Inorganic Chemistry Communications (v.11, #7)

Contents List (iii-xi).

Three new isostructural three-dimensional Lanthanide coordination polymers, namely [Ln2(Ac)2(ip)2(H2O)4  · H2O] n [Ln = Gd(1), Sm(2), Nd(3)], where Ac = acetate, ip = isophthalate, present the second lanthanide-based, non-interpenetrating, decorated rutile net constructed from the six-connected dinuclear lanthanide SBUs and three-connected organic spacers, with the (4 × 62) (42  × 610  × 83)2 topology notation, which will enrich the family of non-interpenetrating decorated rutile nets.Three new three-dimensional Lanthanide coordination polymers, namely [Ln2(Ac)2(ip)2(H2O)4  · H2O] n [Ln=Gd(1), Sm(2), Nd(3)], where Ac = acetate, ip = isophthalate, have been synthesized in hydrothermal method and characterized by single-crystal X-ray diffraction. Compounds 13 are isostructural and crystallize in the monoclinic system, space group P2(1)/C. Thermogravimetry, infrared spectra, elemental analysis have also been used to characterize 1. From topological view, the compounds present the second lanthanide-based, non-interpenetrating, decorated rutile net with the (4 × 62)(42  × 610  × 83)2 topology notation. Notably, within them, (H2O)6 cluster formed by free and coordinated water molecules via H-bonds is observed; and based on the consideration of the average O⋯O distance and IR spectrums, it is similar to those of liquid water.
Keywords: Crystal engineering; Metal-organic framework; Network topology; Water cluster; Characterization;

A peculiar heterotrimetallic MnII–CoII–NiII complex: Synthesis, crystal structure and magnetic properties by Gong-Feng Xu; Bin Liu; Hai-Bin Song; Qing-Lun Wang; Shi-Ping Yan; Dai-Zheng Liao (714-716).
The first complex Mn(H2O)6[NiCo(TTHA)(H2O)2] · 4H2O 1 (TTHA6−  = triethylenetetraminehexaacetate) containing MnII–CoII–NiII three different 3d metal ions is synthesized and magnetic measurement suggests that ferromagnetic interactions occur between high-spin Ni2+ ions and rarely found low-spin Co2+ ions.The first complex [Mn(H2O)6][NiCo(TTHA)(H2O)2] · 4H2O 1 (TTHA6−  = triethylenetetraminehexaacetate) containing MnII–CoII–NiII three different 3d metal ions is synthesized and magnetic measurement suggests that ferromagnetic interactions occur between Ni2+ ions and rarely found low-spin Co2+ ions.
Keywords: Triethylenetetraminehexaacetic acid (H6TTHA); MnII–CoII–NiII complex; Crystal structure; Ferromagnetic interactions;

A cross-net-shaped metallamacrocycle was synthesized and characterized. In this complex, two opening 13-membered metallacrown rings and two strands, Mn–N–N–Mn, are bridged by eight μ-maleoyl groups. The high nuclearity of the system shows large magnetic moments.A novel cross-net-shaped metallamacrocycle, [ Mn 10 III Mn 4 II ( L ) 8 ( HL ) 2 ( H 2 O ) 2 ( CH 3 OH ) 14 ] · 8 H 2 O · 8 CH 3 OH (H4L = (Z)-3-(salicylhydrazinocarbonyl) propenoic acid), has been prepared and characterized. The crystal structure contains seven crystallographically unique manganese ions, in which two opening 13-membered metallacrown rings and two strands, Mn–N–N–Mn, are bridged by eight μ-maleoyl groups. The high nuclearity of the molecule shows large magnetic moments, with the value of μ eff at 300 K is 19.01 μB.
Keywords: Metallamacrocycle; Manganese complex; Crystal structure; Magnetic properties;

In a novel reaction two new C–C bonds were formed leading to cyclic ammonium salts when aluminum trichloride was treated with sodium dialkyldithiocarbamate in acetone.Sodium salts of N,N-dibenzyldithiocarbamate, N,N-diisopropyldithiocarbamate and pyrrolidine-1-carbodithioate gave cyclic products, 4-oxo-2,6-diphenyl-piperidinium, 2,2,6,6-tetramethyl-4-oxo-piperidinium and 3-oxo-8-azonia-bicyclo[3.2.1]octane cations, respectively, when treated with aluminum trichloride in acetone. The 2,2,6,6-tetramethyl-4-oxo-piperidinium thiocyanate salt has been characterized by X-ray crystallography. A plausible mechanism has also been suggested on the basis of preliminary DFT calculations.
Keywords: Aluminum trichloride; Dithiocarbamate; Ionic liquid; Desulfurization; Piperidinium;

