Inorganic Chemistry Communications (v.12, #10)

Contents List (iii-xiii).

A 3D supramolecular architecture constructed from the {Cu6}-containing sandwich-type tungstoantimonite has been successfully synthesized under hydrothermal conditions, in which the {Cu6} cluster was stabilized by both the inorganic O-donor polyoxometalate ligands and the organic N-donor ligands.A hexagonal {Cu6} cluster-containing tungstoantimonite, [Cu(enMe)2(H2O)]2{Cu(enMe)2[Cu(enMe)]3[Cu(H2O)]3(SbW9O33)2}·5H2O (1, enMe = 1,2-diaminopropane) has been successfully synthesized under hydrothermal conditions. The {Cu6} cluster in 1 is stabilized by both the inorganic O-donor ligand {B-α-SbW9O33}9− and the organic N-donor ligand enMe, leading to a hybrid inorganic-metal-organic sandwich-type polyoxometalate. The sandwich-type polyoxoanions are further connected into a 3D supramolecular framework via hydrogen bonding interactions between 1,2-enMe molecules and the sandwich-type polyoxoanions. The magnetic study indicates that intramolecular ferromagnetic Cu–Cu interactions exist in the hexanuclear metal-cluster.
Keywords: Polyoxometalate; Tungstoantimonite; Copper; Magnetism;

A new 3D supramolecular compound containing 1D [ Na 2 ( H 2 O ) 8 ] n 2 + chains and 1D water chains by Jing-cai Yao; Xue-lan Mei; Kai Jiang; Yan-ge Li; Lu-fang Ma (941-944).
A 3D supermolecular compound, [Na2(H2O)8] n (trz)2 n [trz = 1,2,4-triazolate], have been synthesized and structurally characterized, which contains 1D zigzag Na(I) chains and 1D water chains.The first crystal structure involving the discrete unsubstituted 1,2,4-triazolate anion is reported. In the title compound, [Na2(H2O)8] n (trz)2 n [trz = 1,2,4-triazolate] (1), each sodium(I) ion is coordinated by six water molecules with a slight distorted octahedron geometry. Each Na(I) are bridged by two μ 2-aqua ligands and arranged in an alternating fashion to construct a 1D zigzag {[Na2(H2O)8]2+} n chain. The 3D supermolecular framework is formed with 1D {[Na2(H2O)8]2+} n chain as the assembly units, by 1D water chain and 1,2,4-triazolate anion as the hydrogen bonding spacers.
Keywords: Crystal structure; 1,2,4-Triazolate; Supermolecular compound; Hydrogen bonding;

First X-ray structure of discrete anion [HgBr5]3−: Synthesis, characterization and single crystal X-ray structure determination of [Co(NH3)6][HgBr5] by Raj Pal Sharma; Rajni Sharma; Ajay Kumar; Paloth Venugopalan; Paula Brando; Vitor Felix (945-947).
A new cobalt(III) complex salt, [Co(NH3)6][HgBr5], has been synthesized and characterized by spectroscopic techniques and single crystal X-ray structure determination. This is a first structural report of the anion [HgBr5]3−. The cations and anions are associated in chains by strong NH⋯Br hydrogen bonds.A new cobalt(III) complex salt, [Co(NH3)6][HgBr5](1) was crystallized from a solution of hexaamminecobalt(III)bromide and potassium tetrabromomercurate(II) in aqueous medium in 1:1 molar ratio. This complex salt has been characterized by elemental analyses, spectroscopic techniques (e.g. UV/Visible, IR), solubility product and conductance measurements. The complex salt crystallizes in Orthorhombic crystal system with space group Pnma. Single crystal X-ray structure determination revealed the presence of discrete ions: [Co(NH3)6]3+ cation and a new anion [HgBr5]3−. This is the first structural report of a complex salt containing this new anion. The structure consists of stacks of cations and anions demonstrating supramolecular arrangements through N–H⋯Br hydrogen-bond interactions. The crystal lattice is stabilized by these non-covalent interactions besides electrostatic interaction.
Keywords: Cobalt(III); Coordination chemistry; Pentabromomercurate(II); X-ray crystallography; IR spectroscopy; UV/Visible spectroscopy;

A novel luminescent Pb(II) coordination framework, {Pb(II)(C6H4O2N)2} n , have been prepared in situ hydrolysis of 4-cyanopyridine under hydrothermal condition and characterized by the elemental analyses, IR spectra, TG and single crystal X-ray diffraction. The compound presents the first framework compound constructed from isonicotinic acids and lead(II) ions, showing three-dimensional architecture with (4, 4) net self-penetrating (4867) topology.A novel luminescent Pb(II) coordination framework, {Pb(II)(C6H4O2N)2} n , have been prepared in situ hydrolysis of 4-cyanopyridine under hydrothermal condition and characterized by the elemental analyses, IR spectra, TG and single crystal X-ray diffraction. The compound presents the first framework compound constructed from isonicotinic acids and lead(II) ions, showing three-dimensional architecture with (4, 4) net self-penetrating (48 67) topology.
Keywords: Pb(II) coordination; 4-Cyanopyridine; Hydrolysis; Three-dimensional architecture; Self-penetrating topology;

Formation of an unusual copper(II) complex from the degradation of a novel tricopper(II) carbohydrazone complex by E. Manoj; M.R. Prathapachandra Kurup; Rohith P. John; M. Nethaji; Alex Punnoose (952-955).
An unusual copper(II) complex [Cu(L1a)2Cl2]·CH3OH·H2O·H3O+Cl (1a) was isolated from a solution of a novel tricopper(II) complex [Cu3(HL1)Cl2]Cl3·2H2O (1) in methanol, where L1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine. The tricopper(II) complex of potential biscarbohydrazone ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H2L1) was synthesized and physico-chemically characterized. The variable temperature magnetic susceptibility measurement and EPR spectral studies reveal exchange coupled Cu(II) centers in complex 1. The complex 1a was characterized by single crystal X-ray diffraction study and found to be having an octahedral Cu(II) center. The time-dependant monitoring of the UV–visible spectra of a solution of 1 in methanol reveals loss of intensity of bands corresponding to O → Cu(II) charge transfer, which is inferred as a consequence of aerobic degradation of –CO– group and cyclization of ligand unit to yield the complex 1a.An unusual copper(II) complex [Cu(L1a)2Cl2] CH3OH·H2O·H3O+Cl (1a) was isolated from a solution of a novel tricopper(II) complex [Cu3(HL1)Cl2]Cl3·2H2O (1) in methanol, where L1a is 3-(2-pyridyl)triazolo[1,5-a]-pyridine, and characterized with single crystal X-ray diffraction study. The tricopper(II) complex of potential ligand 1,5-bis(di-2-pyridyl ketone) carbohydrazone (H2L1) was synthesized and physico-chemically characterized, while the formation of the complex 1a was followed by time-dependant monitoring of the UV–visible spectra, which reveals degradation of ligand backbone as intensity loss of bands corresponding to O → Cu(II) charge transfer.
Keywords: Carbohydrazone; Cu(II) complex; Synthesis; Dipyridyl ketone; Antiferromagnetism; EPR; Crystal structure;

