Inorganic Chemistry Communications (v.6, #8)

Contents List (iii-v).

[(tren)Co(N3)2]Br (I) and [(tren)Co(N3)2]I (III) was prepared and its crystal structure determined at 293 and at 120 K. At room temperature (293 K), (I) crystallizes as a conglomerate in space group P212121 and remains so at 120 K, (data sets Ia and Ib, respectively). The iodide crystallizes as a racemate, space group P21/n (z=4), data set (IIIa); but, cooling to 120 K results in a phase change whereby the crystal is enantiomorphic (IIIb) + (IIIc), space group P21(z=4). There is no damage to the crystal upon undergoing the phase transition (IIIa) → (IIIb) + (IIIc). In fact, the same crystals were used to collect the data sets which were cycled as follows: 293 → 120 → 293 K. The two molecules in the asymmetric unit of (IIIb and IIIc) are homochiral demanding that the phase transition observed causes the inversion of the axial chirality of one of the five-membered rings of the iodide. This result is reproducible and was observed for all crystals cooled to 120 K. Differential scanning calorimetry confirms the existence of phase changes in the crystalline material as a result of cooling.
Keywords: Conglomerate crystallization; Phase changes; Co(III) azides; Tetraamine ligands; Differential scanning calorimetry; Thermogravimetric analysis;

Synthesis and properties of an iron hydrogenase active site model linked to a ruthenium tris-bipyridine photosensitizer by Henriette Wolpher; Magnus Borgström; Leif Hammarström; Jonas Bergquist; Villy Sundström; Stenbjörn Styring; Licheng Sun; Björn Åkermark (989-991).
A dinuclear iron complex, related to the active site of Fe hydrogenases, has been covalently linked to a redox active ruthenium tris-bipyridine type photosensitizer. Photophysics and electrochemistry of this system are studied in solution. IR spectra of this complex together with its precursor, the dinuclear iron complex, were also shown.
Keywords: Iron hydrogenase; Biomimetic model; Dinuclear iron complex; Ruthenium tris-bipyridine; Photosensitizer;

Nanocrystallites of spinel ZnCrFeO4 were synthesized through sol–gel method, and were characterized by X-ray diffractometer (XRD), transmission electron microscopy (TEM), SQUID magnetometer and Mössbauer spectrometer. It is found that the nanocrystallites are spherical and show antiferromagnetism with a higher T N of 14 K for the sample with diameter of 14 nm and larger magnetic susceptibility than the bulk sample. These are associated with some A ions (Zn2+) and B ions (Fe3+, Cr3+) jumped to each other sites, which therefore enhances both the A–B interaction and B–B interaction. The Mössbauer spectrum of the nanomaterial is different from that of the bulk sample. Additional sextet appears in the Mössbauer spectrum of the nanomaterial except for a doublet. The appearance of the sextet suggests the magnetically ordered state between Fe3+ ions at A and B sites.
Keywords: Nanocrystalline; ZnCrFeO4; Sol–gel synthesis; Susceptibility; Mössbauer;

Ruthenium(II) acetylacetonato–sulfoxide complexes by Adam Wu; David C Kennedy; Brian O Patrick; Brian R James (996-1000).
The water-soluble RuII acetylacetonato–sulfoxide complexes, cis-Ru(acac)2(DMSO)2 (1) and Ru(acac)2(meso-BESE) (2), were synthesized (BESE=1,2-bis(ethylsulfinyl)ethane=EtS(O)(CH2)2S(O)Et). Both complexes were characterized by 1H and 13C{1H} NMR, UV–Vis, and IR spectroscopies, as well as MS, elemental analysis, solution conductivity, and cyclic voltammetry, while the molecular structure of 2 was determined also by X-ray crystallography. All sulfoxide ligands are S-bonded. The complexes were tested against human breast cancer cells (MDA-MB-435S) using an in vitro MTT assay, a colorimetric determination of cell viability; IC50 values of >2000 and 1500 ± 100 μM were determined for 1 and 2, respectively, while cisplatin exhibits an IC50 value of 30 ± 5 μM.
Keywords: Ruthenium; Acetylacetonato; Sulfoxides; 2D NMR spectroscopy;

Dioxouranium complexes with ‘Jaeger-type’ ligands by Claudia C. Gatto; Ernesto Schulz Lang; Ulrich Abram (1001-1003).
Azomethine ligands with electron-withdrawing groups such as bis{N,N -(2-ethoxycarbonyl-3-oxo-but-1-en(1)yl)-1,2-diaminobenzene (H2L1) or N-(2-ethoxycarbonyl-3-oxo-but-1-en(1)yl)-2-aminophenol (H2L2) react with uranyl nitrate under deprotonation and formation of chelate complexes. The composition of the products can be controlled by the reaction conditions and the denticity of the ligands. Structure determinations have been performed on [NEt3H][UO2(L1)(OMe)], [UO2(L1)(DMSO)] and [NEt3H]2[{UO2(L2)}33-O)].
Keywords: Uranium; Jäger-type ligands; Actinides; Crystal structure;

