A New Europium(II) Oxide Iodide: Eu2OI2

Red single crystals of Eu₂OI₂ were obtained from a reaction mixture of barium metal, EuI₂, Eu₄OI₆ and some NH₄I in a tantalum tube at 780/500 °C. The crystal structure (orthorhombic, Imcb, Z = 4, a = 648.93(11), b = 742.85(13), c = 1307.1(3) pm, R1(all) = 0.0605) contains {Eu₄O} tetrahedra connected via trans‐edges to infinite chains. The iodide ions surround and connect these chains to a three‐dimensional structure.     

New Saccharinato/Ammonia Complexes of Nickel(II) and Zinc(II). A Structural and Spectroscopic Study

Two new saccharinate/NH₃ complexes of composition [Ni(sac)₂(NH₃)₄] and [Zn(sac)₂(NH₃)₂] were obtained and their crystal structures determined by single crystal X‐ray diffractometry. The elongated octahedral Ni^II complex crystallizes in the monoclinic P2₁/c space group with Z = 2 whereas the tetrahedral Zn^II complex is triclinic (space group and Z = 2). For [Ni(sac)₂(NH₃)₄] the magnetic moment and electron absorption spectrum were obtained and discussed. The infrared spectra of both complexes were also recorded and briefly commented.     

Synthesis and Structure of Europium Aluminium Garnet (EAG)

Europium aluminium garnet (Eu₃Al₅O₁₂, EAG) was synthesized by an aqueous sol‐gel process and subsequent thermal annealing at 800 – 850 °C. Eu₃Al₅O₁₂ crystallizes cubic ( and its crystal structure was refined from X‐ray powder data. The refined oxygen position in the structure of EAG yields four shorter and four longer distances between europium and the eight surrounding oxygen atoms, forming a distorted dodecahedron. Pure Eu₃Al₅O₁₂ can be treated at temperatures around 1000 °C before it converts into perovskite‐like EAP near 1300 °C.     

Synthesis,Structural, and Optical Characterization of a New Europium(II) Tin Selenide,Eu8(Sn4Se14)(Se3)2 with a (Sn4Se14)12– Building Block

A new phase in europium‐tin‐chalcogenide chemistry has been prepared using the reactive flux method: Eu₈(Sn₄Se₁₄)(Se₃)₂. The compound crystallizes in the orthorhombic space group P2₁2₁2 with cell parameters a = 11.990(2) Å, b = 16.425(4) Å, c = 8.543(1) Å, and Z = 2. Eu₈(Sn₄Se₁₄)(Se₃)₂ is a three dimensional structure with Eu^II cations linked together with an unusual (Sn₄Se₁₄)^12– anionic unit and (Se₃)^2– chains. UV‐VIS‐NIR band‐gap analysis shows that these black metallic crystals are likely semiconductors with an optical band‐gap of 1.07 eV.     

Spectroscopic and Crystal Structure of Europium(III) Picrate Complexes with Novel BINOL Derivatives

Two novel ligands N‐Benzyl‐2‐{2′‐[(benzyl‐phenyl‐carbamoyl)‐methoxy]‐[1,1′]binaphthalenyl‐2‐yloxy}‐N‐phenyl‐acetamide (L1) and N‐Methyl‐2‐{2′‐[(methyl‐phenyl‐carbamoyl)‐methoxy]‐[1,1′]binaphthalenyl‐2‐yloxy}‐N‐phenyl‐acetamide (L2), and their europium(III) complexes with picrate, [Eu(pic)₃(L1)] and [Eu(pic)₃(L2)], were synthesized and characterized by elemental analysis, IR, UV‐Vis and fluorescence spectroscopy. The crystal structure of [Eu(pic)₃(L1)]·2CHCl₃ was determined by single crystal X‐ray diffraction. The europium atom is coordinated by nine oxygen atoms of four from the L1 and five from two bidentate and one unidentate picrates. The fluorescent intensity of [Eu(pic)₃(L2)] is about 2.6 times that of [Eu(pic)₃(L1)] in solid states. But in CHCl₃ solution, the fluorescent intensity of [Eu(pic)₃(L1)] is stronger slightly than [Eu(pic)₃(L2)].     