Ionothermal synthesis of a new cobalt metal-organic framework based on tetranuclear cobalt clusters by Jian-Wei Ji; Wei Zhang; Guo-Xin Zhang; Zheng-Bo Han (956-958).
A new metal-organic framework, (EMIM)[Co2(hip)2(μ 3-OH)] (1), (H2hip = 5-hydroxyisophthalic acid and EMIM = 1-ethly-3-methylimidazolium), has been ionothermally synthesized and exhibits a two-dimensional bilayer structure constructed from tetranuclear [Co4(μ 3-OH)2] building units and hip linkers. The imidazolium cations [EMIM]+ acting as solvent and charge compensating agent located in the cavities of the bilayer framework.A new metal-organic network (EMIM)[Co2(hip)2(μ 3-OH)]·H2O (1), (H2hip = 5-hydroxyisophthalic acid and EMIM = 1-ethly-3-methylimidazolium), has been synthesized by the ionothermal reaction of cobalt nitrate, H2hip and [EMIM]Br ionic liquid. Single-crystal X-ray diffraction analysis reveals that 1 exhibits a two-dimensional (2D) bilayer constructed from tetranuclear [Co4(μ 3-OH)2] building units and hip2− linkers. There are square cavities with the dimension of 10.161 × 10.868 Å. The [EMIM]+ cations are located in the cavities, which have the hydrogen bonding interactions with the bilayer. Further more, the strong hydrogen bonds between the carboxylate and hydroxyl oxygen atoms of hip2− ligands and lattice water molecules extend the 2D layer into a 3D supramolecular network. The magnetic properties of 1 have been investigated by variable-temperature magnetic susceptibility and magnetization measurements, and the results reveal that there exist antiferromagnetic interactions.
Keywords: Ionothermal synthesis; Ionic liquid; Metal-organic framework; Tetra nuclear cobalt clusters;

A novel 2D copper(II) coordination polymer with bidentate coligands and alternating double EO- and single EE-azido bridges by Yan-Fei Wu; Dun-Ru Zhu; You Song; Kang Shen; Zhen Shen; Xuan Shen; Yan Xu (959-963).
A novel azido-bridged Cu(II) coordination polymer, [CuL(N3)2] n (1), (L  = 2-aminomethylpyridine), has been synthesized and structurally characterized. Complex 1 displays a 2D (6, 3) layered structure formed by alternating double EO- and single EE-azido bridges between Cu(II) ions. The complex also reveals an overall weak antiferromagnetic coupling between Cu(II) ions.A novel two-dimensional (2D) copper(II) coordination polymer, [CuL(N3)2] n (1) (L = 2-aminomethylpyridine), has been synthesized and characterized by elemental analysis, IR, X-ray crystallography and magnetic susceptibility. The complex crystallizes in space group P21/c with a  = 9.940(3), b  = 8.057(2), c  = 12.310(4) Å, β  = 104.119(4)°, V  = 956.1(5) Å3, Z  = 4, with final R  = 0.0543. The copper(II) ion in 1 is coordinated through two N atoms of the ligand L and four N atoms from the azido ligands in an elongated octahedron. The polymer consists of (6, 3) layers in which alternate double end-on (EO) and single end-to-end (EE) N 3 - bridging modes are found. The pyridine rings coming from adjacent layers are stacked by ππ interactions. Magnetic measurements reveal a weak antiferromagnetic exchange between copper(II) ions in 1.
Keywords: Copper(II) complex; Azido ligand; Crystal structure; Magnetic property; Coordination polymer; π–π interactions;

Copper-mediated intramolecular oxidative N-dealkylation of a bis(ferrocenyl)pyridyl ligand by Sk.Md. Nasiruzzaman; Pattubala A.N. Reddy; Tae-Jeong Kim (964-968).
Novel copper-mediated N-dealkylation in a bis(ferrocenyl)pyridyl ligand Bis(ferrocenyl)pyridyl diamide shows intramolecular N-dealkylation as well as N-oxidation in the presence of copper perchlorate in air, while the phenyl analogue shows no reaction.Spontaneous reduction of copper(II) by a bis(ferrocenyl)pyridyl diamide ligand was observed which causes a novel intramolecular N-dealkylation as well as N-oxidation in air. Also observed was the unusual formation of vinyl ferrocene which was confirmed by HPLC and mass spectral techniques. Interestingly, the phenyl analogue of the pyridyl ligand does not show any such transformation. The absorption spectral and electrochemical properties were also reported.
Keywords: Bis(ferrocene)amides; Copper complexation; Dioxygen activation; N-dealkylation;

A novel luminescent 3D metal–organic framework possessing 4-fold interpenetrating (3,4)-connected net by Guang-Juan Xu; Ya-Hui Zhao; Kui-Zhan Shao; Gang Yuan; Zhong-Min Su; Li-Kai Yan (969-971).
A novel 3D polymer [Zn(L1)(1,4-BDC)0.5] (1) (HL1  = 3,5-bis(pyridin-4-ylmethoxy)benzoic acid, 1,4-BDC = 1,4-benzenedicarboxylate anion) has been isolated under hydrothermal condition and characterized by single crystal X-ray diffraction. Compound 1 displays a 3D 4-fold interpenetrating (3,4)-connected net with (4 · 82)(4 · 85) topology. In addition, powder X-ray diffraction, photoluminescent property and thermogravimetric analysis for 1 are investigated in detail.A novel 3D polymer [Zn(L1)(1,4-BDC)0.5] (1) (HL1  = 3,5-bis(pyridin-4-ylmethoxy)benzoic acid, 1,4-BDC = 1,4-benzenedicarboxylate anion) has been isolated under hydrothermal condition and characterized by single crystal X-ray diffraction. Compound 1 displays a 3D 4-fold interpenetrating (3,4)-connected net with (4 · 82)(4 · 85) topology. In addition, powder X-ray diffraction, photoluminescent property and thermogravimetric analysis for 1 are investigated in detail.
Keywords: Coordination polymer; 3,5-Bis(pyridin-4-ylmethoxy)benzoic acid; Crystal structure; Photoluminescent property;