Mn and Cu–Na coordination compounds containing the tetrazole-5-acetato anion (tza) ligands by Gao-Wen Yang; Qiao-Yun Li; Yi Zhou; Peng Sha; Yun-Sheng Ma; Rong-Xin Yuan (723-726).
The two new coordination compounds, [Mn(tza) · (H2O)2] n (1) and [CuNa2(tza)2  · (H2O)4] n (2) have been synthesized by the conventional aqueous solution synthesis. Compound 1 forming a 1D polymeric chain structure by tza bridging linker and compound 2 forming a 2D layer structure by tza seven-coordinated bridging ligand, which are further linked together via the hydrogen-bonding interactions to form 3D supramolecular framework.Two novel coordination compounds [Mn(tza) · (H2O)2] n (1) and [CuNa2(tza)2  · (H2O)4] n (2) (tza = tetrazole-5-acetato) were synthesized by reaction of tetrazole-5-ethyl acetate with Mn(ClO4)2  · 6H2O and CuCl2  · 2H2O in sodium hydroxide solution, respectively. Compound 1 has a one-dimensional (1D) polymeric chain that are bridged by tza linker, while compound 2 has two crystallographically independent metal centers (Cu and Na), that are bridged by tza into a 2D layer structure. The magnetic susceptibility study of 1 demonstrates the presence of antiferromagnetic interaction between two adjacent Mn(II) ions.
Keywords: Tetrazole; Manganese (II); Copper(II)–sodium(I); Crystal structure; Magnetic properties;

A novel supramolecular complex [(H4BTC)(TPT)] n (H4BTC = benzene-1,2,4,5-tetracarboxylic acid, TPT = 1,2,3,4-tetra(4-pyridlyl)thiophene) (1) was obtained via hydrothermal method. Single-crystal structural analysis reveals that it is a one-dimensional chain assembled through strong hydrogen bonds. Theoretical calculations have been performed on the crystal structure and fluorescent property of the complex.Hydrothermal reaction of benzenetetracarboxylatic acid (H4BTC) with 1,2,3,4-tetra(4-pyridlyl)thiophene (TPT) afforded a novel supramolecular complex [(H4BTC))(TPT)] n (1), which was characterized by FT-IR spectroscopy, elemental analysis, luminescence and thermogravimetric analysis. X-ray single-crystal diffraction reveals that 1 exhibits a one-dimensional (1-D) wave-shape chain assembled through strong hydrogen bonds. Density functional theory (DFT) calculations show that the optimized structures closely resemble the experimental structures. The electronic absorption spectrum of the model dimer in its singlet state has been studied by a time-dependent DFT (TD-DFT) calculation and the nature of the molecular orbitals involved in the fluorescent property was verified.
Keywords: Supramolecular complex; Crystal structure; Fluorescent spectrum; DFT and TD-DFT calculation;

1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H2O)4] · H2O} n (1) and {[Ni(dba)(H2O)4] · H2O} n (2) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H2O} n (3) and [Ni(dba)(bpy)(H2O)2] n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H2O)4] · H2O} n (1) and {[Ni(dba)(H2O)4] · H2O} n (2) (H2dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H2O} n (3) and [Ni(dba)(bpy)(H2O)2] n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.
Keywords: 2,5-Dihydroxy-p-benzenediacetic acid; Mixed ligands; Cobalt(II); Nickel(II); Coordination polymer;

Ultrasound assisted synthesis of metal-1,3-diketonates by Nitin S. Nandurkar; Dinkar S. Patil; Bhalchandra M. Bhanage (733-736).
A simple and convenient methodology for complex formation of wide variety of transition metals/alkaline earth metals with 1,3-diketones under sonication have been reported. The present method showed a significant rate enhancement for metal complex formation in the presence of ultrasound as compared to their silent counterpart, thereby providing higher yields. The role of ultrasound and solvent were also discussed. Moreover, the metal-1,3-diketonates were characterized by various techniques like FT-IR, 1H NMR, mass spectrometry and magnetic susceptibility.A simple and convenient methodology for complex formation of wide variety of transition metals/alkaline earth metals with 1,3-diketones under sonication have been reported. The present method showed a significant rate enhancement for metal complex formation in the presence of ultrasound as compared to their silent counterpart, thereby providing higher yields. The role of ultrasound and solvent were also discussed. Moreover, the metal-1,3-diketonates were characterized by various techniques like FT-IR, 1H NMR, mass spectrometry and magnetic susceptibility.
Keywords: Ultrasound; Diketonate; Complex; Organometallic; Chemical vapour deposition; Structure;

