bridged complex [(η6-p-cymene)2Ru2(μ-OH)3]+ to give the dicationic complex [(η6-p-cymene)2Ru2(μ-OH)2(1,1′- (NC5H4–OOC)2–Fc)]2+, isolated as a tetrafluoroborate salt. The new ferrocenoyl pyridine ligand acts as μ22 chelating ligand in the trinuclear complex.1,1′-Ferrocene dicarboxylic acid pyridin-4-yl ester (1) is prepared from 1,1′-ferrocene dicarbonyl chloride and 4-hydroxypyridine. This new bidentate ferrocenoyl ligand reacts with the monocationic complex [(η6-p-cymene)2Ru2(μ-OH)3]+ to give the dicationic complex [(η6-p-cymene)2Ru2(μ-OH)2(1,1′- (NC5H4–OOC)2–Fc)]2+ (2) (Fc: C5H4–Fe–C5H4), isolated as a tetrafluoroborate salt. The single-crystal X-ray structure analysis of [2][BF4]2 reveals the ferrocenoyl pyridine ligand 1 to act as μ22 chelating ligand in the dinuclear complex, having replaced a μ21-hydroxo ligand.
Keywords: Arene-ruthenium complexes; Hydroxo bridges; Bidentate ligands; Ferrocene; UV spectra;

We prepared three isomeric bipyridyl-type ligands (L n  = (n-py)–CH=N–C6H10–N=CH–(n-py); n  = 2–4) and two cadmium coordination polymers, [ Cd L 1.5 4 ( NO 3 ) 2 ] · ( CH 2 Cl 2 ) (1) and [ Cd L 1.5 3 ( NO 3 ) 2 ] (2). The 2-D α-arsenic-type polymer 1 has a 102-membered cyclohexane-like ring unit, and the 1-D stair-like polymer 2 has a 60-membered ring unit.We prepared three isomeric bipyridyl-type ligands (L n  = (n-py)–CH=N–C6H10–N=CH–(n-py); n  = 2–4). Two cadmium coordination polymers, [ Cd L 1.5 4 ( NO 3 ) 2 ] · ( CH 2 Cl 2 ) (1) and [ Cd L 1.5 3 ( NO 3 ) 2 ] (2), were prepared from cadmium nitrate and ligands L 4 and L 3, respectively. The N⋯N separations between the two terminal pyridyl groups in the free ligands L 4, L 3, and L 2 are 15.798(6), 15.036(4), and 12.417(5) Å, respectively. The 2-D α-arsenic-type polymer 1, which contains CH2Cl2 guest molecules, has two distinct N⋯N separations of 15.706(10) Å and 14.479(9) Å and a large 102-membered cyclohexane-like ring unit. The 1-D stair-like polymer 2 has also two distinct N⋯N separations and a 60-membered ring unit. The various lengths of the observed N⋯N separations are due to the ring flip of the intervening cyclohexyl fragment in the ligands.
Keywords: Bipyridyl-type linking ligands; 2-D α-arsenic; 1-D stair; Coordination polymer;

A new copper(II) di-μ2-carboxylato bridged dinuclear complex: [Cu(oda)phen]2  · 6H2O (oda = oxydiacetate, phen = phenanthroline) by Ricardo Baggio; Rafael Calvo; Maria T. Garland; Octavio Peña; Mireille Perec; Leonardo D. Slep (1249-1252).
A new dinuclear complex [Cu(oda)(1,10-phen)] · 3H2O (oda = oxydiacetate dianion, 1,10-phen = 1,10-phenanthroline) was synthesized and structurally characterized. The complex is centrosymmetric with a Cu2O2 core and a Cu–Cu distance of 3.417(2) Å. Each copper atom resides in a CuN2O4 octahedral environment. Variable-temperature magnetic susceptibility (2–300 K) shows weak ferromagnetic interactions with J  = +3.3 cm−1. The intramolecular exchange coupling constant was calculated by the DFT-BS methodology.The oxydiacetate-bridged copper(II) complex [Cu(oda)(1,10-phen)] · 3H2O (oda = oxydiacetate dianion, 1,10-phen = 1,10-phenanthroline) has been characterized. The complex is dinuclear and centrosymmetric with each copper atom residing in a CuN2O4 octahedral environment. The Cu(II) ions are bridged by two carboxylate-oxygen atoms in a strictly planar Cu2O2 core with a Cu–Cu distance of 3.417(2) Å. The magnetic susceptibility measurements (2–300 K) show weak ferromagnetic coupling between the copper ions with J  = 3.3 cm−1. The results are compared with those of the homologous [Cu(tda)(1,10-phen)]2tda (tda = thiodiacetate dianion). A model proposed for the electronic structures of the complexes based on the density functional theory (DFT) satisfactorily accounts for the magnetic results.
Keywords: Crystal structure; Copper(II); Oxydiacetate; Magnetism;