Two new azide complexes, [Cd2(3-abpt)(N3)4] n (1) and [Cu(3-abpt)2(N3)2] (2) (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole), have been prepared and structurally characterized. Complex 1 displays an interesting 2D polymeric structure with rarely reported 3,7-connected (32;4)(34;46;56;65) network in the Schafli notation. Complex 2 contains mononuclear pieces, and they are linked each other through weak Cu⋯N interactions and intra-molecular hydrogen bonds to form a 2D sheet with (4, 4) topology.Two new azide complexes, [Cd2(3-abpt)(N3)4] n (1) and [Cu(3-abpt)2(N3)2] (2) (3-abpt = 4-amino-3,5-bis(3-pyridyl)-1,2,4-triazole), have been prepared and structurally characterized. Complex 1 displays an interesting 2D polymeric structure with rarely reported 3,7-connected (32;4)(34;46;56;65) network in the Schafli notation. Complex 2 contains mononuclear pieces, and they are linked each other through weak Cu⋯N coordination bonds to form a 2D sheet with (4, 4) topology. The thermal stability and fluorescent property of 1 have also been investigated.
Keywords: 4-Amino-3,5-bis(3-pyridyl)-1,2,4-triazole; Azide; Coordination polymer; Crystal structure; Topology; Fluorescence;

Synthesis, crystal structure and photoelectric property of two novel coordinated complexes constructed by 4,4′-bipyridine and sebacic acid by Yan Xie; Yong-Heng Xing; Zhuo Wang; Hai-Yan Zhao; Xiao-Qing Zeng; Mao-Fa Ge; Shu-Yun Niu (975-977).
The single-crystal X-ray diffraction showed that both complexes crystallized in monoclinic system, space group P21 /c, and isomorphous. Sebacate ligand displays a μ3o 2o 1o 1-bridging fashion linking Ni(II)/Co(II) atoms to generate an infinite 1D chain along the a axis. Then the adjacent chains are connected by 4,4′-bipy ligands to form a 2D layer in the ac plane.Two two-dimensional (2D) new complexes: [M(bpy)(C10H16O4)H2O] [M = Ni (1), Co (2); bpy = 4,4-bipyridine, C10H18O4  = sebacic acid] were synthesized by the hydrothermal reaction at 180 °C and characterized by elemental analysis, infrared spectra, and thermogravimetric spectra, single-crystal X-ray diffraction and surface photovoltage spectrum (SPS). The single-crystal X-ray diffraction showed that both complexes are isomorphous, crystallized in monoclinic system, and space group P21/c. In addition, The results of SPS for complexes (1) and (2) indicate that these two complexes exhibit positive surface photovoltage response in the range of 300–800 nm, which can be assigned to LMCT and d → d electronic transition. The SPS spectra of the two complexes are consistent with their UV–Vis spectra.
Keywords: Sebacic acid; Crystal structures; Surface photovoltage spectrum; Lanthanide coordination polymer;

Colorimetric detection of cyanide in water using a highly selective Cu2+ chemosensor by Paramjit Kaur; Sandeep Kaur; Kamaljit Singh (978-981).
In this manuscript, we report that easily available N,N-dimethyldipyrromethane (1) demonstrates a high chromogenic selectivity for Cu2+ over other cations with detection limit 4.76 ppm. The complex of Cu2+ with 1 displayed ability to detect up to 6.5 ppm CN from water. Both the processes proceed with distinct visual color changes.In this manuscript, we report that easily available N,N-dimethyldipyrromethane (1) demonstrates a high chromogenic selectivity for Cu2+ over other cations with detection limit 4.76 ppm. The complex of Cu2+ with 1 displayed ability to detect up to 6.5 ppm CN from water. Both the processes proceed with distinct visual color changes.
Keywords: Dipyrromethane; Chemosensor; Copper; Cyanide; Selectivity;

Three lanthanide coordination polymers, [Ln(Hpdc)(ox)0.5(H2O)2]·H2O (Ln = Nd(1), Eu(2), Er(3)) (H3pdc = 3,5-pyrazoledicarboxylic acid, ox = oxalate), have been synthesized by the hydrothermal reaction of lanthanide nitrates, 3,5-pyrazoledicarboxylic acid, and oxalic acid (H2ox) and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that complexes 13 are isomorphous and exhibit three-dimensional metal–organic frameworks with uncommon (4,5)-connected topology.Three lanthanide coordination polymers, [Ln(Hpdc)(ox)0.5(H2O)2]·H2O (Ln = Nd(1), Eu(2), Er(3)) (H3pdc = 3,5-pyrazoledicarboxylic acid, ox = oxalate), have been synthesized by the hydrothermal reaction of lanthanide nitrates, 3,5-pyrazoledicarboxylic acid, and oxalic acid (H2ox) and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. Single-crystal X-ray diffraction studies indicate that complexes 13 are isomorphous and exhibit three-dimensional metal–organic frameworks with uncommon (4,5)-connected topology, which contain open channels occupied by the lattice water molecules. The photoluminescent properties of complex 2 were also studied.
Keywords: Coordination polymer; Hydrothermal synthesis; Lanthanide; Photoluminescent properties;

A novel metal–organic framework [Zn(TPT)(MPDCO)(H2O)·H2O]n (TPT = 1,2,3,4-tetra(4-pyridyl) thiophene, MPDCO = 6-methylpyridine-2,4-dicarboxylic acid N-oxide) (1) was obtained via hydrothermal synthesis and structurally characterized. It exhibits efficient blue luminescence at room temperature, and the framework is stable below 235 °C.A novel metal–organic framework (MOF) [Zn(TPT)(MPDCO)(H2O)·H2O]n (TPT = 1,2,3,4-tetra (4-pyridyl)thiophene, MPDCO = 6-methylpyridine-2,4-dicarboxylic acid N-oxide) (1) was obtained via hydrothermal synthesis and characterized by the elemental analysis, IR spectroscopy, TG analysis, luminescent spectroscopy and single-crystal X-ray diffraction analysis. Single-crystal structural analysis reveals that a one-dimensional (1-D) ladderlike MOF is constructed through the mixed ligands, and it is further connected by the intermolecular hydrogen bonds to form a 3-D supramolecular network. Complex 1 exhibits efficient blue luminescence at room temperature, and the framework is stable below 235 °C.
Keywords: Zinc(II) complex; Crystal structure; Metal–organic framework; Luminescence;