Photochemical production of nitric oxide from a nitrosyl phthalocyanine ruthenium complex by irradiation with light in the phototherapeutic window by Zênis Novais da Rocha; Renata Galvão de Lima; Fabio Gorzoni Doro; Elia Tfouni; Roberto Santana da Silva (737-740).
The photolysis of [Ru(NO)(NO)2pc] (pc = phthalocyanine) at 366 and 660 nm releases NO with quantum yield depending on oxygen concentration. A range from 1.4 × 10−3 to 2.3 × 10−2  mol einstein−1 was observed and the photochemical pathway is depending on wavelength light irradiation.The photochemical behavior of [Ru(NO)(NO)2pc] (pc = phthalocyanine) is reported in this paper. In addition to ligand localized absorption bands (λ  < 300 nm), the electronic spectrum of this complex in dichloromethane solution was dominated by an intense absorption at 640 nm characterized as Q-bands. Irradiation of [Ru(NO)(NO)2pc] at 366 and 660 nm led to the production of nitric oxide (NO) as detected by a NO-sensor. NO production by light irradiation at high energy involved excitation of d π – π ∗ transition, while a photoinduced electron transfer occurred at long wavelength irradiation. The NO quantum yields varied from 1.4 × 10−3 to 2.3 × 10−2  mol einstein−1, depending on oxygen concentration.
Keywords: Nitrosil; Ruthenium complexes; Nitric oxide; Phthalocyanine;

Two Ag(I) coordination polymers without any solvent (guest) molecules, {[Ag(3-pia)](PF6)}n (1) and {[Ag(3-pia)2](PF6)}n (2) (3-pia =  N-pyridin-3-yl-isonicotinamide), have been synthesized using different solvents, and characterized by single X-ray analyses. The coordination environments around Ag(I) atoms in 1 and 2 are linear and tetrahedral, respectively.Two coordination polymers containing Ag(I) atoms, {[Ag(3-pia)](PF6)}n (1) and {[Ag(3-pia)2](PF6)}n (2) (3-pia =  N-pyridin-3-yl-isonicotinamide), have been synthesized using different solvents, and characterized by single X-ray analyses. In compound 1, Ag(I) atoms are linearly coordinated by two 3-pia ligands, resulting in one-dimensional chains. On the other hand, in compound 2, Ag(I) atoms are tetrahedrally coordinated by four 3-pia ligands, resulting in two-dimensional sheets.
Keywords: Silver(I); Coordination polymer; Crystal structure; Amide; Supramolecular assembly;

Synthesis and characterization of macrocyclic nickel(II) complexes with α-methylbenzyl groups as chiral pendants by Jeong Hyeong Han; Min Ju Cha; Bong Gon Kim; Seog K. Kim; Kil Sik Min (745-748).
Novel hexaaza macrocyclic nickel(II) complexes, 1 and 2, containing chiral α-methylbenzyl groups have been synthesized by an efficient one-pot template condensation and characterized. The observation of the Cotton effect and the X-ray crystal structure clearly provided evidence for the chirality of 1 and 2.Novel nickel(II) hexaaza macrocyclic complexes, [Ni(L R,R )](ClO4)2 (1) and [Ni(L S,S )](ClO4)2 (2), containing chiral pendant groups have been synthesized by an efficient one-pot template condensation and characterized (L R,R/S,S  = 1,8-di((R/S)-α-methylbenzyl)-1,3,6,8,10,13-hexaazacyclotetradecane). The crystal structures of 1 and 2 were determined by single-crystal X-ray analysis. Each complex has a square-planar coordination environment for the nickel(II) ion, and is either an R or an S enantiomorph depending on the pendant groups. The circular dichroism spectrum of 1 showed a negative, positive and negative peak at 345, 440, and 492 nm, respectively, and that of 2 exhibited an enantiomeric pattern.
Keywords: Chirality; Circular dichroism; Nickel(II) complex; Macrocyclic ligand; Crystal structure;

The chiral coordination polymer (1) containing Zn(II), and Na(I) metal atoms has been synthesized, and characterized. Linear and non-linear optical properties of grown crystal were investigated by UV/Vis, and Kurtz–Perry powder second-harmonic-generation (SHG) test.The chiral Zn(II)–Na(I) coordination polymer with formula [NaZn(acac)2(AcO)(EtOH)] (1) has been synthesized, and characterized by 1H NMR and FT-IR spectra, elemental, X-ray, and thermogravimetric analysis (TGA). X-ray crystallographic study revealed that 1 crystallizes in the non-centrosymmetric space groups P212121 and exhibits a one-dimensional polymer chain. Linear optical properties were investigated by UV/Vis spectrophotometer techniques. Kurtz–Perry powder second-harmonic-generation (SHG) test confirms the non-linear optical (NLO) property of the grown crystal.
Keywords: Coordination polymer; NLO; Zn(II) complex; Chiral complex; Crystal engineering;

Bis(imido) rhenium complexes bearing C- or N-capped ‘tripodal’ ligands: Bi- versus tri-dentate ligation by Carl Redshaw; Shuzhong Zhan; Sophie H. Dale; Mark R.J. Elsegood (754-756).
The differing geometrical constraints of the tripodal ligands tris(hydroxyphenyl)amine and tris(3,5-di-t-Bu-2-hydroxyphenyl)methane led, on reaction with [Re(t-BuN)3(OSiMe3)], to the isolation of the complexes [Re(t-BuN)2(N-capped)] (1) and [Re(OSiMe3)(t-BuN)2(C-cappedH)] (2), respectively. Both 1  · 1/2MeCN and 2 have been structurally characterized using X-ray synchrotron radiation.The differing geometrical constraints of the tripodal ligands tris(hydroxyphenyl)amine (N-cappedH3) and tris(3,5-di-t-Bu-2-hydroxyphenyl)methane (C-cappedH3) led, on reaction with [Re(t-BuN)3(OSiMe3)], to the isolation of the complexes [Re(t-BuN)2(N-capped)] (1) and [Re(OSiMe3)(t-BuN)2(C-cappedH)] (2), respectively. Both 1  · 1/2MeCN and 2 have been structurally characterized using X-ray synchrotron radiation.
Keywords: Tripodal; Rhenium; Imido; X-ray crystallography; Synchrotron;