Electrochemical syntheses and structures of lead(II) and bismuth(III) complexes of 4-(trimethylammonio)benzenethiolate by Zhi-Gang Ren; Xiao-Yan Tang; Li Li; Guang-Fei Liu; Hong-Xi Li; Yang Chen; Yong Zhang; Jian-Ping Lang (1253-1256).
Two main-group metal zwitterionic ammonium thiolate complexes, [M(Tab)3](ClO4) n (1: M = Pb, n  = 2; 2: M = Bi, n  = 3), were synthesized by electrochemical oxidation of Pb or Bi electrode in MeCN containing Tab and Et4NClO4. Compounds 1 and 2 were structurally characterized by elemental analysis, IR, and X-ray crystallography and their electrochemical properties were studied.Two main-group metal complexes of the zwitterionic ammonium thiolate complexes, [M(Tab)3](ClO4) n (Tab = 4-(trimethylammonio)benzenethiolate) (1: M = Pb, n  = 2; 2: M = Bi, n  = 3), were prepared by electrochemical oxidation of Pb or Bi electrode in MeCN containing Tab and Et4NClO4. Each M atom in 1 and 2 is coordinated by three S atoms of three Tab ligands, forming a trigonal pyramidal coordination geometry. The resulting [M(Tab)3] n+ cations are interconnected by secondary M⋯S interactions to form two different 1D cationic chains. The electrochemical properties of 1 and 2 were also investigated by cyclic voltammetry.
Keywords: Electrochemical synthesis; Lead; Bismuth; Zwitterionic ammonium thiolate; Crystal structure; Electrochemical properties;

pH-controlled the formation of 4-sulfocalix[4]arene-based 1D and 2D coordination polymers by Rong-Guang Lin; La-Sheng Long; Rong-Bin Huang; Lan-Sun Zheng (1257-1261).
Three manganese/4-sulfocalix[4]arene complexes have been synthesized under different pH conditions. Their structures range from one-dimensional to two-dimensional coordination complexes, showing structural effects on pH response.Three manganese/4-sulfocalix[4]arene complexes, namely, {H[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]} n  ·6nH2O (1), {NH4[(C28H20O16S4)Mn(H2O)4Mn0.5(H2O)2]} n  · 5nH2O (2), [(C28H20O16S4)Mn2(H2O)8] n  · 6nH2O (3), have been synthesized under different pH conditions. Complex 1, which exhibits a one-dimensional (1D) structure, is formed at [H+] = 2.0 mol L−1. Reaction at pH 4 leads to another one-dimensional (1D) coordination polymer of 2. At pH 5, a two-dimensional (2D) coordination polymer of complex 3 is formed, showing clearly structural effects on pH response.
Keywords: 4-Sulfocalix[4]arene; Manganese; Coordination polymer; pH-Dependent;

A novel non-symmetric zirconium guanidinato complex, [{Zr{ArNC(NMe2)N(SiMe3)}(μ2-Cl)Cl2}2] (Ar = 2,6- i Pr2-C6H3), was synthesized and structurally characterized. Catalytic studies showed that the zirconium complex was active for ethylene polymerization with the activity up to 4.98 × 105  g PE/mol Zr h. The influences of cocatalysts, Al/Zr molar ratios and ethylene pressures on the activities were investigated.A novel non-symmetric zirconium guanidinato complex, [{Zr{ArNC(NMe2)N(SiMe3)}(μ2-Cl)Cl2}2] (Ar = 2,6-iPr2-C6H3), was synthesized and structurally characterized. Catalytic studies showed that the zirconium complex was active for ethylene polymerization with the activity of 4.98 × 105  g PE/mol Zr h. The influences of cocatalysts, Al/Zr molar ratios and ethylene pressures on the activities were investigated.
Keywords: Zirconium complex; Guanidinate; Catalysis; Ethylene polymerization;

A novel method for construction of the amino-tethered guanidinate ligand in organolanthanide chemistry was described through addition of diamine with carbodiimide, and provides a potential strategy for assembling the amino-tethered guanidines from amines and carbodiimide.Reaction of N,N′-diisopropylcarbodiimide ( i PrN=C=N i Pr) with H2N(CH2)3NH2 and (C5H5)3Ln, give (C5H5)2Ln[H2N(CH2)3N=C(NH i Pr) N i Pr)] in high yields, indicating that the N–H bonds of one NH2 group readily add to the C=N double bonds of carbodiimide and one cyclopentadienyl group is eliminated to construct a novel amino-tethered guanidinate anionic ligand [H2N(CH2)3N= C(NH i Pr)N i Pr)].
Keywords: Addition; Guanidinate; Carbodiimide; Diamine; Organolanthanide;

Synthesis, crystal structure of polyoxovanadate complex of ciprofloxacin: V4O102-O)2[VO(H-Ciprof)2]2  · 13H2O by hydrothermal reaction by Yan-Cheng Liu; Zhen-Feng Chen; Shao-Ming Shi; Hai-Sheng Luo; Di-Chang Zhong; Hong-Li Zou; Hong Liang (1269-1272).
The hydrothermal reaction of ciprofloxacin (H-Ciprof) with NH4VO3 yields the first hexavanadate complex with ciprofloxacin which consists of one {V4O12} cluster and two corner-sharing octahedral {VO6}-ciprofloxacin subunits linked through two μ2-O bridges, and exhibits similar antibacterial activity to that of free ciprofloxacin.The hydrothermal reaction of ciprofloxacin (H-Ciprof) with NH4VO3 yields the first hexavanadate complex with ciprofloxacin, V4O102-O)2[VO(H-Ciprof)2)]2  · 13H2O 1, which is characterized by single crystal X-ray diffraction analysis, elemental analysis, TGA, UV–Vis and IR spectra. Compound 1 consists of one {V4O12} unit and two corner-sharing octahedral {VO6}-ciprofloxacin units linked through two μ2-O bridges. The antibacterial activity assay results show that its behavior is similar to that of free ciprofloxacin.
Keywords: Crystal structure; Ciprofloxacin; Vanadium complex; Antibacterial activity;