New (κ2-C,N)-palladacyclic complexes with benzimidazol-2-ylidene ligand: Synthesis, crystal structures and characterization by M. Emin Günay; Rukiye Gümüşada; Namık Özdemir; Muharrem Dinçer; Bekir Çetinkaya (990-993).
Reaction of unsymmetrical benzimidazolium bromides with Ag2O and subsequent transmetallation with chloro-bridged dinuclear palladacycle, [Pd(dmba)(μ-Cl)]2 (dmba: N,N-dimethylbenzylamine) afforded benzannulated monocarbene complexes [Pd(dmba)(NHC)Cl].Reaction of unsymmetrical benzimidazolium bromides (1) with Ag2O and subsequent transmetallation with chloro-bridged dinuclear palladacycle, [Pd(dmba)(μ-Cl)]2 (dmba: N,N-dimethylbenzylamine) afforded benzannulated monocarbene complexes [Pd(dmba)(NHC)Cl], 2. The palladacycles (2ac) were characterized by elemental analysis; NMR spectroscopy and the molecular structure of 2a and 2c were determined by X-ray crystallography.
Keywords: Palladacycles; N-heterocyclic carbene; Unsymmetrical benzimidazolium salt; Crystal structure;

Synthesis, structure and dielectric constant properties of a novel 1D coordination polymer[K(2-PTA)(H2O)] n by Da-Wei Fu; Jia-Zhen Ge; Jing Dai; Heng-Yun Ye; Zhi-Rong Qu (994-997).
Solvothermal treatment of KOH and 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl) acetic acid at 140 °C for 3 days produced a 1D metal–organic framework [K(2-PTA)(H2O)] n (1) in which [KO2] n chain acts as inorganic skeleton. The compound 1 shows a maximum ε 1 value 38.9 (200 Hz), which drops to 4.6 at a relatively high frequency of 1 MHz.The fern-like 1D coordination polymer, [K(2-PTA)(H2O)] n (1), which is constructed by an inorganic skeleton chain [KO2] n with organic 2-PTA wings on both sides, has been synthesized and characterized by single crystal X-ray crystallography and dielectric constant (ε) measurement (2-PTA = 2-(5-(pyridin-2-yl)-2H-tetrazol-2-yl) acetic acid). The ε of temperature dependence maintains unchanged, and ε of frequency dependence shows a significant decline, which is attributed to the highly ordered polarization mechanism.
Keywords: K(I) complex; Metal–organic framework; Dielectric constant; Atomic polarization; Displacement polarization; Ordered;

Direct synthesis and characterization of novel homo- and heterometallic mixed-ligand tetrazolate complexes, Cu(en)(tz)2 and Cu(en)2Zn(tz)4 [en = ethylenediamine, tz = tetrazolate] by Anastasiya P. Mosalkova; Sergei V. Voitekhovich; Alexander S. Lyakhov; Ludmila S. Ivashkevich; Mikhail M. Degtyarik; Pavel N. Gaponik; Oleg A. Ivashkevich (998-1000).
Two novel homo- and heterometallic mixed-ligand complexes, Cu(en)(tz)2 and Cu(en)2Zn(tz)4, have been prepared using Htz, en, Cu0 and ZnO as starting materials under direct synthesis conditions. The complexes present 1D coordination polymers with tetrazolate units acting as both N1-monodentate and N1,N4-bridging ligands.For the first time, tetrazolate complexes have been prepared by direct synthesis. Two novel homo- and heterometallic mixed-ligand complexes, Cu(en)(tz)2 and Cu(en)2Zn(tz)4, have been synthesized using tetrazole (Htz), ethylenediamine (en), metallic copper and zinc oxide as starting materials. Both tetrazolates were characterized by single-crystal X-ray diffraction, IR spectroscopy and thermal analysis. The complexes present 1D coordination polymers, with tetrazolate anions acting as both monodentate and bridging ligands.
Keywords: Tetrazole; Direct synthesis; Copper(II) complexes; Zinc complexes; Heterometallic complexes;

Synthesis and characterization of a homoleptic titanium dihydrobis(pyrazol-1-yl)borate complex by Gino Paolucci; Marco Bortoluzzi; Laura Sperni (1001-1003).
The titanium(III) complex Ti(BP)3 {BP = dihydrobis(pyrazol-1-yl)borate} has been synthesized and characterized. 11B NMR data suggested a distortion from the ideal octahedral geometry caused by the d1 electronic configuration of the metal centre and this hypothesis has been confirmed by means of DFT calculations.The neutral titanium(III) complex Ti(BP)3 {BP = dihydrobis(pyrazol-1-yl)borate} was synthesized by reacting TiCl3(THF)2 with an excess of the potassium salt of the ligand in THF. The compound was isolated as a green solid and characterized by elemental analysis, NMR and IR spectroscopy, Mass spectrometry and magnetic and conductivity measurements. The molecular ion was detected in the Mass spectrum. 11B NMR data suggested a distortion from the ideal octahedral geometry caused by the d1 electronic configuration of the metal centre and this hypothesis was confirmed by means of DFT calculations.
Keywords: Titanium; Dihydrobis(pyrazol-1-yl)borate; Boron NMR spectroscopy; DFT; Nitrogen ligands;

A chiral diamine bis-phenolate complex of dioxomolybdenum(VI) by Rathna Durga R.S. Manian; Reko Leino; Oula Wichmann; Ari Lehtonen (1004-1006).
A new chiral tetradentate ligand reacts with [MoO2(acac)2] to form a monomeric complex. The syntheses and X-ray crystal structures of the ligand and the complex are reported.A new dioxomolybdenum(VI) complex with a chiral tetradentate ligand is reported. The tripodal ligand containing two nitrogen atoms and two phenolic oxygen atoms was synthesized starting from a chiral diamine precursor. Further reaction with [MoO2(acac)2] yielded a monomeric molybdenum complex as a bright yellow solid. The structures of the molybdenum complex and the free diamine bis-phenol ligand were determined by X-ray diffraction.
Keywords: Molybdenum; Oxo complexes; Phenolate ligands; Chiral ligands;

A novel coordination polymer [Co(BTB)2(NCS)2] n {BTB = 1,4-bis(1,2,4-triazol-1-yl)butane} was prepared and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR and TG-DSC. 1D chains and 2D sheets bridged through BTB in three different configurations interpenetrate in an inclined fashion in the structure.A novel polymeric cobalt(II) complex with flexible ligand, [Co(BTB)2(NCS)2] n 1 {BTB = 1,4-bis(1,2,4-triazol-1-yl)butane} has been prepared and structurally characterized by single-crystal X-ray diffraction as well as with elemental analysis, infrared spectroscopy and thermogravimetric analysis. The complex 1 consists of two discrete constituents, A and B, with the same chemical formula [Co(BTB)2(NCS)2] but different connecting mode. The six-co-ordination of Co2+ in A and B is in a distorted octahedral environment formed by four nitrogen atoms of the triazoles and two nitrogen atoms from two trans thiocyanato ligands. The structures of A and B demonstrate a one-dimensional neutral looped chain through two BTB-bridges and a two-dimensional network in which four BTB bridge four Co(II) atoms, respectively. A and B interpenetrate in an inclined fashion. The flexible BTB ligand exhibits three different configurations in 1.
Keywords: Cobalt(II); BTB bridge; Crystal structure; Interpenetration;