Two-dimensional coordination polymer with tellurium nodes by Veronika Matulova; Marek Necas (757-760).
Bis(diphenylphosphino)hexane disulfide and TeCl4 afforded layered network coordination polymer with Te(II) nodes. The two-dimensional nets are positively charged, the anions TeCl 6 2 - and Te 2 Cl 10 2 - form layers alternating the polymeric networks.Bis(diphenylphosphino)hexane disulfide and TeCl4 afforded layered network coordination polymer with Te(II) nodes. The two-dimensional nets are positively charged, the anions TeCl 6 2 - and Te 2 Cl 10 2 - form layers alternating the polymeric networks.
Keywords: Bis(diphenylphosphino)hexane disulfide; Tellurium(II); Coordination polymers; Crystal structure;

One new metal–organic polymer formulated as [Fe210-btc)0.52-ox)0.52-O)1.5] n 1 (btc = 1,2,4,5-benzenetetracarboxylate, pyramellitate; ox = oxalate) 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. Complex 1 presents the first 3D coordination network structure constructed by bridging btc, ox and O mixed ligands. In 1, carboxyl groups of btc are all deprotonated and they have a new type of μ10-btc coordination mode. The third-order non-linear optical (NLO) properties of the title compound 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 5.98 × 10−30 esu for 1 in a 7.45 × 10−4  mol dm−3 DMF solution.One new metal-organic polymer formulated as [Fe210-btc)0.52-ox)0.52-O)1.5] n 1 (btc = 1,2,4,5-benzenetetracarboxylate, pyramellitate; ox = oxalate) 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. Complex 1 presents the first 3D coordination network structure constructed by bridging btc, ox and O mixed ligands. In 1, carboxyl groups of btc are all deprotonated and they have a new type of μ10-btc coordination mode. The third-order non-linear optical (NLO) properties of the title compound 1 were also investigated and they exhibit the reverse saturable absorption and self-defocusing performance with modulus of the hyperpolarizability (γ) 5.98 × 10−30  esu for 1 in a 7.45 × 10−4  mol dm−3 DMF solution.
Keywords: Metal-organic polymer; Synthesis; Third-order NLO behavior;

Synthesis and characterization of the highest connected 3D α-metatungstate POM/TMC hybrid with AgI⋯AgI interactions by Chun-Jing Zhang; Ya-Guang Chen; Hai-Jun Pang; Dong-Mei Shi; Mi-Xia Hu; Jia Li (765-768).
A novel 3D α-metatungstate POM/TMC hybrid with AgI⋯AgI interactions, Na4[Ag6L4][H2W12O40] · 12H2O (1) (L = nicotinate), has been conventional synthesized and characterized. The periphery of α-metatungstate clusters contains ten Ag–L units, which represents the highest coordination number of the α-metatungstate POMs to date.A novel 3D hybrid based on transition metal complexes (TMCs) modified α-metatungstate polyoxometalate (POMs), Na4[Ag6L4][H2W12O40] · 12H2O (1) (L = nicotinate), has been conventionally synthesized and characterized by elemental analysis, IR, UV, TG and single-crystal X-ray diffraction. Each of the W12 clusters is surrounded by 10 Ag centers, which represents the highest connected number of the α-metatungstate POMs to date. Additionally, compound 1 is stable in air and shows photoluminescence at room temperature.
Keywords: α-Metatungstate polyoxometalate; Conventional synthesis; Silver; Luminescence;

Synthesis, structural characterization, and magnetism of a butterfly-shaped hexanuclear Ni(II) complex by Wei Luo; Xiu-Teng Wang; Gong-Zhen Cheng; Song Gao; Zhen-Ping Ji (769-771).
The butterfly-shaped hexanuclear nickel complex contains two trinuclear bent subunits, which are bridged by two μ2-O(carbonyl) and one μ2-O(H2O) groups with the close Ni(II)⋯Ni(II) separation (2.969 Å) and exhibits strong ferromagnetic properties. It is the first hexanuclear Ni(II) complex obtained from the N-acyl-salicylhydrazide ligands.A new butterfly-shaped hexanuclear complex [Ni6L4H2O(C5H5N)4] · 2DMF (L = anion of N-(3-t-butylbenzoyl)-5-bromosalicylhydrazide) has been synthesized and characterized structurally and magnetically, which contains two trinuclear [Ni3L2(py)2] subunits bridged by two μ2-O(carbonyl) and one μ2-O(H2O) groups. It exhibits obvious ferromagnetic interaction owe to the central Ni(II) dimer with octahedral geometries.
Keywords: Hexanuclear; Butterfly-shaped; Nickel; Magnetism;