Synopsis A bis-Schiff base trinuclear cobalt(II) complex was synthesized under solvolthermal conditions from a mono-Schiff base ligand and cobalt acetate. The complex showed higher urease inhibitory activity than that of the corresponding ligand and the metal ion, and even comparable with that of the acetohydroxamic acid co-assayed as a positive reference against the enzyme.A bis-Schiff base trinuclear cobalt(II) complex was synthesized under solvolthermal conditions from a mono-Schiff base ligand and cobalt acetate. The complex was characterized by elemental analysis, IR spectrum and X-ray single crystal determination. The urease inhibitory activity was evaluated.
Keywords: Synthesis; Schiff base; Cobalt complex; Urease inhibition;

Two-dimensional (2D) metal-organic supramolecular polymer [Co22-4,4′-bipy)22-be)2(be)2] n 1 (4,4′-bipy = 4,4′-bipyridine, be = benzoate) has been synthesized by low-temperature solid-state reaction and characterized by single-crystal X-ray diffraction, elemental analyses, TGA, IR spectra and UV–visible spectra. The 2D structure is built from the linkage of secondary building units of binuclear [Co22-4,4′-bipy)22-be)2(be)2] clusters by a mixed connector of 4,4′-bipyridine and benzoate. The third-order non-linear optical (NLO) properties of the 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 8.30 × 10−30  esu for 1 in a 2.70 × 10−4  mol dm−3 DMF solution.Two-dimensional (2D) metal-organic supramolecular polymer [Co22-4,4′-bipy)22-be)2(be)2] n 1 (4,4′-bipy = 4,4′-bipyridine, be = benzoate) has been synthesized by low-temperature solid-state reaction and characterized by single-crystal X-ray diffraction, elemental analyses, TGA, IR spectra and UV–visible spectra. The 2D structure is built from the linkage of secondary building units of binuclear [Co22-4,4′-bipy)22-be)2(be)2] clusters by a mixed connector of 4,4′-bipyridine and benzoate. The third-order non-linear optical (NLO) properties of the 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 8.30 × 10−30  esu for 1 in a 2.70 × 10−4  mol dm−3 DMF solution.
Keywords: Cobalt(II) polymer; Supramolecular polymer; Third-order NLO behavior;

A novel heterometallic metal–organic framework (MOF) constructed from luminescent building block, [Tb(pydc)3]3−, and alkaline earth ion has been designed and synthesized. It illustrates a three-dimensional (3D) structure with nano-channels, and shows reversible dehydration and rehydration behavior.A novel metal–organic framework constructed from luminescent building block, [Tb(pydc)3]3−, and alkaline earth ion has been designed and synthesized. It illustrates a three-dimensional (3D) structure with nano-channels, and shows reversible dehydration and rehydration behavior.
Keywords: MOF; Luminescent building block; Dehydration; Rehydration;

A novel 3D network structure constructed from centrosymmetric sodium-phosphomolybdate bonding by sodium and zinc atoms by Xinqin Chen; Shen Lin; Lijuan Chen; Xiaohua Chen; Chunlian Liu; Jiebo Chen; Liuyi Yang (1285-1288).
A novel three-dimensional framework based on centrosymmetric {Na(Mo6P4)2} dimers has been hydrothermally synthesized and structurally characterized. It represents the first example that {Na(Mo6P4)2} is integrated by mixed alkali metal and transition metal atoms to form the extended 3D structure. Meanwhile the title compound possessed fascinating photocatalytic activity.A novel molybdenum (V) phosphate compound, (NH3CH2CH2NH3) (NH3CH2CH2NH2)4Zn2Na(2){Na(1)[Mo6O16(HPO4)3(PO4)(OH)3(H2O)]2} · 3 H2O was synthesized hydrothermally and characterized by elemental analysis, IR, TG-DTA, DRS, BET and single crystal X-ray diffraction. In this compound, the centrosymmetric Na(1)[Mo6P4]2 clusters are linked by Na(2) to produce one-dimensional chains along b axis. Then such 1D chains are further connected by [ZnO4] tetrahedra to construct a three-dimensional (3D) framework with channels occupied by protonated ethylenediamine ions and the water molecules. Photocatalytic reduction of Rhodamine B (RB) in a liquid-solid system shows that the title compound has high photocatalytic activity.
Keywords: Polyoxometalates; Hydrothermal synthesis; 3D framework; Photocatalysis;

The novel supramolecular silver(I) compound with formula [Ag6(TST)2(bipy)6(H2O)2] n  · 3nH2O (1) based on assembly of Ag(I) and mixed ligand bipy/TST3−, bipy = 2,2′-bipyridine, H3TST = 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, has been prepared by hydrothermal method. In the solid-state structure of 1, two-dimensional layered polymeric structures extended with subunits [Ag6(TST)2(bipy)6(H2O)2] interact each other in the form of π–π attractions between bipy, forming a three-dimensional supramolecular architecture. Compound 1 represents a Ag-containing polymeric compound possessing room-temperature luminescence.The novel supramolecular silver(I) compound with formula [Ag6(TST)2(bipy)6(H2O)2] n  · 3nH2O (1) based on assembly of Ag(I) and mixed ligand bipy/TST3−, bipy = 2,2′-bipyridine, H3TST = 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, has been prepared by hydrothermal method. In the solid-state structure of 1, two-dimensional layered polymeric structures extended with subunits [Ag6(TST)2(bipy)6(H2O)2] interact each other in the form of π–π attractions between bipy, forming a three-dimensional supramolecular architecture. Compound 1 represents a Ag-containing polymeric compound possessing room-temperature luminescence.
Keywords: Hydrothermal method; Supramolecular compound; Self-assembly; Luminescence;