Two novel d10 frameworks based on a new V-shaped ligand 2,4′-dipyridylamine and a flexible dicarboxylate ligand by Wei-Hong Zhang; Yao-Yu Wang; Chen Ren; Gui-Lin Wen; Chun-Yan Guo; Qi-Zhen Shi (1011-1015).
Via hydrothermal synthesis, the self-assembly of d10 metal, 2,4′-dipyridylamine (L) and 1,3-adamantanediacetic acid (H2ADA) generated two unprecedented coordination polymers [Zn(ADA)(L)] n (1) and [Cd(ADA)(L)2] n (2). Complex 1 possesses a novel 1D looped-chain topology structure decorated with arms. Complex 2 shows an extended threaded framework involving 2D coordination layers of square (44) topology with dangling ligands, which gives the novel (2D → 3D) polythreaded array. To the best of our knowledge, complex 2 is the first example with four dangling arms coordinated in the axial sites of dinuclear nodes. Via hydrothermal synthesis, the self-assembly of d10 metal, 2,4′-dipyridylamine (L) and 1,3-adamantanediacetic acid (H2ADA) generated two unprecedented coordination polymers [Zn(ADA)(L)] n (1) and [Cd(ADA)(L)2] n (2). Complex 1 possesses a novel 1D looped-chain topology structure decorated with arms. Complex 2 shows an extended threaded framework involving 2D coordination layers of square (44) topology with dangling ligands, which gives the novel (2D → 3D) polythreaded array. To the best of our knowledge, complex 2 is the first example with four dangling arms coordinated in the axial sites of dinuclear nodes. In addition, both of the complexes show strong photoluminescence at room temperature, and may be good candidates for potential luminescence materials.
Keywords: Coordination polymer; V-shaped ligand; Fluorescence spectrum; Crystal engineering;

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex by Zhenjun Si; Xiaona Li; Xiyan Li; Chengling Pan; Hongjie Zhang (1016-1019).
[Cu(ABPQ)(DPEphos)]BF4 is synthesized, and its photophysical properties are experimentally and theoretically studied.A novel diimine Cu(I) complex [Cu(ABPQ)(DPEphos)]BF4 [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h;3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF4 are attributed to the ligand-centered π → π* transition and the metal-to-ligand charge transfer dπ(Cu) → π*(N–N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF4 in CHCl3 is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF4.
Keywords: Cu(I) complex; TDDFT; Synthesis; Photoluminescence;

A novel three-dimensional indium phosphite-oxalate hybrid material with intersecting 8-MRs and 12-MRs channels has been prepared under hydrothermal conditions by using 1,4-diazabicyclo[2.2.2]octane (dabco) as structure direct agents.A novel anionic three-dimensional indium phosphite-oxalate hybrid material, formulated as |C6H14N2|[In2(HPO3)3(C2O4)] (1) was prepared under hydrothermal conditions by using 1,4-diazabicyclo[2.2.2]octane (dabco) as a structure directing agent (SDA). Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in the orthorhombic system space group Pna21 (No. 33) having unit cell parameters a  = 12.4143(13) Å, b  = 7.7166(8) Å, c  = 18.327(2) Å, V  = 1755.6(3) Å3, and Z  = 4 with R 1  = 0.0282, wR 2  = 0.0632. The novel 3D open framework is constructed from InO6 octahedra, HPO3 pseudo-tetrahedra and C2O4 units. The assembly of these building units generates intersecting 8- and 12-membered ring (MR) channels along two different directions. To the best of our knowledge, it is the first reported indium phosphite-oxalate hybrid material. Further characterization of compound 1 was performed using X-ray powder diffraction (XRD), infrared (IR) spectra, thermal gravimetric analyses (TGA), inductively coupled plasma (ICP) and elemental analyses.
Keywords: Hydrothermal synthesis; Hybrid material; Indium phosphite-oxalate; Intersecting channels; Helical chain;

A new (3,4,7)-connected topology framework based on [Cd2(CO2)3O4N2] second building unit by Guang-Juan Xu; Ya-Hui Zhao; Kui-Zhan Shao; Lei Chen; Hong-Ying Zang; Zhong-Min Su; Dong-Ying Du (1024-1026).
A new 3D coordination polymer [Cd2(L3)(BTC)(H2O)] has been synthesized under hydrothermal conditions. The L3 and BTC ligands linked CdII atoms to build Cd2-based second building units [Cd2(CO2)3O4N2] and further form a (3,4,7)-connected net. The photoluminescent spectra indicate that it may be a good candidate for blue-luminescent materials.A new 3D coordination polymer [Cd2(L3)(BTC)(H2O)] (1) (HL3  = 3,5-bis(pyridin-3-ylmethoxy)benzoic acid, H3BTC = 1,3,5-benzenetricarboxylic acid), has been isolated under hydrothermal condition and characterized by single-crystal X-ray diffraction. Compound 1 is constructed from Cd2-based second building units (SBUs) [Cd2(CO2)3O4N2] and displays a 3D (3,4,7)-connected net with (42·6)(43·63)(45·611·85) topology. In addition, the photoluminescent spectra indicate compound 1 may be a good candidate for blue-luminescent materials.
Keywords: Coordination polymer; Flexible ligand; Crystal structure; Photoluminescent property;