Ultraviolet photolysis of [Ru(bipy)2(NO)Cl](PF6)2 in bmim PF6 at ca. 90 K (νNO = 1938 cm−1) results in formation of isonitrosyl (νNO = 1809 cm−1) and side-on nitrosyl (νNO = 1638 and 1545 cm−1) linkage isomers.Photolysis of [Ru(bipy)2(NO)Cl](PF6)2 and its 15NO isotopomer in frozen butyl, methylimidazole (bmim) PF6 glass at ca. 90 K results in appearance of bands characteristic of isonitrosyl and side-on nitrosyl linkage isomers. In addition, weak bands corresponding to free NO in the matrix are also observed. These observations suggest that weakly bound linkage isomers of nitric oxide are likely intermediates in the photolytic release of NO in this and other physiologically relevant NO sources.
Keywords: Nitrosyl linkage isomerism; Photochemistry; Matrix photochemistry; Ruthenium;

{[Dy2(4-SBA)3(phen)2(H2O)4] · 2H2O} n (1) has a 1-D chain structure while {[Eu2(4-SBA)3(phen)2  · 2H2O]} n (2) has a 2-D network structure (4-SBA = 4-sulfobenzoate, phen = 1,10-phenanthroline).Two complexes {[Dy2(4-SBA)3(phen)2(H2O)4] · 2H2O} n (1) and {[Eu2(4-SBA)3(phen)2(H2O)2]} n (2) (4-SBA = 4-sulfobenzoate, phen = 1,10-phenanthroline) were synthesized and their structures were determined by X-ray crystallography. The 1 has a 1-D chain structure by bidentate and tridentate 4-SBA ligands as linkages and 3-D network was formed by strong hydrogen bonds. The 2 has a 2-D network structure by tridentate and tetradentate 4-SBA ligands as linkages. The luminescence properties and thermal stability of the two complexes were investigated.
Keywords: Lanthanide coordination polymers; 4-Sulfobenzoic acid; Hydrothermal synthesis; Crystal structure; Luminescence;

The complexes [Ln2(PDOA)3(phen)2(H2O)2] · 2H2O (Ln = Eu (1), Tb (2), and Dy (3); H2PDOA = 1,2-phenylenedioxydiacetic acid; phen = 1,10-phenanthroline) are all binuclear molecules and 3-D supramolecular frameworks are built up by the hydrogen bonds and π–π stacking interactions.The complexes [Ln2(PDOA)3(phen)2(H2O)2] · 2H2O (Ln = Eu (1), Tb (2), and Dy (3); H2PDOA = 1,2-phenylenedioxydiacetic acid; phen = 1,10-phenanthroline) have been synthesized and structurally characterized by single crystal X-ray diffraction methods. The three complexes are all binuclear molecules. The two Ln(III) centers are linked by only one PDOA ligand through its two bidentate-chelating carboxylate groups. PDOA also acts as a terminal ligand using one carboxylate oxygen and ether oxygen atoms to chelate the Ln(III) ion. 3-D supramolecular frameworks are built up by the hydrogen bonds and π–π stacking interactions. The fluorescent spectra of the three complexes show the characteristic emission of the Eu(III) for 1, Tb(III) for 2, and Dy(III) for 3, respectively.
Keywords: Lanthanide binuclear molecule; 1,2-Phenylenedioxydiacetic acid; 3-D supramolecular framework; Hydrothermal synthesis; Crystal structure; Luminescence;

A manganese(III) complex that exhibits spin crossover behavior by Zhiliang Liu; Shengli Liang; Xiaowei Di; Jun Zhang (783-786).
A MnIII(d4) complex, [MnIII(OL1)2]Cl · 3H2O was characterized structurally as well as magnetically. The two tridentate ligands are bound to the manganese(III) ion, resulting in an MnN4O2 chromophore with an axially-compressed octahedral geometry. Magnetic susceptibilities were measured and spin crossover (SCO) phenomenon arising from the spin transition of MnIII is exhibited.A novel MnIII(d4) complex, which exhibit spin crossover (SCO) phenomenon arising from the spin transition of LS ↔ HS state, was characterized structurally as well as magnetically. Single crystal X-ray diffraction methods structurally determined the compound as [MnIII(OL1)2]Cl · 3H2O. Two facially coordinating tridentate ligands are bound to the manganese(III) ion, resulting in an MnN4O2 chromophore with an axially-compressed octahedral geometry. The nitrogen donors are all in the equatorial plane with Mn–N distances ranging from 2.14 to 2.19 Å, the two oxygen donors occupy the axial positions at 1.86 Å. Magnetic susceptibilities were measured between 77 and 300 K. At 77 K, the magnetic moment converges close to the expected low spin (LS) value of 2.8 μB, whereas at 300 K the high spin (HS) limit is entropically inaccessible, as this is a one-electron SCO.
Keywords: Manganese(III) complex; Crystal structure; Magnetic properties; Spin crossover;