X-ray structure and spectroscopic properties of some lanthanides(III) complexes derived from 2,6-diacetylpyridine-bis(benzoylhydrazone) by Farba B. Tamboura; Mayoro Diop; Mohamed Gaye; Abdou S. Sall; Aliou H. Barry; Tahar Jouini (1004-1010).
A series of trivalent lanthanide complexes of type [Ln(L) NO3)(S) n ](NO3) m (S) n , have been synthesized by the reaction of 2,6-diacetylpyridine-bis-(benzoylhydrazone) (H2L) with lanthanide(III) nitrates in ethanol. These complexes have been characterized by analysis, molar conductance, magnetic measurements, infrared spectral studies and X-ray diffraction. The analytical data revealed the formation of 1:1 (metal:ligand) stoichiometry. Molar conductance in dmf gives 2:1 electrolytes in all the complexes. Magnetic moment values are close proximity of the Van Vleck values. IR study suggests the coordination of the ligand through the azomethine and the oxygen of the hydrazonic moiety. The nitrate ion is also found to be bidentate in all the complexes. The crystal structures were determined. 6, C27H31N6O7S2Gd: a=b=8.6821(4) Å, c=84.363(5) Å, tetragonal P41212 and Z=8. bf 7, C25H25N6O6SDy: a=11.750(3) Å, b=13.250(3) Å, c=36.000(6) Å, β=98.50(2), monoclinic, C2/c, Z=8. 9, C24H25N6O7Yb: a=10.750(2) Å, b=17.750(3) Å, c=14.250(4) Å, β=99.00(2), monoclinic, P21/n, Z=4. In these complexes the lanthanide ion assumes a nine coordinated geometry for Gd and an eight coordinated geometry for Dy and Yb.
Keywords: Lanthanide complex; Spectroscopic; Molar conductance; Crystal structure;

The homoditopic ligand L contains two tpy metal-binding domains and reacts with iron(II) chloride to form two multinuclear metallomacrocycles having [3 + 3] and [4 + 4] metal–ligand stoichiometries.
Keywords: 2,2:6,2′′-terpyridine; Metallomacrocycle; Iron(II);

Aromatic–aromatic interaction between metallacycle and phenyl ring by Shubhamoy Chowdhury; Michael G.B Drew; Dipankar Datta (1014-1016).
The X-ray crystal structure of [CuL2]ClO4 where L is the 1:1 condensate of benzil-monohydrazone and 2-pyridinecarboxaldehyde, reveals unprecedented π–π interaction between the metallacycles and phenyl rings. The interaction is intramolecular.
Keywords: Schiff base; Copper(I) complex; Crystal structure; π–π interaction;

A photoluminescent polymeric chain complex: synthesis and structure of [(PPh3)2Cu2(μ-I)2(μ-4,4-bpy)] n by Rong-Zhen Li; Dan Li; Xiao-Chun Huang; Zhi-Yu Qi; Xiao-Ming Chen (1017-1019).
The synthesis and crystal structure of a new one-dimensional mixed-ligand Cu(I) coordination polymer, [(PPh3)2Cu2(μ-I)2(μ-4,4-bpy)] n (4,4-bpy=4,4-bipydine) are reported. The neutral polymer consists of (PPh3)2Cu2(μ-I)2(μ-4,4-bpy) units bridged by 4,4-bpy to construct an infinite chain architecture. Crystal data: C23H19CuINP, M r=530.80, Triclinic space group (P1 , No. 2), a=9.2279(8) Å, b=9.4014(8) Å, c=13.3663(12) Å, α=107.445(2)°, β=106.707(2)°, γ=93.479(2)°, V=1045.8(2) Å3, D calc=1.686 g m−3, Z=2. The solid state of the complex is luminescent with a peak maximum at 535 nm, upon excitation at 300–400 nm at room temperature. The emission is assigned to Copper(I) to 4,4-bpy charge transfer (MLCT).
Keywords: Copper(I); Coordination polymer; Structure; 4,4-Bipyridine; Photoluminescence;