A novel 3D CdII-coordination framework with helical units in a mixed flexible ligand system: Encapsulating right-handed helical water chains by Dong-Sheng Li; Mei-Li Zhang; Jun Zhao; Dan-Jun Wang; Peng Zhang; Ni Wang; Yao-Yu Wang (1027-1030).
In flexible co-ligand system, the P-handed [Cd(bpb)] n and the M-handed [Cd(pda)] n helical chains interweave mutually into a novel 3D coordination framework with diamondoid skeleton, namely, {[Cd(1,4-pda)(bpb)(H2O)]·H2O} n (1) [bpb = 1,4-bi(4-pyridyl)butane , 1,4-H2pda = 1,4-phenylenediacetic acid ]. Interestingly, 1D hydrophilic tunnel of 1 acts as a template for the formation of the P-handed 1D helical water chains, displaying molecular recognition and chirality transfer. The photoluminescent property and thermal stability of 1 were also discussed.In flexible co-ligand system, the P-handed [Cd(bpb)] n and the M-handed [Cd(pda)] n helical chains interweave mutually into a novel 3D coordination framework with diamondoid skeleton, namely, {[Cd(1,4-pda)(bpb)(H2O)]·H2O} n (1) [bpb = 1,4-bi(4-pyridyl)butane , 1,4-H2pda = 1,4-phenylenediacetic acid ]. Interestingly, 1D hydrophilic tunnel of 1 acts as a template for the formation of the P-handed 1D helical water chains, displaying molecular recognition and chirality transfer. The photoluminescent property and thermal stability of 1 were also discussed.
Keywords: CdII-coordination framework; Helical unit; Water chain; Luminescence;

Two 1D [Cu x I x ]-based coordination polymers of tetraphosphine ligands by Ni-Ya Li; Zhi-Gang Ren; Dong Liu; Jing Wang; Ming Dai; Hong-Xi Li; Jian-Ping Lang (1031-1034).
Two 1D [Cu x I x ]-based coordination polymers [Cu2I2(dppeda)]·2MeCN (dppeda = N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine)) and [Cu4I4(dpppda)]·MeCN (dpppda = 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine) were isolated from solvothermal reactions of CuI with dppeda or dpppda. Both complexes were structurally characterized by elemental analysis, IR, 1H and 31P{1H}, and X-ray crystallography and their stability in solution and in solid state were studied by ESI-MS and thermogravimetric analysis.Diffusion reactions of CuI with N,N,N′,N′-tetra(diphenylphosphanylmethyl)ethylene diamine) (dppeda) and 1,4-N,N,N′,N′-tetra(diphenylphosphanylmethyl)benzene diamine (dpppda) in MeCN/toluene in a zigzag glass tube or solvothermal reactions of CuI and dppeda or dpppda in MeCN produced two [Cu x I x ]-based coordination polymers, [Cu2I2(dppeda)]·2MeCN (1·2MeCN) and [Cu4I4(dpppda)]·MeCN (2·MeCN), respectively. Both compounds were characterized by elemental analysis, IR spectroscopy, 1H and 31P{1H} NMR, ESI-MS and thermogravimetric analysis, and their structures were determined by single crystal X-ray diffraction. In 1, [Cu2I2] cores are interconnected by dppeda ligands in a μ-η 2:η 2 end-to-end mode to form a 1D chain, while in 2 stair-like [Cu4I4] cores are linked by dpppda ligands in a unique Z-shaped μ-η 2:η 2 side-by-side mode to produce the other kind of 1D chain.
Keywords: Copper(I); Coordination polymer; Tetraphosphine; Crystal structure;

A zirconium-containing sandwich-type dimer based on trivacant α- and β-[GeW9O34]10− units, [Zr3O(OH)2(α-GeW9O34)(β-GeW9O34)]12− by Lili Chen; Lili Li; Bin Liu; Ganglin Xue; Huaiming Hu; Feng Fu; Jiwu Wang (1035-1037).
The sandwich-type polyanion [Zr3O(OH)2(α-GeW9O34)(β-GeW9O34)]12− contains two different isomer subunits and there are three oxygen atoms alternating with the three zirconium atoms in the central bent.A new zirconium-containing sandwich-type dimer based on trivacant α- and β-[GeW9O34]10− units, [Zr3O(OH)2(α-GeW9O34)(β-GeW9O34)]12−, was synthesized and characterized by IR spectroscopy, UV electronic spectroscopy and single crystal X-ray diffraction. The central bent of the polyanion contains three oxygen atoms alternating with the three zirconium atoms. The polyanion represents a rare example of the sandwich POMs containing two different isomer subunits.
Keywords: Polyoxometalates; Isomer; Zirconium; Sandwich-type;

Two novel HgII and MnII supramolecular complexes with a versatile multidentate ligand showing different isomeric styles and coordination modes are described, which notably are obtained by in situ ligand reaction from an acyclic precursor.Reaction of potassium N′-(pyridine-4-carbonyl)-hydrazinecarbodithioate ([K+(H2 L)]) with HgII or MnII inorganic salt in the presence of 1,10-phenanthroline (phen) or 4,4′-bipyridine (bipy), yields complexes [Hg(pyt)2(phen)] (1) and {[Mn(pyt)2(H2O)2]·(bipy)·(H2O)2} n (2), in which the pyt ligand (Hpyt = 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol) is obtained by in situ ligand formation from the acyclic precursor [K+(H2 L)]. Single crystal X-ray diffraction suggests that the pyt anionic ligands in 1 and 2 behave as thiolate and thione isomers, respectively, and display S- and μ-N pyridyl, N oxadiazole-binding fashions. Complex 1 shows a 1-D fishbone-like supramolecular array via strong aromatic stacking interactions between the discrete mononuclear coordination motifs, whereas 2 has a 2-D layered host coordination framework with the inclusion of bipy and water guests in the cavities.
Keywords: HgII and MnII complexes; In situ ligand synthesis; Crystal structures; Supramolecular architectures; Thermal stability;

A new synthetic route towards a Ru(III) substituted heteropolytungstate anion by Claire Besson; Su-Wen Chen; Richard Villanneau; Guillaume Izzet; Anna Proust (1042-1044).
Microwave irradiation of K7[PW11O39] 14H2O and [Ru(dmf)6](CF3SO3)3 allowed the synthesis of [PW11O39RuIII(OH2)]4−. This study provides a complete set of spectroscopic and electrochemical references for RuIII-incorporating heteropolytungstatesMicrowave irradiation of a mixture of K7[PW11O39]·14H2O and [Ru(dmf)6](CF3SO3)3 allowed the straightforward hydrothermal synthesis of the Keggin-type [PW11O39RuIII(OH2)]4− anion. Physical characterizations of the corresponding tetrabutylammonium (TBA) salt are herein described. This study provides a complete set of spectroscopic and electrochemical references for RuIII-incorporating heteropolytungstates.
Keywords: Ruthenium; Polyoxometalates; EPR spectroscopy; XANES; Microwave activation;