The system iron(II)/mpzbpy mediates the H2O2 oxidation of cyclohexane and cyclooctene and the aerobic oxidative cleavage of ascorbic acid to oxalate by Graham de Ruiter; José Sánchez Costa; Kristian Lappalainen; Olivier Roubeau; Patrick Gamez; Jan Reedijk (787-790).
A new iron complex generated in situ from Fe(CF3SO3)2 and the new tridentate N ligand 6-(3,5-dimethylpyrazol-1-ylmethyl)-6′-methyl-2,2′-bipyridine mediates the room temperature oxidation of cyclohexane to cyclohexanol and cyclohexanone, and the epoxidation of cyclooctene to cyclooctene oxide. The formation of a dinuclear complex, namely [Fe2(mpzbpy)2(C2O4)(CF3SO3)2] where two iron(II) ions are bridged by an oxalato dianion originating from the oxidative cleavage of ascorbic acid has been proven.The iron complex generated in situ from Fe(CF3SO3)2 and the new tridentate N ligand mpzbpy (mpzbpy stands for 6-(3,5-dimethylpyrazol-1-ylmethyl)-6′-methyl-2,2′-bipyridine) mediates the room temperature oxidation of cyclohexane to cyclohexanol and cyclohexanone, and the epoxidation of cyclooctene to cyclooctene oxide. X-ray diffraction studies of single crystals obtained by reaction of iron(II) triflate with mpzbpy in methanol in the presence of ascorbic acid reveals the formation of a dinuclear complex, namely [Fe2(mpzbpy)2(C2O4)(CF3SO3)2] (1), where two iron(II) ions are bridged by an oxalato dianion originating from the oxidative cleavage of ascorbic acid. Magnetic susceptibility measurements of 1 show that the two metallic centres are weakly antiferromagnetically coupled, with a J value of −1.74(1) cm−1.
Keywords: Iron; Catalysis; Alkane oxidation; Ascorbic acid cleavage; Oxidative degradation;

Complementary amide H-bond interactions of chiral C 2-symmetric bis(amide) ligand BINDC, (N,N′-bis(isonicotinoyl)-(1R,2R)-diaminocyclohexane) in Zn(BINDC)Cl2 (1), Zn(BINDC)Br2 (2) and Ag(BINDC)NO3 (3) metal-organic frameworks (MOFs) lead to the formation of hierarchical network structures. The MOFs show solid state second harmonic generation (SHG) and good optical transparency in the visible range.Complementary amide H-bond interactions of chiral C 2-symmetric bis(amide) ligand BINDC, (N,N′-bis(isonicotinoyl)-(1R,2R)-diaminocyclohexane) in Zn(BINDC)Cl2 (1), Zn(BINDC)Br2 (2) and Ag(BINDC)NO3 (3) metal-organic frameworks (MOFs) lead to the formation of hierarchical network structures. The strong H-bond interactions coupled with coordinate bond leads to enhanced thermal stability to the materials. Moreover, the MOFs show solid state second harmonic generation (SHG) and good optical transparency in the visible range.
Keywords: C 2-symmetric ligand; Hydrogen bonds; Metal-organic frameworks; SHG;

The two new coordination compounds, [PbCl(atza)] n (1) and [PbCl(a4-ptz)] n (2) have been synthesized by the conventional aqueous solution synthesis. In 1 or 2, the Pb(II) centers are connected through the atza or a4-ptz bridging ligand to form a two-dimensional layered structure. The luminescence properties of 1 and 2 were investigated at room temperature in the solid state.Reactions of Katza (atza  = 5-aminotetrazole-1-acetato) or Ka4-ptz (a4-ptz  = 5-[N-acetato(4-pyridyl)]tetrazole) with PbCl2in aqueous solution, produced two new Pb(II) compounds, [PbCl(atza)] n (1) and [PbCl(a4-ptz)] n (2). Both compounds were structurally characterized by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction. In 1 or 2, the Pb(II) centers are connected through the atza or a4-ptz bridging ligand to form a two-dimensional layered structure. The luminescence properties of 1 and 2 were investigated at room temperature in the solid state.
Keywords: Lead(II); 5-aminotetrazole-1-acetato; 5-[N-acetato(4-pyridyl)]tetrazole; Crystal structure; Luminescence;