The yellow colour of silver hyponitrite is attributed to an LMCT band at λ max  = 419 nm. Solid Ag2N2O2 and its suspensions in water or acetonitrile are light sensitive. LMCT excitation leads to photolysis according to the equation Ag2N2O2  → 2Ag + 2NO. In the presence of air and water, NO is finally converted to HNO2.The yellow colour of silver hyponitrite is attributed to an LMCT band at λ max  = 419 nm. Solid Ag2N2O2 and its suspensions in water or acetonitrile are light sensitive. LMCT excitation leads to a photolysis according to the equation Ag2N2O2  → 2Ag + 2NO. In the presence of air and water, NO is finally converted to HNO2.
Keywords: Electronic spectra; LMCT; Hyponitrite complexes; Silver complexes; Photochemistry; Nitric oxide;

Syntheses are described for two new ligands that contain a central benzene to which are attached via oxygen atoms two pyrazine or quinoxaline rings. These react with copper(I) iodide to form complexes whose crystal structure structures reveal coordination polymers consisting of ladders of Cu2I2 rings crosslinked into two-dimensional sheets by the new bridging ligands. The ligands separate the ladders by a distance of ca. 1.6 nm.Syntheses are described of two new ligands that contain a central benzene to which are attached via oxygen atoms two pyrazine or quinoxaline rings. These react with copper(I) iodide to form complexes, whose crystal structures reveal coordination polymers consisting of ladders of Cu2I2 rings crosslinked into two-dimensional sheets by the new bridging ligands. The ligands separate the ladders by a distance of ca. 1.6 nm.
Keywords: Copper; Pyrazine; Quinoxaline; Coordination polymers;

Synthesis of molybdo-methylphosphate and -ethylphosphate with inverted-Keggin structure by Tadaharu Ueda; Toshiaki Yonemura; Motoo Shiro; Masahiko Fukudome; Masashi Hojo (1301-1303).
Novel heteropolymolybdates with inverted-Keggin structure containing methylphosphate or ethylphosphate as hetero ions were prepared and isolated as tetra-alkylammonium salts from aqueous-CH3CN solution. They were characterized by elemental analysis, X-ray analysis, FTIR, Raman, UV–vis and cyclic voltammetry.Novel heteropolymolybdates containing methylphosphate or ethylphosphate as hetero ions were prepared and isolated as tetra-alkylammonium salts from aqueous-CH3CN solution. They were characterized by elemental analysis, X-ray analysis, FT-IR, Raman, UV–vis and cyclic voltammetry. They were elucidated to have so-called inverted-Keggin structure. The phosphorus-containing polyoxometalates with inverted-Keggin structure have been found for the first time.
Keywords: Polyoxometalate; Inverted-Keggin; X-ray analysis; Acetonitrile;

Platinum tetrasulfophthalocyanine as selective catalyst for the aerobic oxidation of shikimic acid by Marco Nicastro; Lucia Tonucci; Nicola d’Alessandro; Mario Bressan; Luana Katia Dragani; Antonino Morvillo (1304-1306).
The paper reports on an aerobic catalytic and selective oxidation of shikimic acid, a natural product of wide interest, used as starting material for the well-known drug Tamiflu, as well as for other new molecules of pharmaceutical/medicinal importance.A new catalytic, green procedure to produce dehydroshikimic acid (DHS) was developed. Platinum sulfophthalocyanine (PtPcS) was able to catalyze the aerobic oxidation of shikimic acid in water solution and at room temperature and 1 atm, giving selectively DHS as unique reaction product.
Keywords: Platinum tetrasulfophthalocyanine; Shikimic acid; Aerobic oxidation; Green synthesis; Homogeneous catalysis;

Acetophenone thiosemicarbazone bridging of {Ag(μ-P,P)2Ag} core has formed an unusual hetero-bridged dimer, [Ag(μ-P,P-dppm)2(μ-S-Haptsc)Ag(ONO2)]NO3 1, with a short Ag⋯Ag contact.Acetophenone thiosemicarbazone (Haptsc) with silver(I) nitrate and Ph2P–CH2–PPh2 (dppm) has formed a first example of triply hetero-bridged [Ag(μ-P,P-dppm)2(μ-S-Haptsc)Ag(ONO2)]NO3 dimer with a short Ag⋯Ag contact of 2.9939(7) Å.
Keywords: Acetophenone thiosemicarbazone; Silver(I); Bis(diphenylphosphino)methane; Triply bridging; Asymmetrically coordinated;

New [2 × 2] cyclic framework that induces distortions from square planar to tetrahedral around the copper(II) centers by Mitsuru Kondo; Yuhki Shibuya; Keiko Nabari; Makoto Miyazawa; Sachie Yasue; Kenji Maeda; Fumio Uchida (1311-1314).
A new [2 × 2] metallacyclic framework was constructed by combination of four copper(II) ions and four bis-didentate bridging ligands, bis(N-salicylidene)benzene-1,4-diamine (bsbd). The complex, [Cu4(bsbd)4], gives tetrahedrally distorted copper(II) centers, and a resulting rhombus cyclic framework.A new tetracopper(II) complex [Cu4(bsbd)4] (bsbd = bis(N-salicylidene)benzene-1,4-diamine) has been prepared and structurally characterized. The complex constructs a [2 × 2] cyclic coordination framework, which inhibits formation of square planar copper(II) centers, and induces distortion to a tetrahedral structure. The effects of the distortions on the absorption spectra are characterized.
Keywords: Cyclic framework; Schiff base complex; [2 × 2] Grid; Tetracopper(II) complex; Distorted coordination center;