Tree novel nanoporous compounds, [Cu3(TMA)2(H2O)3]4[{(CH3)4N}2(H2SiMo12O40)] ·≈40H2O (1), [Cu3(TMA)2(H2O)3]4[{(CH3)4N}2(HPW12O40)] ·≈40H2O (2), and [Cu3(TMA)2(H2O)3]4[{(CH3)4N}2(HPMo6W6O40)] ·≈40H2O (3) (TMA=acidtrimesic acid=1,3,5-benzentricaboxylate) have been synthesized via hydrothermal process, and characterized by X-ray structure analysis, IR and NMR spectroscopy, and thermogravimetry. All the compounds crystallize isostructurally consisting of a nanoporous coordination polymer framework [Cu3(TMA)2(H2O)3] n accommodating α-Keggin polyoxomolybdate and -tungstate anions. Results of the IR and 29Si and 31P MAS NMR spectra reveal the existence of α-Keggin species with no other impurity.
Keywords: Keggin; Polyoxometalate; Nanoporous material; Crystal structure; Coordination polymer; Supramolecular material; Organic/inorganic hybrid material;

Two one-dimensional chain complexes: [Mn(Hpdc)(H2O)2] n (1) and [Cu2(Hpdc)2][4,4-dpdo] (2) have been synthesized from hydrothermal solutions at 150 °C. Both structures are mainly constructed by a single multifunctional ligand, monopotassium 3,5-pyrazoledicarboxylate (KH2pdc). All metal atoms are six-coordinated in 1, two kinds of carboxylic bridges are found between manganese atoms to form a one-dimensional chain and further construct three-dimensional structure by hydrogen bonds. In 2, all copper atoms are five-coordinated, Cu1 and Cu1A are linked by the nitrogen atoms in the pyrazole ring to form a dimmer and two-dimensional structure is formed by weak coordination bonds and hydrogen bonds. Susceptibility data of 1 and 2 show antiferromagnetic coupling interactions.
Keywords: Crystal structures; Mn(II) complexes; Cu(II) complexes; One-dimensional chain complexes; Hydrothermal synthesis;

The reaction of both tris(2-aminoethyl)amine and tris(2-dimethylaminoethyl)amine with Zn(ClO4)2 in the presence of equimolar amount of NaBPh4 in methanol afforded two different zinc(II) complexes, namely ({[tren]Zn(HOMe)} · ClO4  · BPh4) 1 and ({[trenMe6]Zn} · ClO4  · BPh4) 2. Zinc(II) Complex 1, which has been structurally characterized by X-ray crystallography, takes up CO2 in methanol in the presence of base to fix it into monomethyl carbonato complex ({[tren]Zn(OCO2Me)} · BPh4  · 2MeOH) 3.
Keywords: Zinc(II) complexes; X-ray crystal structure; CO2 fixation;

A neutral zincophosphate monomer [Zn(2,2-bipy)]2(H2PO4)4 has been synthesized under hydrothermal condition in the presence of 2,2-bipyridine ligands. The structure consists of a 4-membered ring formed by vertex-sharing ZnO3N2 square pyramids and H2PO4 tetrahedra, with two H2PO4 groups hanging from the zinc atoms. This compound exhibits intense photoluminescence upon photoexcitation at 388 nm.
Keywords: Zinc phosphate; Hybrid materials; Hydrothermal synthesis; Crystal structure; Luminescence;

η⇌μ exchange bonding mode of bidentate tmeda ligand. Molecular structure of [Y(tmhd)3]2(μ-tmeda) by J. Terrematte; S. Daniele; L.G. Hubert-Pfalzgraf; J.M. Decams; H. Guillon; P. Richard (1039-1043).
The reaction between the yttrium β-diketonate complexes Y(tmhd)3(H2O) x (x=0 or 1) and 0.5 or 1 equivalent of N,N,N ,N -tetramethylethylenediamine (tmeda=Me2NCH2CH2NMe2) in hexane at room temperature afforded [Y(tmhd)3]2(tmeda) (1) and Y(tmhd)3(tmeda) (2) derivatives, respectively. They have been characterized by FT-IR, 1H NMR spectroscopy and by single crystal X-ray diffraction for 1. Variable temperature 1H NMR experiments indicated an equilibrium between 1 and 2. Their thermal behaviors were characterized by TGA and sublimation experiments. 2 is converted into compound 1 by heating over 100 °C. These precursors were used for the growth of Y2O3 and YBa2Cu3O7 −  x films by pulsed injection metal organic chemical vapor deposition (PI-MOCVD).
Keywords: Yttrium; β-Diketonate; X-ray structure; PI-MOCVD;

Methoxy-alkenyl carbenes 1 and 2 have been synthesized by treating a dichloro-methane/methanol solution of the [(η6-Me6C6)Ru(Ph2PCHCH2)Cl2] complex with an excess of 1-ethynyl-1-cyclohexanol and 1-ethynyl-1-cyclopentanol in the presence of NaPF6. The compounds were characterized by IR and 1H, 13C{1H}, 31P{1H} NMR spectroscopies and by elemental analyses. The crystal structure of 2 has also been determined by X-ray crystallography.
Keywords: Crystal structure; Ruthenium(II) complexes; Multinuclear NMR; Allenylidene; Vinylidene;