Crystal Structure and Spectroscopic Properties of trans‐Dibromidobis(propane‐1, 3‐diamine)chromium(III) Perchlorate

The structure of trans‐[Cr(tn)₂Br₂]ClO₄ (tn = propane‐1, 3‐diamine) has been determined by a single‐crystal X‐ray diffraction study at 100 K. The complex crystallizes in the space group P$\bar{1}$ of the triclinic system with two mononuclear formula units in a cell of dimensions a = 6.8220(4), b = 8.86199(9), c = 12.6644(8) Å and α = 77.859(7)°, β = 81.765(6)°, and γ = 77.764(7)°. The chromium atom is in a slightly distorted octahedral environment coordinated by four nitrogen atoms of two tn ligands and two bromine atoms in trans positions. The two six‐membered chelate rings in the complex cations are oriented in an anti chair‐chair conformation with respect to each other. The mean Cr–N(tn) and Cr–Br bonds are 2.093(3) and 2.4681(4) Å, respectively. The crystal packing is stabilized by hydrogen bonds. The infrared and electronic absorption spectral properties are consistent with the result of X‐ray crystallography. It is confirmed that the nitrogen atoms of the tn ligand are strong σ‐donors, but the bromido ligands have weak σ‐ and π‐donor properties toward the chromium(III) ion.     

Crystal Structure and Characterization of Two Layered Copper(II) Coordination Polymers with Anions of 3‐Phosphonopropionic Acid and (RS)‐2‐Phosphonobutyric Acid

Blue single crystals of Cu[μ₃‐O₃P(CH₂)₂COOH] · 2H₂O ( 1 ) and Cu[(RS)‐μ₃‐O₃PCH(C₂H₅)COOH] · 3H₂O ( 2 ) were prepared in aqueous solutions (pH = 2.5–3.5). 1 crystallizes in space group Pbca (no. 61) with a = 812.5(2), b = 919.00(9), and c = 2102.3(2) pm. Cu²⁺ is fivefold coordinated by three oxygen atoms stemming from [O₃P(CH₂)₂COOH]^2– anions and two water molecules. The Cu–O bond lengths range from 194.0(3) to 231.8(4) pm. The connection between the [O₃P(CH₂)₂COOH]^2– anions and the Cu²⁺ cations yields a polymeric structure with layers parallel to (001). The layers are linked by hydrogen bonds. 2 crystallizes in space group Pbca (no. 61) with a = 1007.17(14), b = 961.2(3), c = 2180.9(4) pm. The copper cations are surrounded by five oxygen atoms in a square pyramidal fashion with Cu–O bonds between 193.6(4) and 236.9(4) pm. The coordination between [O₃PCH(C₂H₅)COOH]^2– and Cu²⁺ results in infinite puckered layers parallel to (001). The layers are not connected by any hydrogen bonds. Each layer contains both R and S isomers of the [O₃PCH(C₂H₅)COOH]^2– dianion. Water molecules not bound to Cu²⁺ are intercalated between the layers. UV/Vis spectra suggest three d–d transition bands at 743, 892, 1016 nm for 1 and four bands at 741, 838, 957, and 1151 nm for 2 , respectively. Magnetic measurements suggest a weak antiferromagnetic coupling between Cu²⁺ due to a super‐superexchange interaction. Thermoanalytical investigations in air show that the compounds are stable up to 95 °C ( 1 ) and 65 °C ( 2 ), respectively.     

Crystal Structure and IR Spectrum of Diaqua(o‐phenanthroline) bis(saccharinato)lead(II)

The crystal structure of [Pb(sac)₂ophen(H₂O)₂] (sac = saccharinate anion; ophen = 1,10‐phenanthroline) has been solved by single X‐ray diffractometry. It crystallizes in the monoclinic space group C2/c with Z = 4. The Pb^II atom presents the coordination number eight with unusual coordination of the ligand atoms between square‐antiprism and dodecahedron. The saccharinate anion acts as a bidentate ligand. The i. r. spectrum of the complex has been analyzed in detail and assigned on the basis of the structural peculiarities.     