The first ditelluride having Schiff base functionality (2-HOC6H4(CH3)C=NCH2CH2Te)2 (4) has been synthesized. It gives in 125Te NMR spectrum signal at 98.0 ppm, which is characteristic of a ditelluride. The 125Te NMR spectral studies on the mixture of 4 and (4-CH3OC6H4Te)2 indicate the instantaneous formation of 2-HOC6H4(CH3)C=NCH2CH2Te–TeC6H4-4-OCH3 (6) in equilibrium with the precursor ditellurides. It is supported by 13C{1H} NMR spectra also.The first ditelluride having Schiff base functionality (2-HOC6H4(CH3)C= NCH2CH2Te)2 (4) has been synthesized by reacting H2NCH2CH2TeTeCH2CH2NH2 with 2-hydroxyacetophenone under anaerobic conditions. Compound 4 gives in 125Te{1H} NMR spectrum signal at 98.0 ppm, which is characteristic of a ditelluride. The 125Te{1H} NMR spectral studies on the mixture of 4 and (4-CH3OC6H4Te)2 indicate the instantaneous formation of 2 HOC6H4(CH3)C=NCH2CH2Te–TeC6H4-4-OCH3 (6) in equilibrium with the precursor ditellurides. This ligand exchange equilibrium is attained instantaneously. It is supported by 13C{1H} NMR spectra also.
Keywords: 125Te NMR spectra; Ligand exchange reaction; Ditelluride; Schiff base functionality;

Synthesis and description of the first helical double chain of [ V 4 O 12 ] ∞ 4 - . A novel organic–inorganic hybrid manganese vanadate [PnH2][Mn(V4O12)(H2O)2] (1) has been synthesized under hydrothermal reaction conditions. The most interesting feature of 1 is that a left-handed and a right-handed [ V 4 O 12 ] ∞ 4 - double chain are connected together by MnO6 octahedral to generating a double helical structure.A novel organic–inorganic hybrid manganese vanadate, [C3N2H12][Mn(V4O12)(H2O)2] (1), has been hydrothermally synthesized and structurally characterized. The structure of the title compound is layered and can be described as manganese vanadium oxide layers with diprotonated 1,3-propanediammonium with water molecules occupying the interlayer space. The presence of [ V 4 O 12 ] ∞ 4 - helical double chains in compound 1 is noteworthy.
Keywords: Organic–inorganic hybrid manganese vanadates; Hydrothermal synthesis; Helical chains; Layered structure;

A new double bitrack Cu–N coordination polymeric chain-modified Wells–Dawson POMs, [Cu(4,4′-bipy)]2[H4P2W18O62] · 2H2O (1), has been synthesized and characterized, which represents the first example that saturated Wells–Dawson POMs are covalently linked by transition metal coordination polymers into a 3D structure with a (6482)(6482) topology.A new double bitrack Cu–N coordination polymeric chain-modified Wells–Dawson POMs, [Cu(4,4′-bipy)]2[H4P2W18O62] · 2H2O (1), has been synthesized and characterized by IR, TG and single crystal X-ray diffraction. It represents the first example that saturated Wells–Dawson POMs are covalently linked by transition metal coordination polymers into a 3D structure. Additionally, its electrochemical property has been studied, undergoing three two-electron reversible redox processes.
Keywords: Hydrothermal synthesis; Wells–Dawson; Polyoxometalates; Electrochemistry;

Novel heterobimetallic Cu/Mn coordination polymers prepared by “direct permanganate” synthesis by Asya O. Beznischenko; Valeriya G. Makhankova; Vladimir N. Kokozay; Roman I. Zubatyuk; Oleg V. Shishkin (1325-1329).
Two heterometallic Cu/Mn complexes [Cu(Me2en)2][Mn2(ox)3] · 2H2O (1) (Me2en =  N,N-dimethylethylenediamine, H2ox-oxalic acid) and [Cu(1,3-n)(ox)(H2O)][Mn(ox)(H2O)2] · H2O (2) (1,3-pn = 1,3-diaminopropane) are prepared by the one-pot reaction of copper powder, tetrabutylammonium permanganate, oxalic acid and N-chelating ligands. Their structures are investigated by single-crystal X-ray analysis that reveals interesting variation in bridging motives of the oxalate groups composing the Mn-polymeric fragments.Two heterometallic Cu/Mn complexes [Cu(Me2en)2][Mn2(ox)3] · 2H2O (1) (Me2en =  N,N-dimethylethylenediamine, H2ox – oxalic acid) and [Cu(1,3-pn)(ox)(H2O)][Mn(ox)(H2O)2] · H2O (2) (1,3-pn = 1,3-diaminopropane) are prepared by the one-pot reaction of copper powder, tetrabutylammonium permanganate, oxalic acid and N-chelating ligands. Their structures are investigated by single-crystal X-ray analysis that reveals interesting variation in bridging motives of the oxalate groups composing the Mn-polymeric fragments.
Keywords: Heterometallic oxalates; Elemental copper; Tetrabutylammonium permanganate; Crystal structure;