Two bimetallic tetranuclear (K3–Fe or K3–Cr) complexes with three-blade propeller shape contain double helical water chains and exhibit second-order NLO properties.Two isostructural bimetallic tetranuclear chiral complexes, [K(18-crown-6)]3[Fe(ox)3] · 9H2O and [K(18-crown-6)]3[Cr(ox)3] · 9H2O, crystallize in rhombohedral R3 space group, the tetranuclear cluster is respectively built from one [Fe(ox)3]3− or [Cr(ox)3]3− species with three K(18-crown-6 ether) supramolecular cations linked by oxalate groups, and lattice water molecules form the double helical chains. Two complexes are second-harmonic-generation (SHG) active with the SHG response about 0.5 times that of urea.
Keywords: Tetranuclear cluster; Crystal structure; Double helical water chain; NLO;

Organically templated Np(IV) coordination polymer with in situ formed oxalate anion (ImidazoleH)[Np(C2O4)(CH3SO3)3(H2O)2] by Grigory B. Andreev; Nina A. Budantseva; Ivan G. Tananaev; Boris F. Myasoedov (802-804).
The reaction of Np(V) methanesulfonate solution with imidazole led to the in situ formation of oxalic acid and the reduction of Np(V) to Np(IV). As a result, the novel organically templated organic polymer, (ImidazoleH)[Np(C2O4)(CH3SO3)3(H2O)2], was formed.The reaction of Np(V) methanesulfonate solution with imidazole led to the in situ formation of oxalic acid and the reduction of Np(V) to Np(IV). As a result, the novel organically templated organic polymer, (ImidazoleH)[Np(C2O4)(CH3SO3)3(H2O)2], was formed. The structure consists of infinite chains of [Np(C2O4)(CH3SO3)3(H2O)2] and imidazolium cations. The crystal structure is confirmed by IR and UV–vis spectroscopic data. This complex is the first example of structurally characterized 1:1 An(IV) oxalate.
Keywords: Neptunium; Coordination polymer; Crystal structure; Electronic spectrum; IR spectrum; In situ synthesis;

Bis(4′-phenyl-2,2′:6′,2″-terpyridine)ruthenium(II): Holding the {Ru(tpy)2}2+ embraces at bay by Edwin C. Constable; Catherine E. Housecroft; Elaine A. Medlycott; Markus Neuburger; Federica Reinders; Sébastien Reymann; Silvia Schaffner (805-808).
The solid state structure of [Ru(Phtpy)2][PF6]2  · 4MeCN has been determined (Phtpy = 4′-phenyl-2,2′:6′,2″-terpyridine); [Ru(Phtpy)2]2+ cations pack into sheets with {M(tpy)2}2 embraces; generalizations about packing motifs in salts containing [M(Phtpy)2]2+ or [M(pytpy)2]2+ cations (pytpy = 4′-pyridyl-2,2′:6′,2″-terpyridine) are discussed.The solid state structure of [Ru(Phtpy)2][PF6]2  · 4MeCN has been determined (Phtpy = 4′-phenyl-2,2′:6′,2″-terpyridine); [Ru(Phtpy)2]2+ cations pack into sheets by virtue of {M(tpy)2}2 embraces, and the MeCN solvent molecules are involved in N⋯H–C interactions which prevent the efficient packing of adjacent sheets. Comparisons with related structures lead to some generalizations about packing motifs in salts containing [M(Phtpy)2]2+ or [M(pytpy)2]2+ cations (pytpy = 4′-pyridyl-2,2′:6′,2″-terpyridine).
Keywords: 2,2′:6′,2′′-Terpyridine; Ruthenium; Coordination; Crystal structure; Supramolecular;

Novel Cd(II) and Co(II) 2-D frameworks based on terephthalate and 1-substitutedimidazole mixed-ligands by Qing-Xiang Liu; Xiao-Jun Zhao; Xiu-Mei Wu; Su-Wen Liu; Yan Zang; Shu-Sheng Ge; Xiu-Guang Wang; Jian-Hua Guo (809-813).
The two Cd(II) and Co(II) 2-D frameworks have been prepared by means of self-assemblies of Cd(II) or Co(II) salts and 1-substitutedimidazole and terephthalic acid, and structurally characterized by X-ray diffraction analyses. In complex 1 2-D frameworks with rhombic cavity are formed, in which the each top point of rhombus contains one hexa and two heptacoordinated Cd(II). In complex 2 2-D networks with rectangular cavities are formed, and the opposite benzene rings from carboxyls in each rectangular cavity are parallel.The two Cd(II) and Co(II) 2-D frameworks have been prepared by means of self-assemblies of Cd(II) or Co(II) salts and 1-substituted imidazole and terephthalic acid, and structurally characterized by X-ray diffraction analyses. In complex 1 2-D frameworks with rhombic cavity are formed, in which the each top point of rhombus contains one hexa and two heptacoordinated Cd(II). In complex 2 2-D networks with rectangular cavities are formed, and the opposite benzene rings from carboxyls in each rectangular cavity are parallel.
Keywords: Coordination polymer; Imidazole; Terephthalic acid; Cadmium; Cobalt;