A new V(V)-substituted isopolytungstate, (n-C3H7)5[H4VW11O40], with Keggin structure was synthesized in an acidic aqueous–CH3CN solution and characterized by elemental analysis, FT-IR, Raman, 1H NMR, and cyclic voltammetry.
Keywords: Polyoxometalate; Isopolytungstate; Keggin; Vanadium; Acetonitrile;

Two novel complexes, [Cu2(Hsal)4(4,4-bipyridine)(H2O)2(DMF)2] (1) (H2sal=salicylic acid) and {[Cu(Hsal)2(4,4-bipyridine)](H2O)(H2sal)} n (2), were synthesized by layered-solution method and structurally characterized. Geometries of copper atoms in both complexes exhibit square pyramidal. Complex 1 is a dimer and hydrogen bonds between water and DMF molecules extend the structure into 1D hydrogen bonding network. Complex 2 consists of two-dimensional square framework structure.
Keywords: Crystal structure; Copper complex; Salicylic acid; 4,4-Bipyridine; Dimer; Network;

Di-2-pyridyl ketone oxime in 3d-metal carboxylate cluster chemistry: a new family of mixed-valence Mn2 IIMn2 III complexes by Constantinos J Milios; Catherine P Raptopoulou; Aris Terzis; Ramon Vicente; Albert Escuer; Spyros P Perlepes (1056-1060).
Several reaction schemes involving di-2-pyridyl ketone oxime, (py)2CNOH, Mn sources, RCO2 ligands and X in MeCN or MeCN/EtOH lead to the new family of mixed-valence complexes [Mn2 IIMn2 III(O2CR)2X2{(py)2CNO}2{(py)2CO2}2] (R=Me, Ph; X=Cl, Br; (py)2CO2 2−=the gem-diolate(-2) form of di-2-pyridyl ketone). The products have been characterized by single crystal X-ray crystallography and exhibit the same structural motif. Magnetic studies indicate weak antiferromagnetic exchange interactions in the complexes.
Keywords: Crystal structures; Di-2-pyridyl ketone oxime; Magnetic properties; Tetranuclear mixed-valence manganese complexes;

Novel coordination polymers {[M(bpmb)(H2O)2(C2H5OH)2]·(NO3)2} n (M=Zn 1, Cd 2; bpmb= N,N -bis (3-pyridinylmethyl)-1,4-benzenedicarboxamide) have been synthesized by the reaction of bpmb with zinc(II) salt and cadmium(II) salt in ethanol–water solution, respectively. Elemental analysis, IR spectra and X-ray crystal structure analysis were carried out to determine the compositions and crystal structures of the two compounds, which reveal that bpmb bridges the metal centers to from a one-dimensional chain. These chains were linked through noncovalent interactions to form three-dimensional networks.
Keywords: One-dimensional coordination polymer; Noncovalent interaction; Zinc complex; Cadmium complex;

The germyl borate 1 was prepared by the reaction of triphenylborane with an excess of unsolvated triethylgermyllithium in a hexane/benzene mixed solvent. The polymeric structure of 1 was observed in the solid state and in a hydrocarbon solvent. The lithium atoms were located near the center of the benzene ring and interacted with the neighboring borate molecules by the Li+–π interaction. The polymeric structure was destroyed by the addition of MeOH, however, 1 was coordinated by three MeOH molecules to form the dimeric structure without alcoholysis reaction.
Keywords: Germanium; Boron; Germylborate; Li+–π interaction; Crystal structure;

Macrocyclic dinuclear copper(II) complex with a novel chloride bridged zigzag chain by Tongbu Lu; Shi Chen; Zongwan Mao; A.E. Martell; Liangnian Ji (1068-1070).
A macrocyclic dinuclear copper complex Cu2LCl(ClO4) · H2O, where L=15,31-dimethyl-3,11,19,27,33,35-hexaazapentacyclo[27.3.1.1.5,91.13,171.21,25]-hexatriaconta-5,7,9(33),13,15,17(34),21,23,25(35),29,31,1(36)-dodecaene-34,36-diol, has been synthesized and characterized by single-crystal X-ray diffraction. In the complex, each Cu(II) ion is coordinated with three macrocyclic nitrogen atoms and one phenolate oxygen anion. The dinuclear copper complexes are linked by the bridged Cl to form a novel zigzag chain with a folded chair conformation.
Keywords: Macrocyclic dinuclear copper complex; 1D chain; Bridging chloride; Folded chair conformation;