Two novel organotin(IV) complexes of the types [(Ph3Sn)4(O3POPh)2] n 1 and [(Ph3Sn)6(O3POPh)3]2 2 have been prepared by treatment of phenylphosphoric acid and the Ph3SnCl under different conditions. The complexes 1 and 2 were characterized by elemental analysis, IR and NMR (1H,13C,119Sn) spectroscopy and X-ray crystallography diffraction analysis. The structure analyses reveal that complex 1 is an infinite 1D polymer and complex 2 is a dimer which contains two 24-membered macrocycles.Two novel organotin(IV) complexes of the types [(Ph3Sn)4(O3POPh)2] n 1 and [(Ph3Sn)6(O3POPh)3]2 2 have been prepared by treatment of phenylphosphoric acid and the Ph3SnCl under different conditions. The complexes 1 and 2 were characterized by elemental analysis, IR and NMR (1H,13C,119Sn) spectroscopy and X-ray crystallography diffraction analysis. The structure analyses reveal that complex 1 is an infinite 1D polymer and complex 2 is a dimer which contains two 24-membered macrocycles.
Keywords: Triphenyltin(IV); Phenylphosphoric acid; Crystal structures; Macrocycle;

Magnetic properties and structure of a new one-dimensional azido-bridged nickel(II) coordination polymer by Xiao-li Yu; Wan-sheng You; Xin Guo; Lan-cui Zhang; Yan Xu; Zhen-gang Sun; Rodolphe Clérac (1335-1338).
A novel one-dimensional nickel(II) coordination polymer with azido-bridge, [Ni(dpa)(N3)2] · H2O 1 exhibits a zig-zag chain structural arrangement, which is built via three EO and one EE azido-bridges. The study of the magnetic properties reveals dominating antiferromagnetic interactions between Ni(II) ions through the EE bridges.A new one-dimensional nickel(II) coordination polymer with azido-bridge, [Ni(dpa)(N3)2] · H2O 1 (where dpa is the 2,2′-dipyridylamine ligand) has been synthesized and crystal structure was determined by single-crystal X-ray diffraction. Complex 1 exhibits a zig-zag chain structural arrangement, and the hexa-coordinated Ni(II) ion exhibits a distorted octahedral coordination sphere. The chains topologies are built via three EO and one EE azido bridges. The study of the magnetic properties reveals dominating antiferromagnetic interactions between Ni(II) ions through the EE bridges.
Keywords: Coordination polymer; Magnetic properties; Azide; Ni(II) complex;

1-(3,5-Di-tert-butyl)pyrazolyldiphenylphosphine was prepared from 3,5-di-tert-butyl)pyrazole and chlorodiphenylphosphine. It reacted with (Me2S)AuCl to afford a Au(I) complex bearing the pyrazolylphosphine ligand in a monodentate coordination mode.1-(3,5-Di-tert-butyl)pyrazolyldiphenylphosphine was prepared from 3,5-di-tert-butyl)pyrazole and chlorodiphenylphosphine. It reacted with (Me2S)AuCl to afford a Au(I) complex bearing the pyrazolylphosphine ligand in a monodentate coordination mode.
Keywords: Unsymmetrical ligands; Hemilabile property; Pyrazolylphosphine; Gold(I) complex;

A novel supramolecular compound based on the heptamolybdate anion, formulated as (Hapy)4[Co(H2O)5Mo7O24] · 9H2O (1) (apy = 2-aminopyridine), has been synthesized hydrothermally and characterized by elemental analyses, IR, and X-ray single crystal diffraction. Compound 1 crystallizes as alternating layers of inorganic anions and organic cations linked by hydrogen-bonding interactions.A new supramolecular compound based on the heptamolybdate anion, formulated as (Hapy)4[Co(H2O)5Mo7O24] · 9H2O (1) (apy = 2-aminopyridine), has been synthesized hydrothermally and characterized by elemental analyses, IR, and X-ray single crystal diffraction. Compound 1 crystallizes as alternating layers of inorganic anions and organic cations linked by hydrogen-bonding interactions. A variable-temperature magnetic susceptibility measurement of 1 demonstrated the presence of antiferromagnetic interactions. Furthermore, the cyclic voltammogram of 1 shows two reversible redox couples both of which are associated with two-electron processes of molybdenum.
Keywords: Supported polyoxometalate; Heptamolybdate anions; Supramolecular; Magnetic property; Electrochemical property;

Unusual metal–organic network constructed from Zn(II), benzenetricarboxylate and bis(1,2,4-triazolyl)pyridine by Sheng-Wen Liang; Ming-Xing Li; Min Shao; Hong-Jiang Liu (1347-1350).
A metal–organic network {[Zn3(btp)2(btc)2(H2O)2] · 4H2O} n (1) and a supramolecular cocrystal [H3btc · btp · H2O] n (2) were synthesized and structurally characterized. Complex 1 exhibits an unusual polymeric network contains two molecular squares and a rectangle.Hydrothermal reaction of ZnSO4  · 7H2O with 1,3,5-benzenetricarboxylic acid (H3btc) and 2,6-bis(1,2,4-triazolyl)pyridine (btp) afforded a novel metal–organic network {[Zn3(btc)2(btp)2(H2O)2] · 4H2O} n (1) with a supramolecular cocrystal [H3btc · btp · H2O] n (2). The complex 1 exhibits an unusual network containing two molecular squares and a rectangle. The networks interpenetrate to make a 3D metal–organic framework, which is quite thermal stable. Compound 2 shows a 2D supramolecular network assembled through strong hydrogen bonds.
Keywords: 1,3,5-Benzenetricarboxylic acid; 2,6-Bis(1,2,4-triazolyl)pyridine; Metal–organic framework; Crystal structure;