A 3d–3d heterometallic organic framework consisting of two cross-linked coordination polymers by Gui-Li Wang; Xiao-Li Yang; Yan Liu; Yi-Zhi Li; Hong-Bin Du; Xiao-Zeng You (814-817).
A novel 3d–3d heterometallic metal-organic framework, [Zn2(ox)3][{CuI(4,4-bipy)}2] · C2H6O2 (ox = oxalate, 4, 4-bipy = 4, 4-bipyridine), 1 has been synthesized by using two bidentate ligands under hydrothermal condition. Compound 1 is a rare three-dimensional framework constructed by intercalation of the metal oxalate [ Zn 2 ( ox ) 3 ] n 2 - honeycomb sheets with the [ { Cu I ( 4 , 4 -bipy ) } 2 ] n 2 + 1-D coordination polymer.A novel 3d–3d heterometallic metal-organic framework, [Zn2(ox)3] [{CuI(4,4-bipy) }2] · C2H6O2 (ox = axalate, 4,4-bipy = 4,4-bipyridine), 1 has been synthesized by using two bidentate ligands under hydrothermal condition. The Cu(II) ion in the starting materials was reduced to Cu(I) along with the partial oxidation of the ethylene alcohol molecules to the oxalate, leading to the formation of 1. Compound 1 is a rare three-dimensional framework constructed by intercalation of the metal oxalate [ Zn 2 ( ox ) 3 ] n 2 - honeycomb sheets with the [ { Cu I ( 4 , 4 -bipy ) } 2 ] n 2 + 1-D coordination polymer.
Keywords: Heterometallic; Metal-organic framework; Hydrothermal condition; Intercalation; Metal oxalate;

A novel palladium(I) compound, [Pd3(dppp)33-Cl)2][Pd2(PPh3)22-Cl)3] · (PPh3)2, has been synthesized and characterized by X-ray single-crystal diffraction. The result reveals that the compound is composed of [Pd3(dppp)33-Cl)2]+ cations having triangulo-palladium clusters, [Pd2(PPh3)22-Cl)3] anions in which the coordination environment of palladium(I) is an unusual tetrahedral geometry, and two uncoordinated PPh3 molecules.Pd(PPh3)2Cl2 reacts with PdCl2 and 1,3-bis(diphenylphosphine)propane (dppp) in ethanol–DMF–pyridine mixed solvent to yield a novel palladium(I) compound [Pd33-Cl)2(dppp)3][Pd22-Cl)3(PPh3)2](PPh3)2. It features an isolated structure based on [Pd33-Cl)2(dppp)3]+ cations having triangulo-palladium clusters and [Pd22-Cl)3(PPh3)2] anions in which the coordination environment of palladium is an unusual tetrahedral geometry. Its photoluminescence is measured.
Keywords: Crystal structure; Palladium(I); Trinuclear palladium clusters; Tetrahedral geometry; Photoluminescence;

Synthesis and structure of a dimeric scandium bis(μ-methoxy) complex by Simon A. Cotton; Victoria M.A. Fisher; Paul R. Raithby; Stefanie Schiffers; Simon J. Teat (822-824).
Reaction of hydrated scandium nitrate with 1,10-phenanthroline led to the formation and structural characterisation of the first di-methoxy bridged dimeric complex [(phen)(NO3)2Sc(μ-OMe)2Sc(NO3)2(phen)], in which the scandium centres are eight co-ordinate.Reaction of hydrated scandium nitrate with 1,10-phenanthroline (phen) in methanol leads to formation of the unusual dimeric complex [(phen)(NO3)2Sc(μ-OMe)2Sc(NO3)2(phen)], in which the scandium centres are eight co-ordinate. The complex features two bridging methoxy ligands, as well as bidentate nitrates and chelating 1,10-phenanthroline ligands.
Keywords: Crystal structure; Scandium complex; Eight co-ordinate complex; Nitrate complex; Alkoxide group;

The first example of disubstituted Lindqvist-type polyoxomolybdate {[V(2,2-bipy)2]2(4,4-bipy)[Te2Mo4O19]} has been synthesized hydrothermally, which consists of a novel Lindqvist-type polyanion [Te2Mo4O19]6− supporting two vanadyl moieties [V(2,2-bipy)2]3+, and a non-coordinating “guest” 4,4-bipys molecule.The first example of disubstituted Lindqvist-type polyoxomolybdate {[V(2,2-bipy)2]2(4,4-bipy)[Te2Mo4O19]} has been synthesized hydrothermally and characterized by elemental analyses, XPS, IR, TG-DTA and X-ray single crystal diffraction. The structural analysis shows that the neutral molecular unit [V(2,2-bipy)2]2[Te2Mo4O19] consists of a novel Lindqvist-type polyanion [Te2Mo4O19]6− supporting two vanadyl moieties [V(2,2-bipy)2]3+, and such neutral molecules are joined together by π  −  π stacking interactions between the pyridine groups to form a two-dimensional grid-like network with non-coordinating “guest” 4,4-bipys encapsulated.
Keywords: Hydrothermal synthesis; Lindqvist anion; Polyoxomolybdate; Crystal structure;