Photolysis in the charge-transfer-to-solvent bands of the nickel(II) azamacrocyclic complexes in aqueous solutions yields trivalent nickel azamacrocyclic complexes.
Keywords: Charge-transfer-to solvent transition; UV-photolysis; Nickel(III)azamacrocyclic complexes; Electron spin resonance; Photochemistry; Nickel(II) complexes;

The structure of a Pb(II) complex of a tridentate ligand namely, N-(2-pyridylmethyl)-l-alanine (Hpala) has been found to have single stranded helical structure, pillared by Pb⋯O⋯Pb interactions from ClO4 anions.
Keywords: Pb(II) complex; Coordination polymers; Helical structures; Self-assembly;

A new metal–metal bonded diruthenium(II, III) compound with a dianionic tridentate ligand, N-(2-pyridyl)-2-oxy-5-chlorobenzylaminate (5-Clsalpy2−), was synthesized and structurally characterized as Li2(THF)4Cl[Ru2(5-Clsalpy)3] (1). The 5-Clsalpy2− ligand that acts as a bridging/chelating co-ligand afforded a unique coordination mode of [M–M bridging/equatorial-chelating] in addition to the “common” mode of [M–M bridging/axial-chelating] around the diruthenium unit of 1.
Keywords: Metal–metal bond; Ruthenium complex; Tridentate ligand; Crystal structure;

A hydrophilic chiral diamine from d-glucose in the Rh(I) catalysed asymmetric hydrogenation of acetophenone by Carmela Borriello; Maria Elena Cucciolito; Achille Panunzi; Francesco Ruffo; Angela Saporito (1081-1085).
A strategy for the synthesis of a new hydrophilic chiral diamine derived from α-d-glucose is described. The compound is obtained by introducing proper nitrogen functions at C2 and C3 positions of the sugar ring, and by deprotecting positions 4 and 6. The efficiency of the ligand in the Rh(I)-catalysed hydrogenation of acetophenone has been examined by using isopropanol and ethanol as hydrogen sources. The secondary alcohol has been obtained in ees up to 50%.
Keywords: Rhodium; Asymmetric hydrogenation; Nitrogen ligands; Carbohydrates;

Novel reactivity of unconjugated diimines with [PtCl2(coe)]2 (coe=cis-cyclooctene) by Eric J Derrah; Haiwen Zhang; Liliya G Nikolcheva; Christopher M Vogels; A Decken; Stephen A Westcott (1086-1090).
The addition of unconjugated diimines [ArC(H)NCH2CH2NC(H)Ar, L1: Ar=3-C6H4Bpin (pin=1,2-O2C2Me4), L2: Ar=4-C6H4Bpin, and L3: Ar=4-C6H4OMe] to [PtCl2(coe)]2 (coe=cis-cyclooctene) affords the corresponding dinuclear species [trans-PtCl2(coe)]2 L (13), where the diimine coordinates in a monodentate fashion to each of the metal centres. Compounds have been characterized by multinuclear NMR spectroscopy, FT-IR spectroscopy, elemental analyses, and for the case of 2, by X-ray diffraction.
Keywords: Unconjugated diimines; Platinum; Boronate esters; Aminoboron;

A new 2-D selenic vanadate network decorated by a coordination complex fragment: [Cu(phen)(H2O)2][V3Se3O14] · H2O by Gejihu De; Yangguang Li; Rudan Huang; Enbo Wang; Mei Yuan; Changwen Hu; Lin Xu (1091-1095).
A new organic–inorganic hybrid selenic vanadate [Cu(phen)(H2O)2][V3Se3O14] · H2O (1) has been hydrothermally synthesized and characterized by elemental analyses, IR, EPR spectra and the single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P 1 ̄ , a=6.3112(13) Å, b=13.249(3) Å, c=14.060(3) Å, α=100.88(3)°, β=90.48(3)°, γ=97.54(3)°, V=1143.9(4) Å3, Z=2, R1=0.0310. Compound 1 exhibits a novel 2-D selenic vanadate network on the basis of an unprecedented {V6Se6O28} oxide cluster building block. Furthermore, this new selenic vanadate layer is decorated by [Cu(phen)(H2O)2]2+ coordination complex fragments.
Keywords: Organic–inorganic hybrid; Selenic vanadate; Hydrothermal synthesis; Crystal structure;

Ni(II) reacts with Ni(0) complexes in toluene solution to yield diamagnetic phosphido-bridging Ni(I)–Ni(I) complexes of the type Ni22-PPh2)(CNR)22-dppa)2. The great thermodynamic stability of these complexes is discussed on the light of their electrochemical properties. The X-ray crystal structure of the complexes Ni22-PPh2)(CNR)22-dppa)2, R=n-Bu, Xylyl is also presented.
Keywords: Phosphorus–nitrogen bond cleavage; Nickel complexes; Phosphido; Dppa;