Synthesis, crystal structure and bioactivity of a novel linear trinuclear nickel(II) complex by Wei Luo; Xianggao Meng; Xuzhuo Sun; Fengping Xiao; Junfeng Shen; Yan Zhou; Gongzhen Cheng; Zhenping Ji (1351-1354).
The three nickel ions in this novel trinuclear complex arrange in a strictly linear structure, and exhibit alternating square-planar and octahedral coordination environments. It shows a wave-like 2D structure formed by intermolecular H bonds.A novel linear trinuclear nickel(II) complex, [Ni3(H2O)2(DMA)2(acbshz)2]·2DMF (DMA = dimethylamine; acbshz =  N-acryloyl-5-bromosalicylhydrazide), has been prepared by self-assembly approach. The three nickel atoms arrange in a strictly linear structure, adjacent molecules are linked by intermolecular H bonds to form a 2D infinite wave-like structure. Antibacterial screening data indicate the formation of the trinuclear complex reduced the antimicrobial activity of the ligand.
Keywords: Self-assembly; Nickel complex; Linear trinuclear; Antimicrobial activity;

Mixed-ligand platinum and palladium complexes based on dinitrogen chelating ligands and a pyridine bearing the nitronylnitroxide radical by Ahsan M. Shemsi; Bassam El Ali; Khalil A. Ziq; Mohamed Morsy; Tony D. Keene; Silvio Decurtins; Mohammed Fettouhi (1355-1359).
The first cationic mixed-ligand palladium and platinum complexes based on the chelating ligands 4,7-dimethyl-1,10-phenanthroline and 2,2′-bipyridine with a pyridine bearing the nitronylnitroxide radical are reported.Novel cationic mixed-ligand palladium and platinum complexes based on the chelating ligands 4,7-dimethyl-1,10-phenanthroline and 2,2′-bipyridine with a pyridine bearing the nitronylnitroxide radical are reported. The synthesis, X-ray crystal structures and magnetic properties of the two complexes [Pd(4,7-dimethyl-1,10-phenanthroline)(NIT-pPy)2](PF6)2. DMF and [Pt(2,2′-bipyridine-N,N′)(NIT-pPy)2](PF6)2  · 0.25H2O, (where NIT-pPy = 2-(p-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) are described. The two metal complexes show a strained square planar geometry. Short intermolecular contacts take place through the nitroxide groups and weak intermolecular antiferromagnetic interactions are dominant at low temperature.
Keywords: Palladium; Platinum; Nitronylnitroxide; X-ray crystal structures; Magnetic properties;

A novel two-dimensional square grid cobalt complex: Synthesis, structure, luminescent and magnetic properties by Ju-Zhou Zhang; Wei-Ran Cao; Jian-Xin Pan; Qian-Wang Chen (1360-1364).
A novel cobalt complex, showing a perfect 2D square grid framework with dimensions of 11.42 × 11.42 Å, has been easily synthesized by hydrothermal technology. The complex demonstrates luminescent and antiferromagnetic dual functionalities, which suggests that conjugated ligand is a good candidate for construction of magneto-optical multifunctional materials.A novel cobalt(II) coordination polymer, [Co(L)2] n (1) (HL = 4-(imidazol-1-yl)-benzoic acid), has been hydrothermally synthesized and structurally characterized by X-ray diffraction, IR spectrum and elemental analyses. Structure determination of complex 1 reveals that the two-dimensional (2D) network framework consists of regular square grid with dimensions of ca. 11.42 × 11.42 Å. Complex 1 exhibits a strong blue luminescence centering at 409 nm in the solid. Variable temperature magnetic susceptibility study shows there is a weak antiferromagnetic interaction in complex 1. Thermal property is also investigated.
Keywords: Cobalt; Hydrothermal synthesis; Square grid; Luminescent property; Magnetic property;

Polymeric structures of a pair of linear, dicarboxylate (tpy)2Ru2+ analogues by Michael W. Cooke; Pierre M. Tremblay; Garry S. Hanan (1365-1370).
The first X-ray structure of a homoleptic Ru(II) complex based on 4′-(para-carboxyphenyl)-terpyridine ligand is found to possess a polymeric solid-state structure due to hydrogen-bonding interactions. The introduction of four solubilizing tert-butyl groups into the complex gives rise to a more porous solid-state structure.The preparation and solid-state structures of homoleptic Ru(II) complexes based on the ligands 4′-(4-carboxyphenyl)tpy (L1) (where tpy = 2,2′:6′,2″-terpyridine) and 4′-(4-carboxyphenyl)-4,4″-di-(tert-butyl)tpy (L2) are described. Both complexes are found to possess polymeric solid-state structures due to hydrogen-bonding interactions. The first complex, [Ru(L1)2]2+, exhibits a more closely-packed structure relative to that of [Ru(L2)2]2+, which was found to have a porous solid-state structure due to the steric bulk of the tert-butyl groups.
Keywords: Ruthenium complexes; Tridentate ligands; N ligands; Solid-state structure; Hydrogen-bonding;