Surface-modified aluminogermanate nanotube by OPA: Synthesis and characterization by Bui Hoang Bac; Yungoo Song; Myung Hun Kim; Young-Boo Lee; Il Mo Kang (1045-1048).
The surface of the synthesized short, single-walled aluminogermanate nanotube [(HO)3Al2O3GeOH] was successfully modified by using an amphiphilic molecule, octadecylphosphonic acid [CH3(CH2)17PO(OH)2] (OPA).In this study, the surface of the synthesized short, single-walled aluminogermanate nanotube was modified by using an amphiphilic molecule, octadecylphosphonic acid (OPA). The synthetic products were characterized by using X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and thermogravimetric analysis (TGA). The obtained evidences indicated that the alkyl chains of OPA were successfully absorbed on the surface of aluminogermanate nanotube. This modification is useful for applying the aluminogermanate nanotube to producing potential polymer nanocomposite.
Keywords: Aluminogermanate; Nanotube; OPA; Surface modification;

Syntheses, characterization and biological activity of diorganotin(IV) derivatives of 2-amino-6-hydroxypurine (guanine) by Mala Nath; Hitendra Singh; George Eng; Xuequing Song; Ashok Kumar (1049-1052).
Novel diorganotin(IV) derivatives of guanine have been synthesized by the reaction of R2SnCl2 with sodium salt of guanine. The polyhedron around tin in R2Sn(HGu)2 is distorted trigonal–bipyramidal or pseudo-tetrahedral involving very weak interaction from C=O group of neighboring molecule leading to polymerized structure. All the compounds exhibited potent anti-inflammatory activity with no appreciable side effects on blood pressure as evidenced by their very mild cardiovascular activity.Novel organotin(IV) derivatives of guanine of the general formula, R2Sn(HGu)2 (where, R = Me (1), n-Bu (2) and Ph (3)) have been synthesized by the reaction of R2SnCl2 with sodium salt of guanine (H2Gu or 2-amino-6-hydroxypurine). The IR spectral studies suggest that guanine acts as a monobasic ligand coordinating through N(9) after its deprotonation. The weak bonding through C(6)=O may also be evidenced, whereas 119Sn Mössbauer data suggest that the coordination number of tin is superior than four. The polyhedron around tin in R2Sn(HGu)2 is distorted trigonal–bipyramidal or pseudo-tetrahedral involving very weak interaction from C=O group of neighboring molecule leading to polymerized structure. All the compounds exhibited potent anti-inflammatory activity with no appreciable side effects on blood pressure as evidenced by their very mild cardiovascular activity.
Keywords: 2-Amino-6-hydroxypurine; Anti-inflammatory activity; Cardiovascular activity; Organotin(IV); 119Sn Mössbauer;

Two-dimensional assembly of the type Cd10Te4 thiolate cluster with 4,4′-trimethylenedipyridine by Chao Xu; Yan-Gong Han; Taike Duan; Qian-Feng Zhang; Wa-Hung Leung (1053-1056).
A new inorganic–organic hybrid polymeric cluster {Cd10Te4(SC6H4Me-p)12(tmdp)2} n with a unique two-dimensional super-structure was solvothermally synthesized and structurally characterized.Cadmium tellurium cluster molecule [Cd10Te4(SC6H4Me-p)12] and bifunctioanal organic ligand 4,4′-trimethylenedipyridine (tmdp) are joined together through metal–ligand coordination bonds, forming a new inorganic–organic hybrid polymeric cluster {Cd10Te4(SC6H4Me-p)12(tmdp)2} n (1) with a unique two-dimensional super-structure. The room temperature absorption and the diffuse reflectance UV–Vis spectra along with the photo-luminescence behavior were determined in the solid state. The thermal stability of the polymeric cluster was studied by thermal gravimetric analysis.
Keywords: Cadmium; Tellurium; Cluster compound; Crystal structure; Solvothermal synthesis; 4,4′-Trimethylenedipyridine;

The molecular configuration of complex 1 is described as a windmill, observing along the [0 0 1] direction. The line through Fe1 and Fe1A atoms is the axis with four benzene rings being wings.A novel tetranuclear silver(I) heterocyclic cluster, which is of nano-hole structure, based on 1,1′-bis[(2-hydroxybenzylidene)thiocarbonohydrazono-1-ethyl] ferrocene (FcL) has been prepared and structurally characterized by single-crystal X-ray diffractions. In addition, its electrochemical properties are also discussed. The results confirm that the receptor FcL is responsive to Ag+.
Keywords: Silver complex; Ferrocene derivative; Crystal structure; Electrochemical properties;

Diplatinum(III) [ Pt 2 III Cl2(μ 2-amidinate)4] compound derived from air oxidation of mononuclear cis-[PtII(NH3)2(amidine-κ 1)2]2+ complex by Nadezhda A. Bokach; Marina R. Tyan; Grigory G. Aleksandrov; Matti Haukka; Vadim Yu. Kukushkin (1061-1063).
Complex [Pt2Cl2{μ 2-N(H)C(Et)N(H)}4], which represents the second PtIII dimer stabilized by the amidinate ligand ever known, has been prepared by heating cis-[Pt(NH3)2{NH=C(NH2)Et}2](Cl)2 under aeration conditions in an EtOH/H2O mixture.The dinuclear platinum(III) complex [Pt2Cl2{μ 2-N(H)C(Et)N(H)}4] (2) has been prepared by heating cis-[Pt(NH3)2{NH=C(NH2)Et}2](Cl)2 (cis-1) under aeration conditions in an EtOH/H2O mixture at 70 °C for 2 d and it was characterized by elemental analyses (C, H, N), ESI+-MS, IR, 1H and 13C NMR spectroscopies and also by X-ray diffraction. Complex 2 represents the second PtIII dimer stabilized by the amidinate ligand ever known and it has a lantern-type structure with four amidinate ligands bridging two PtIII centers with Pt–Pt distance of 2.4809(2) Å.
Keywords: Dinuclear complexes; Platinum(III); Platinum–platinum bond; Bridging ligands; Amidinates; Oxidation;

Photoinduced linkage isomerism of binuclear bis(pyrazole-3,5-dicarboxylato)-bridged {RuNO}6 centres by Anna Zangl; Peter Klüfers; Dominik Schaniel; Theo Woike (1064-1066).
The pyrazole-3,5-dicarboxylato ligand is able to bridge two {RuNO}6 centres to binuclear complexes. The figure shows the crystallographically characterised nitrosyl aqua complex. Metastable photoinduced linkage isomers were detected in both this aqua complex and its chlorido analogue by means of IR spectroscopy after laser irradiation at low temperatures.The two novel binuclear pyrazole-3,5-dicarboxylato-bridged {RuNO}6 complexes K2[{Ru(NO)Cl}2(μ-pzdc)2] (1) and [{Ru(NO)(H2O)}2(μ-pzdc)2]·4H2O (2) (pzdc = pyrazole-3,5-dicarboxylate) were synthesized and characterized by elemental analysis, mass spectrometry and spectroscopic methods (NMR, UV–vis, IR). 2 was investigated by means of single-crystal X-ray diffraction analysis. On irradiation, in both 1 and 2 the existence of photoinduced long-lived metastable isonitrosyl states SI were detected by low-temperature infrared spectroscopy.
Keywords: Photoinduced linkage isomerism; Ruthenium; Nitrosyl ligands; Pyrazole-type ligands;