Synthesis,Spectrothermal Behaviour and Molecular Structure of Aquaorotatotriethanolaminenickel(II) Monohydrate

The aquaorotatotriethanolaminenickel(II) monohydrate, [Ni(HOr)(H₂O)(tea)]·H₂O ( 1 ), was synthesized and characterized by means of elementel analysis, IR and UV‐Vis, spectroscopy, magnetic susceptibility, thermal analysis and X‐ray diffraction techniques. The nickel ion in [Ni(C₅H₂N₂O₄)(H₂O)(N(C₂H₄OH)₃)] is chelated to the deprotonated N3 pyrimidine atom and to the carboxylate oxygen atom of the bidentate orotate dianion, and to the one nitrogen and two oxygen atoms of the tridentate triethanolamine molecule and its octahedral geometry is completed by an aqua ligand. It crystallizes in the monoclinic system, space group P2₁/c with lattice parameters a = 7.1528(5) Å, b = 19.4903(14) Å, c = 11.8085(8) Å, β = 106.237(5)°, V = 1580.55(19) ų, Z = 4. An extensive three dimensional network of O_w‐H…O, N‐H…O and O‐H…O hydrogen bonds, π‐π and π‐ring interactions are responsible for crystal stabilization. The decomposition reaction take places in the temperature range 20‐1000 °C in the static air atmosphere. Thermal decomposition of 1 proceeds in three stages.     

[Be(OH2)4]Cl2 – Herstellung,IR‐Spektrum und Kristallstruktur

[Be(OH₂)₄]Cl₂ – Preparation, IR spectrum, and Crystal Structure Single crystals of [Be(OH₂)₄]Cl₂ were prepared by the reaction of thionyl chloride at 20 °C with samples which result from evaporated, HCl containing, aqueous solutions of BeCl₂. With excess of boiling thionyl chloride BeCl₂ is formed. [Be(OH₂)₄]Cl₂ is characterized by IR spectroscopy and by X‐ray crystal structure determination: Space group P2₁/c, Z = 4, lattice dimensions at 193 K: a = 653.53(5), b = 1298.15(14), c = 789.52(6) pm, β = 103.005(9)°, R1 = 0.027. The structure consists of slightly distorted tetrahedral [Be(OH₂)₂]²⁺ ions, which are connected with the chloride ions via nearly linear O–H···Cl hydrogen bonds to give a 3D network.     

A New 3D Manganese(II) Coordination Polymer with 4,4‐Dicarboxy‐2,2′‐bipyridine and 1,10‐Phenanthroline: Synthesis,Structural, and Magnetic Properties

A new 3D Mn^II metal‐organic framework compound {Mn(phen)(dcbp)}_n (H₂dcbp = 4,4‐dicarboxy‐2,2′‐bipyridine, phen = 1,10‐phenanthroline) was isolated under hydrothermal conditions and structurally characterized. In the compound, the dcbp ligand is deprotonated to give a neutral species (metal:ligand with 1:1 stoichiometry). Along the c axis, the neighboring Mn^II ions are linked by two carboxylate bridges in µ₂‐coordinating mode to generate a 1D zigzag chain, and these chains are interlinked by dicarboxylate groups of long dcbp ligands to generate a 3D (4,4)‐connected structure with the (4².8⁴) net topology. IR and UV/Vis spectroscopy and variable temperature magnetic susceptibility measurements were made, which indicated weak antiferromagnetic interactions between the Mn^II ions of the compound.     

An Ytterbium(II) Complex with Triethanolamine

Bis(triethanolamine)ytterbium(II) diperchlorate was obtained by electrochemical reduction. The metal ion is surrounded by two triethanolamine molecules only, and its first sphere of coordination consists of six O and two N atoms. The compound shows weak luminescence at 77 K with a very broad emission band (488—667 nm). The complexation of triethanolamine shifts the Yb (III) reduction potential of 0.46 V towards more negative values.     