The reactions of potentially tridentate ligands, derived from N-arylpiperazines, with [NEt4]2[Re(CO)3Br3] have been investigated. The compounds [Re(CO)3{NC5H4CH2N(H) CH2CH2–Fphenpip}]Br (1Br), [Re(CO)3{(NC5H4CH2)2NCH2CH2CH2–CH3OphenpipH}]Br2  · 2CH2Cl2  · H2O (2Br2  · 2CH2Cl2  · H2O) and [Re(CO)3{(CH3N2C3H2CH2)(O2CCH2)N(CH2)3–CH3OphenpipH2}]BrCl · 1.5MeOH · H2O (3BrCl · 1.5MeOH · H2O) have been prepared and structurally characterized. The compounds exhibit fac-[Re(CO)3N3] or fac-[Re(CO)3N2O] coordination geometry in the cationic molecular units. Both compounds are chemically robust and survive histidine and cysteine challenges with greater than 95% recovery. Crystal data for C21H23BrFN4O3Re (1Br): monoclinic P21/c, a=11.344(1) Å, b=14.433(1) Å, c=13.730(1) Å, β=103.092(2)°, V=2189.5(2) Å3, Z=4; C31H41Br2Cl4N5O5Re (2Br2  · 2CH2Cl2  · H2O): monoclinic P21/c, a=30.015(1) Å, b=8.9324(4) Å, c=14.7361(6)Å, β=103.195(1)°, V=3846.5(3) Å3, Z=4; C25.5H39BrClN5O8.5Re (3BrCl · 1.5MeOH · H2O): triclinic P 1 ̄ , a=11.818(2) Å, b=13.292(2) Å, c=14.517(2) Å, α=63.915(2)°, β=66.373(2)°, γ=67.416(2)°, V=1815.6(4) Å3, Z=2.
Keywords: {Re(CO)3}+ core; Radiopharmaceuticals; N-arylpiperazine derivatives;

Reaction of the [1-(4-H2N–C6H4)-closo-1-CB9H9] anion 1 with Me2CHCH2CH2ONO and dilute HCl gives neutral [1-(4-N2–C6H4)-closo-1-CB9H9] 3, which reacts with PhNH2 to form the 19.5 Å [1-{4-(4-H2N–C6H4–NN)–C6H4}-closo-1-CB9H9] azo anion 2. Anion 1 with ketones and aldehydes gives imino compounds: with (CH3)2CO it gives neutral [1-{4-(Me2CNH)–C6H4}-closo-1-CB9H9] 6 and with the para-dialdehyde C6H4-1,4-(CHO)2 it gives the 30.5 Å extended rod-like neutral species [C6H4-1,4-{1-(CHNH–C6H4)-closo-1-CB9H9}2] 8.
Keywords: Borane cluster; X-ray structure; Monocarbaborane; Rod-like molecules; Carbaborane C-functionalisation;

A pentanuclear complex derived from manganese(III) Schiff-based complex and hexacyanoferrate(III): synthesis, structure and magnetic properties by Shu-Feng Si; Jin-Kui Tang; Zhan-Quan Liu; Dai-Zheng Liao; Zong-Hui Jiang; Shi-Ping Yan; Peng Cheng (1109-1112).
A cyano-bridged MnIII–FeIII complex, [Mn(salpn)(CH3OH)]4·[Fe(CN)6]ClO4·9(H2O), was prepared and characterized. Single crystal X-ray analysis reveals that the complex assumes a cyano-bridged Mn4Fe unit. The magnetic measurement showed this complex exhibiting ferromagnetic behavior.
Keywords: Prussian blue analogues; Crystal structure; Magnetism;

Clear Ag–Ag bonds in three silver(I) carboxylate complexes with high cytotoxicity properties by Hai-Liang Zhu; Xian-Ming Zhang; Xiu-Ying Liu; Xian-Jiang Wang; Gao-Feng Liu; Anwar Usman; Hoong-Kun Fun (1113-1116).
The reaction of Ag2O and carboxylate ligands in ammonium solution results in three coordination polymers, [Ag(fbc)] n 1, [Ag2(cpd)] n 2 and [Ag2(idc)] n 3, where fbcH is 4-fluorobenzoic acid, cpdH2 is cyclopentane-1,1-dicarboxylic acid and idcH2 is iminodiacetic acid. The X-ray crystal structural analysis indicates that compounds 1 and 2 are two-dimensional frameworks and 3 is a three-dimensional framework. All the three complexes show clear Ag–Ag bonds and high cytotoxicity properties to normal cells and carcinoma cells.▪
Keywords: Silver coordination complex; Ag–Ag bonds; Cytotoxicity; Supramolecular chemistry;