Novel indium(III) complexes with sterically hindered o-iminobenzoquinone by Alexandr V. Piskunov; Irina N. Mescheryakova; Artyem S. Bogomyakov; Galina V. Romanenko; Vladimir K. Cherkasov; Gleb A. Abakumov (1067-1070).
The first examples of indium(III) derivatives based on 4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzoquinone (imQ) were synthesized. The interaction of sodium o-iminobenzosemiquinolate with indium(III) iodide produces bis[4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzosemiquinonato]-iodo-indium(III) (1). The interaction of imQ with InI3 results in the formation of indium(III) compound (2) containing neutral form of o-iminobenzoquinone ligand.The first examples of indium(III) derivatives based on sterically hindered 4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzoquinone (imQ) were synthesized and characterized in details. The interaction of sodium o-iminobenzosemiquinolate with indium(III) iodide produces bis[4,6-di-tert-butyl-N-(2,6-di-iso-propylphenyl)-o-iminobenzosemiquinonato]-iodo-indium(III) (1). The same product 1 was obtained by the reactions of imQ with InI or imQ disodium derivative with indium(III) iodide. The interaction of imQ with InI3 results in the formation of indium(III) compound (2) containing neutral form of o-iminobenzoquinone ligand. Structures of complexes 1 and 2 were determined by X-ray diffraction analysis.
Keywords: o-Iminoquinone; o-Iminobenzosemiquinone; Indium; Magnetochemistry; X-ray diffraction;

The structural characterization and hydroformylation activity of the tri-rhodium complex [Rh32-dppm)22-CO)3(K 1-CO)3]BF4 by Fabio Lorenzini; Eoghain O’Hara; Shimeng Qian; Fabio Marchetti; James M. Birbeck; Anthony Haynes; Alexander J. Blake; Graham C. Saunders; Andrew C. Marr (1071-1073).
Rh2(cod)22-dppm)(μ2-Cl)]BF4 rearranges under carbon monoxide to give [Rh32-dppm)22-CO)3(K 1-CO)3]BF4. The tri-rhodium complex has been structurally characterized by single crystal X-ray crystallography. The hydroformylation activities of the complexes were compared for substrates styrene and 1-hexene and the activity of tri-rhodium complex found to be unexpectedly high.Rh2(cod)22-dppm)(μ2-Cl)]BF4 (1) rearranges under carbon monoxide to give [Rh32-dppm)22-CO)3(K 1-CO)3]BF4 (2). Complex 2 has been structurally characterized by single crystal X-ray crystallography. The hydroformylation activities of 1 and 2 were compared for substrates styrene and 1-hexene and the activity of 2 found to be unexpectedly high.
Keywords: Binuclear; Trinuclear; Rhodium; Hydroformylation;

Dimethyltindichloride reacts with 1,5-diphenylthiocarbazone at a 2:1 ratio forming the complex [Sn(CH3)2(C12H11N4S)Cl]. The crystal structure shows that the tin(IV) atom adopts distorted trigonal bipyramidal geometry.The reaction of dimethyl tin dichloride with 1,5-diphenylthiocarbazone affords the complex [Sn(CH3)2(C12H11N4S)Cl]. Its X-ray structure reveals a five-coordinated Sn atom in distorted trigonal bipyramidal geometry. The complex has been additionally characterized by IR and UV–Vis spectroscopy. Geometry optimization calculations support the experimental data.
Keywords: Dimethyl tin dichloride; Dithizone; Organotin complex; Crystal structure;

Coordinationally driven and hydrogen-bonding directed self-assembly of 2,6-diformyl-4-methylphenol and tris(hydroxymethyl)aminomethane in the presence of copper(II) acetate and sodium azide formed an unprecedented 3D copper(II) coordination cluster {[(H5L)Cu2(μ-N3)]2[Cu(N3)4]·2CH3OH} n (1) comprised of double-stranded ladders involving repeating pentacopper building blocks. Complex 1 shows an overall antiferromagnetic spin-exchange interaction between metal centers.Reaction between 2,6-diformyl-4-methylphenol (DFMP) and tris(hydroxymethyl)aminomethane (THMAM) with copper(II) acetate and sodium azide formed the antiferromagnetically coupled, polymeric copper(II) coordination cluster {[(H5L)Cu2(μ-N3)]2[Cu(N3)4]·2CH3OH} n (1), with a novel double-stranded ladder like structure in which [Cu(N3)4]2− anions link single-chains comprised of dinuclear subunits, forming a 3D-structure of interconnected ladders through H-bonding. The 3D-structure is the result of coordinatively driven and hydrogen-bonding directed self-assembly.
Keywords: Copper(II) complex; Antiferromagnetically coupled; Ladder structure;

A 3-D bismuth–organic framework containing 1-D cationic inorganic [Bi2O2]2+ chains by Dat T. Tran; Deryn Chu; Allen G. Oliver; Scott R.J. Oliver (1081-1084).
A three-dimensional Bi(III) based metal–organic framework, bismuth oxide 3,5-pyridinedicarboxylate, Bi2O2[NC5H3(CO2)2], is described. The coordination framework contains 1-D cationic extended inorganic [Bi2O2]2+ chains that propagate along the crystallographic c-axis and link into a 3-D bismuth–organic framework.A three-dimensional Bi(III) based metal–organic framework was synthesized under hydrothermal conditions using the multidentate organic linker 3,5-pyridinedicarboxylate. Bismuth oxide 3,5-pyridinedicarboxylate, Bi2O2[NC5H3(CO2)2], contains embedded 1-D cationic bismuth oxide chains that propagate along the crystallographic c-axis. The oxygens of the Bi2O2 core are three-coordinate and bond strongly to the Bi atoms. Thermogravimetric analysis shows that the material possesses high thermal stability up ca. 400 °C before decomposing to phase-pure Bi2O3 at 800 °C. The structure, crystallinity, morphology and properties of the material are discussed.
Keywords: Metal–organic framework; Hydrothermal synthesis; 3,5-Pyridinedicarboxylate; 1-D bismuth oxide chains; 1-D extended inorganic chains; Bismuth–organic framework;