Reactions of Me2Si(2‐Me‐4,5‐BenzInd)Zr(Cl)(NEt2) and Me2Si(2‐Me‐4,5‐BenzInd)ZrCl2 (BenzInd = benzindenyl) with trimethylaluminum and methylaluminumoxane: Correlation of spectroscopy and propene polymerizations

The activity of metallocene/methylaluminumoxane (MAO) catalysts in olefin polymerization is highly dependent on both the alkylation and activation of the complexes. The leaving ligands have an important role in the complex activation, influencing the activity of the system. The aim of this work was to study the reactions of complexes Me₂Si(2‐Me‐4,5‐BenzInd)₂ZrCl₂ ( A ; BenzInd = benzindenyl) and Me₂Si(2‐Me‐4,5‐BenzInd)₂Zr(Cl)(NEt₂) ( B ) with trimethylaluminum (TMA) and MAO. The reaction kinetics and products were studied by both ultraviolet–visible and NMR spectroscopy. In addition, the polymerization behavior of the different species was investigated in propene polymerizations. Complex B was more easily monomethylated by TMA than complex A and resulted in L₂Zr(Me)(NR₂)‐type species. Monomethylation of the complexes before polymerization enhanced the polymerization activity of both complexes. When complexes A and B reacted with MAO, similar cationic species were formed, giving equal polymerization activities. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6455–6464, 2005     

KEu(CH3COO)3, das erste ternäre Europium(II)-acetat

KEu(CH₃COO)₃, the First Ternary Europium(II) Acetate On of EuCl₂ with a melt of dry potassium acetate yields pale greenish-yellow single crystals (300°C, sealed glass ampoule, EuCl₂ and K(CH₃COO) in a molar ratio of 1 : 3). The crystal structure determination (orthorhombic, P2₁2₁2₁ (no. 19), Z = 8, a = 1166.3(1) pm, b = 1288.4(2) pm, c = 1493.9(2) pm, R = 0.043, R_w = 0.032) revealed the composition KEu(CH₃COO)₃. The structure consists of one-dimensional chains built up by bridging acetate groups in the [100] and [001] directions in which potassium and europium alternate as central atoms. Eu²⁺ is surrounded by nine and eight and K⁺ by seven and six oxygen atoms, respectively. These chains are linked in the [010] direction so that a three-dimensional network is formed. The high coordination numbers of the acetate oxygen atoms of up to four are remarkable. Therefore, the acetate groups have highly bridging functions in addition to their chelating coordination of the cations.     

Wasserstoffbrücken in 1,1‐Bis(2‐hydroxyethyl)‐3‐benzoylthioharnstoff und seinen Nickel(II)‐ und Kupfer(II)‐Chelat‐Komplexen

Hydrogen Bonds in 1,1‐Bis(2‐hydroxyethyl)‐3‐benzoylthiourea and its Nickel(II)‐ and Copper(II)‐Chelate Complexes The ligand 1,1‐bis(2‐hydroxyethyl)‐3‐benzoylthiourea HL, ( 1 ), yields with nickel(II) and copper(II) ions neutral complexes [NiL₂], ( 2 ), and [CuL₂], ( 3 ). By X‐ray structure analysis and IR spectroscopy different intramolecular hydrogen bonds (OH…O) and (OH…N) could be identified in both equally coordinated ligands of the [NiL₂] molecule. For comparison X‐ray and IR data were also estimated for 1 and 3 .     

Synthesis,Crystal Structure and Spectroscopic Properties of [2,13‐Bis(1‐naphthalenylmethyl)‐5,16‐dimethyl‐2,6,13,17‐tetraazatricyclo(14,4,01.18,07.12)docosane]copper(II) Diperchlorate Acetonitrile Disolvate

The N‐functionalized macrocyclic ligand 2,13‐bis(1‐naphthalenylmethyl)‐5,16‐dimethyl‐2,6,13,17‐tetraazatricyclo(14,4,0^1.18,0^7.12)docosane (L³) and its copper(II) complex were prepared. The crystal structure of [Cu(L³)](ClO₄)₂·2CH₃CN was determined by single‐crystal X‐ray diffraction at 150 K. The copper atom, which lies on an inversion centre, has a square planar arrangement and the complex adopts a stable trans‐III configuration. The longer distance [2.081(2) Å] for Cu–N(tertiary) compared to 2.030(3) Å for Cu–N(secondary) may be due to the steric effect of the attached naphthalenylmethyl group on the tertiary nitrogen atom. Two perchlorate ions are weakly attached to copper in axial sites and are further connected to the ligand of the cation through NH ··· O hydrogen bonds [N ··· O 3.098 Å]. IR and UV/Vis spectroscopic properties are also described.     