Hydrothermal deposition of cerium hydroxycarbonate thin films on glass by Zhaohui Han; Yitai Qian; Kaibin Tang; Gaoqing Lu; Shuhong Yu; Neng Guo (1117-1121).
The first success in the preparation of rare earth hydroxycarbonate thin films has been achieved. Cerium hydroxycarbonate films were prepared by a hydrothermal deposition method, the sample of a single orthorhombic phase was deposited at a lower temperature while those of orthorhombic and hexagonal phases were obtained at higher temperatures. The crystals in the films could be ellipsoidal, prismatic, or rhombic, depending on the deposition conditions applied. The thin films could be candidates for developing novel optical materials and for advanced ceramics processing.
Keywords: Hydrothermal deposition; Cerium hydroxycarbonate; Thin film; Luminescence;

A new chelating radical ligand 4ImNNH (2-(4-imidazolyl)-4,4,5,5-tetramethylimidazolin-1-yloxyl 3-oxide) was prepared, and complexation with nickel(II) nitrate gave [Ni(4ImNNH)2(NO3)2] as a discrete mononuclear complex. Magnetic measurements revealed that [Ni(4ImNNH)2(NO3)2] had a ground high-spin state (S total=2) and exhibited metamagnetic behavior below 3.4 K.
Keywords: Nickel(II); Free radical; Ferromagnetic interaction; Hydrogen bond;

Treatment of the group 4 halides TiCl4 and ZrCl4 with various stoichiometries of [(6-Me-TMS-Apy)Li(Et2O)] (6-Me-TMS-ApyH=2-(trimethylsilylamino)-6-methylpyridine) has been studied yielding [(6-Me-TMS-Apy)TiCl3]2 (1), [(6-Me-TMS-Apy)3TiCl] (2) or [(6-Me-TMS-Apy)3ZrCl] (3). The structures of compounds (1), (2) and (3) were characterised by spectroscopic and X-ray crystallographic methods. The X-ray structure of (1) is a centrosymmetric dimer through bridging chlorides. Compounds (2) and (3) are isostructural mononuclear complexes with seven-coordinate metal centres.

The reaction of dafone (4,5-diazafluoren-9-one, 1) and iron(III) chloride in concentrated hydrochloric acid medium yields an unusual complex containing hemiprotonated dafone, [(dafone)2H]+[FeCl4]. The crystal structure reveals that two coordinating ligands share a single proton to form the new cation [(dafone)2H]+ while the accompanying tetrachloroferrate(III) anion stabilizes the ion pair. The [FeCl4] anion is close to tetrahedral in geometry with four chloro ligands in the first coordination sphere which is only slightly affected by the interactions with the di-dafonium unit.
Keywords: Iron; Diazafluorenone; Crystal structure; Phenanthroline; Magnetism;

The novel manganese (II) complex of 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene (bpd) [Mn(bpd)(NCS)2(CH3OH)2] n was synthesized. Its crystal structure was determined, together with the results of variable temperature magnetic susceptibility and IR spectrum. The structure of the complex demonstrates a sheet-like dimensional network by both bpd bridge and hydrogen bond interactions.
Keywords: Manganese; N,N -bidentate ligands; Crystal structure; Preparation;

A one-dimensional compound (NH3CH2CH2NH3)AgAsS4 with ladder-like chains was synthesized solvothermally. This compound crystallizes in the monoclinic system, space group C2/c, with a=13.5805(8) Å, b=6.5331(3) Å, c=22.7711(9) Å, α=90°, β=106.42(3)°, γ=90°, Z=8. The rare type hydrogen bonding of N–H⋯S and electrostatic force hold the anionic chains together.
Keywords: Solvothermal synthesis; Quaternary thioarsenate; Chain structure;

Hydride ruthenium complexes, RuHCl(CO)(PPh3)2(L–L) 3 (L–L=bidentate ligand having nitrogen and oxygen) react with allenes to give Ru(η3-allyl)(CO)(PPh3)(L–L) complexes 5 in good yields via hydrometalation reaction. The complexes 5 have planar chirality at the η3-allyl ligand and central chirality at the Ru metal, and consist of one pair of enantiomers. Ligand substitution reaction of Ru(η3-allyl)Cl(CO)(PPh3)2 complexes 6 with bidentate ligands (L–L) also afford the complexes 5 which have the same stereochemistry as those formed by the hydrometalation reaction. The planar chirality is controlled by the central chirality at the Ru metal in both the formations of the complexes 5. The structure of 5a (L–L=N–N bidentate ligand) was determined by the X-ray crystal structure analysis.
Keywords: η3-Allyl ruthenium complex; Hydrometalation; Ligand substitution; Diastereotopic relation; Planar and central chiralities;