Oral administration versus intra-peritoneal injection of Pb affects its concentration in selected rat tissues by Gregory E. Steinbaugh; Richard W. Taylor; Douglas R. Pfeiffer (1371-1374).
The relative percent changes in the three oral groups compared to the IP group. Brain doesn’t contain a high concentration of Pb and we wouldn’t expect to see much change between the test groups. In brain, Pb effects manifest at low overall levels and include cognitive impairment and reduced IQ.During studies in our laboratory, a significant difference in Pb concentration was observed depending upon Pb administration: rats that were given Pb by intra-peritoneal injection showed a higher concentration of Pb and smaller relative errors compared to their oral counterparts. The relative percent changes in several tissues between oral and IP groups were calculated to determine whether Pb concentrations were statistically significant or not.
Keywords: Heavy metal intoxication; Pb; ICP mass spectroscopy; EAA spectroscopy;

The new imine ligand (E)-2,4,6-Me3C6H2CH2N=CH t Bu (1) has been prepared from 2,4,6-trimethylbenzylamine and trimethylacetaldehyde. In this imine, the ortho-positions of the benzyl group are blocked by methyl groups, and there are no β-hydrogen atoms susceptible for imine–enamine rearrangement. Thus, reaction with [PdCl2(C6H5CN)2] leads to the complex trans-[PdCl2(2,4,6-Me3C6H2CH2N=CH t Bu)2] (2) that cannot undergo cyclopalladation.The new imine ligand (E)-2,4,6-Me3C6H2CH2N=CH t Bu (1) has been prepared from 2,4,6-trimethylbenzylamine and trimethylacetaldehyde. In this imine, the ortho-positions of the benzyl group are blocked by methyl groups, and there are no β-hydrogen atoms susceptible for imine–enamine rearrangement. Thus, reaction with [PdCl2(C6H5CN)2] leads to the complex trans-[PdCl2(2,4,6-Me3C6H2CH2N=CH t Bu)2] (2) that cannot undergo cyclopalladation. The single-crystal X-ray structure analysis of trans-[PdCl2(2,4,6-Me3C6H2CH2N=CH t Bu)2] (2) confirms the trans-coordination of the imine ligands in this square-planar complex.
Keywords: Imine ligand; ortho-Metallation; Imine–enamine rearrangement; Palladacycle; Palladium complex;

K10[Co4(H2O)2(B-α-SiW9O34H)2] · 21H2O: A sandwich polyoxometalate based on the magnetically interesting element cobalt by Li-Zhi Zhang; Wen Gu; Xin Liu; Zhili Dong; Yong-Sheng Yang; Bing Li; Dai-Zheng Liao (1378-1380).
The magnetism of a sandwich tetracobalt(II) substituted tungstosilicate K10[Co4(H2O)2(B-α-SiW9O34H)2] · 21H2O has been studied based on an isotropic Heisenberg model supplemented by a zero-field splitting term.The magnetism of a sandwich tetracobalt(II) substituted tungstosilicate K10[Co4(H2O)2(B-α-SiW9O34H)2] · 21H2O has been studied based on an isotropic Heisenberg model supplemented by a zero-field splitting term.
Keywords: Cobalt(II); Sandwich; Polyoxometalate; Magnetism;

The first dinuclear bis(mercaptoimidazolyl)methane metal complex, the lead(II) derivative [Pb2(BmmMe)5](ClO4)4, has been prepared and fully characterized using a combination of analytical and spectroscopic techniques, including electrospray ionization mass spectrometry (ESI-MS) and X-ray crystallographyThe first dinuclear bis(mercaptoimidazolyl)methane metal complex, the lead(II) derivative [Pb2(BmmMe)5](ClO4)4, has been prepared and fully characterized using a combination of analytical and spectroscopic techniques. X-ray crystallography confirmed the presence in the solid state of two dicationic [Pb(BmmMe)2]2+ fragments bridged by the fifth BmmMe ligand, which uses an unprecedented unidentate:bidentate (μ-κ1-S2-S,S) coordination mode to link the two metal centers.
Keywords: Lead; Bis(mercaptoimidazolyl)methanes; Soft scorpionates; Thione ligands; Dinuclear complexes;

Bi- and tri-nuclear complexes of the types [MCl(ECH2CH2NMe2)(PR3)M′Cl2(PR3)] and [{PtCl(SeCH2CH2NMe2)(PR3)}2M′Cl2] (M, M′ = Pd, Pt; E = Se, Te) have been prepared. The molecular structure of [{PtCl(SeCH2-CH2NMe2)(PEt3)}2PtCl2] comprises of three square planar platinum atoms which are held together by the single bridging selenolate group in a linear chain arrangement.Bi- and tri-nuclear palladium/platinum complexes of the types [MCl(ECH2CH2NMe2)(PR3)M′Cl2(PR3)] (M, M′ = Pd or Pt) and [{PtCl(SeCH2CH2NMe2)(PR3)}2M′ Cl2] (M′ = Pd or Pt; PR3  = PEt3 or PPr 3 n ) have been prepared. All complexes were characterized by elemental analysis, NMR (1H, 31P, 77Se, 125Te, 195Pt) data. The structures of [PdCl(SeCH2CH2NMe2)(PPh3)PtCl2(PPh3)] and [{PtCl(SeCH2CH2NMe2)(PEt3)}2PtCl2] have been established by single crystal X-ray diffraction analysis. In the latter complex, three square planar platinum atoms are held together by the single bridging selenolate group in an almost linear chain arrangement.
Keywords: Chalcogenolate; Bi-nuclear; Tri-nuclear; Platinum(II);