Synthesis and Crystal Structure of Europium(II) Tartrate Tetrahydrate, [Eu(C4H4O6)(H2O)2](H2O)2

Single crystals of [Eu(C₄H₄O₆)(H₂O)₂](H₂O)₂ were obtained from the combination of solutions of EuCl₂, previously obtained by electrolysis of an aqueous solution of EuCl₃, and tartraric acid, neutralized by LiOH. The crystal structure (orthorhombic, P2₁2₁2₁, Z = 4, a = 948.9(1), b = 954.6(1), c = 1098.4(1) pm; R(F) = 0.0242 and R_w(F²) = 0.0585 for I > 2σ(I); R(F) = 0.0256 and R_w(F²) = 0.0592 for all data) is isotypic with [Ca(C₄H₄O₆)(H₂O)₂](H₂O)₂ and [Sr(C₄H₄O₆)(H₂O)₂](H₂O)₂ exhibiting a three‐dimensional structure. The divalent cations (Eu²⁺, Ca²⁺, Sr²⁺) are eight‐coordinate by oxygen atoms that originate from carboxylate and hydroxyl groups of the tartraric dianion and two of the four water molecules.     

Synthesis and Spectroscopic Characterization of New Lead(II) Thiosaccharinates. Molecular Structure of Bis(thiosaccharinato)tetrakis(pyridine)dilead(II) and Thiosaccharinato‐bis(1,10‐phenantroline)lead(II) Thiosaccharinate

Four new lead(II) thiosaccharinate complexes: [Pb(tsac)₂H₂O] (1) (tsac: thiosaccharinate anion), [Pb₂(tsac)₄(py)₄] (2) (py: pyridine), [Pb(tsac)(o‐phen)₂](tsac)·CH₃CN (3) (o‐phen: 1,10‐phenantroline), and [Pb(tsac)₂(bipy)] (4) (bipy: 2,2′‐bipyridine) were prepared. The infrared and electronic spectra as well as the thermal analysis of all the compounds were recorded and discussed. The thiosaccharinate anion acts in three different coordination forms, one of then reported for the first time. The crystal structures of complexes 2 and 3 have been determined by single crystal X‐ray diffractometry. In complex 2 , two monomeric moieties are joined together forming a symmetric bis‐μ‐sulphur bridged dimer by interaction of two lead(II) atoms through the exocyclic sulphur atoms of two thiosaccharinate ligands. The seven‐fold coordination sphere of each lead atom is completed by two pyridine nitrogen atoms and by another sulfur and two nitrogen atoms of the thiosaccharinate anions. In complex 3 , the lead(II) atom is coordinated by four nitrogen atoms of two 1,10‐phenantroline molecules and by the sulfur and nitrogen atoms of one thiosaccharinate ion. The second anion has an electrostatic interaction with the nucleus.     

A Novel Route to Triphenylgermyl Europium Complexes. Crystal Structure of (Ph3Ge)2Eu(DME)3

(Ph₃Ge)₂Eu(THF)₄ ( 1 a ) and (Ph₃Ge)₂Eu(DME)₃ ( 1 b ) have been synthesized by reacting Ph₃GeH with europium naphthalene, C₁₀H₈Eu(THF)₂, in THF or DME, respectively. The reaction of Ph₃GeH with C₁₀H₈[EuI(DME)₂]₂ in DME yielded Ph₃GeEuI(DME)₂ ( 2 ). The addition of two equivalents of CH₃I to a solution of 1 b in THF produced Ph₃GeMe and EuI₂(DME)₂ with almost quantitative yields. Complex 2 easily disproportionates forming mixtures of 1 b and EuI₂(DME)₂. The molecular structure of 1 b was determined from X-ray diffraction data.