One-dimensional nanoporous M2L2 rhombohedral molecular square with strong blue fluorescent emission by Yong-Xiu Li; Yong-Hua Li; Xi-Rui Zeng; Ren-Gen Xiong; Xiao-Zeng You; Hoong-Kun Fun (1144-1147).
The hydrothermal reactions of Zn(ClO4)2  · 6H2O and Cd(ClO4)2  · 6H2O with the ligand N,N -bis(pyridylcarbonyl)-4,4-diaminodiphenyl ether (L) afford two one-dimensional (1D) coordination polymers, ([CdL(ClO4)2  · (H2O)2] · 2H2O) (1) and [ZnL(ClO4)2  · (H2O)2] · 2H2O, (2) having a nanoporous M2L2 rhombohedral molecular square with an approximately accessible cavity of 12.9 × 12.9 (1) and 12.7 × 12.7 (2) Å without any interpenetrations. Both 1 and 2 are isostructural and display very strong blue fluorescent emission in the solid state at room temperature.
Keywords: Rhombic molecular square; Nano-sized; Zn and Cd; Coordination polymer;

Conversion of olefins into trans-diols or trans-diol mono-ethers by using iron porphyrin(III) complex and H2O2 by Sang-Kun Yoo; Jung Hee Han; Sung Jea Lee; Ji Young Ryu; Cheal Kim; Sook Won Jin; Youngmee Kim; Wonwoo Nam (1148-1151).
Iron porphyrin complex showed an excellent catalytic activity on conversion of various olefins into 1,2-diols or 1,2-diol mono-ethers by H2O2 under mild and neutral conditions to produce relatively regioselective products.
Keywords: Iron(III) porphyrins; Epoxidation; Ring opening; Diols; Diol mono-ethers;

A copper(II) complex {[Cu(H2btc) (H2O)3]2(H4btc)(C5H11N)2  · 3H2O} n (1) has been synthesized and characterized structurally (H4btc=1,2,4,5-benzenetetracarboxylic acid). Open channels were formed and can accommodate piperidine molecules. TGA data show that guest water and piperidine molecules are lost at 130 °C.
Keywords: Crystal structure; Copper(II) complex; 1,2,4,5-Benzenetetracarboxylate; TGA; XRPD;

The Zn(II) complexes of 4,6-O-butylidene/ethylidene-N-(α-hydroxynaphthylidene/o-hydroxybenzylidene)-β-d-glucopyranosylamine have been synthesized and characterized using spectral and analytical methods and structure for one of the products was established. The geometry of the complexes vary from unusual distorted trigonal bipyramidal to pseudo-bicapped tetrahedron depending upon the extent of binding of pyranose ring oxygens to the Zn(II) ion, as evidenced from crystal structures. Such interaction is also reflected on the optical rotation and CD spectral properties of these complexes in solution.Unusual interaction extended between the pyranose ring oxygen and Zn(II) center in the complexes derived from 4,6-O-butylidene/ethylidene-N-(α-hydroxynaphthylidene/o-hydroxybenzylidene)-β-d-glucopyranosylamine: evidence for a pseudo-bicapped tetrahedral complex of Zn(II) based on the crystal structure.
Keywords: Zn(II) complexes; Pyranose ring oxygen; β-d-Glucopyranosylamine; Pseudo bicapped tetrahedron;

Highly efficient phosphate diester hydrolysis and DNA interaction by a new unsymmetrical FeIIINiII model complex by Suzana Cimara Batista; Ademir Neves; Adailton J. Bortoluzzi; Ivo Vencato; Rosely A. Peralta; Bruno Szpoganicz; Veronika V.E. Aires; Hernán Terenzi; Patricia Cardoso Severino (1161-1165).
A new heterodinuclear mixed valence complex [FeIIINiII(BPBPMP)(OAc)2]ClO4 1 with the unsymmetrical N5O2 donor ligand 2-bis[{(2-pyridylmethyl)-aminomethyl}-6-{(2-hydroxybenzyl)(2-pyridylmethyl)}-aminomethyl]-4-methylphenol (H2BPBPMP) has been synthesized and characterized. 1 crystallizes in the monoclinic system, space group P21/n, a=12.497(2), b=18.194(4), c=16.929(3) Å, β=94.11(3)°, V=3839.3(12) Å3 and has an FeIIINiII(μ-phenoxo)-bis(μ-carboxylato) core. Solution studies of 1 indicate that a pH-induced change in the bridging acetate occurs and the formation of an active [(OH)FeIII(μ-OH)NiII(OH2)]+ species as the catalyst for phosphate diester hydrolysis and DNA interaction is proposed. In addition, the results presented here suggest that NiII would be a good candidate as a substitute of MII in purple acid phosphatases.
Keywords: Crystal Structure; Dinuclear FeIIINiII complex; Unsymmetric ligand; Phosphatase-like activity; DNA interaction; Cyclic voltammetry;