Lanthanoid‐Peroxo‐Komplexe mit μ3‐η2:η2:η2‐(O22—)‐Koordination. Die Kristallstrukturen von [Ln4(O2)2Cl8(Py)10] · Py mit Ln = Sm,Eu, Gd

Lanthanoid Peroxo Complexes with μ₃‐η²:η²:η²‐(O₂^2—) Coordination. Crystal Structures of [Ln₄(O₂)₂Cl₈(Py)₁₀] · Py mit Ln = Sm, Eu, Gd The four‐nuclear peroxo complexes [Ln₄(O₂)₂Cl₈(Py)₁₀]·py (py = pyridine) with Ln = Sm ( 1 ·py), Eu ( 2 ·py) und Gd ( 3 ·py) are formed as pale yellow ( 1 ·py) and colourless ( 2 ·py and 3 ·py) crystals by action of atmospheric oxygen on heated solutions of the anhydrous trichlorides LnCl₃ in pyridine/ diacetone alcohol (4‐hydroxy‐4‐methyl‐2‐pentanone). According to the X‐ray structural analyses the three complexes crystallize isostructural in the triclinic space group PP1¯ with two formula units per unit cell. 1—3 form centrosymmetrical molecular structures, in which the four lanthanoid atoms in coplanar array are linked via the two peroxo groups in a hitherto unobserved μ₃‐η²:η²:η² coordination. Additionally, they are bonded by four �μchloro bridges. Two of the Ln atoms complete their coordination sphere by three pyridine molecules each, the other two by two chlorine atoms and two pyridine molecules. The gadolinium compound is additionally characterized by its complete vibrational spectrum (i.r. and Raman).     

Pyridinium‐Chlorometallate von Lanthanoid‐Elementen. Die Kristallstrukturen von [HPy]2[LnCl5(Py)] mit Ln = Eu,Er, Yb und von [H(Py)2][YbCl4(Py)2] · Py

Pyridinium Chlorometallates of Lanthanoid Elements. Crystal Structures of [HPy]₂[LnCl₅(Py)] mit Ln = Eu, Er, Yb und von [H(Py)₂][YbCl₄(Py)₂] · Py The pyridinium chlorometallates [HPy]₂[LnCl₅(Py)] with Ln = Eu, Er and Yb, as well as [H(Py)₂][YbCl₄(Py)₂]·Py have been obtained by the reaction of diacetone alcohol with solutions of the corresponding metal trichlorides in pyridine at 100 °C. According to the crystal structure determinations the anions [LnCl₅(Py)]^2— are linked by bifurcated Cl···H···Cl bridges with the protons of the [HPy]⁺ cations forming chains along [001]. The anions of [H(Py)₂][YbCl₄(Py)₂]·Py form discrete octahedrons with trans‐positions of the pyridine ligands. [HPy]₂[EuCl₅(Py)] ( 1a ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1874.4(2), b = 1490.2(2), c = 741.5(1) pm, R₁ = 0.0466. [HPy]₂[ErCl₅(Py)] ( 1b ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1864.3(1), b = 1480.7(2), c = 739.7(1) pm, R₁ = 0.0314. [HPy]₂[YbCl₅(Py)] ( 1c ): Space group Pnma, Z = 4, lattice dimensions at —80 °C: a = 1858.9(2), b = 1479.0(1), c = 736.8(1) pm, R₁ = 0.0306. [H(Py)₂][YbCl₄(Py)₂]·Py ( 2 ·Py): Space group Ia, Z = 4, lattice dimensions at —80 °C: a = 1865.5(1), b = 827.5(1), c = 1873.4(1) pm, ß = 103.97(1)°, R₁ = 0.0258.     

2D LnIII(Nd/La)‐AgI Heterometallic and TmIII Homometallic Coordination Polymers Based on Pyridine Dicarboxylate ­Ligands

Two 2D 4d‐4f heterometallic coordination polymers, [LnAg(Py26DC)₂(H₂O)₃] · 3H₂O [Ln = Nd ( 1 ), La ( 2 ); H₂Py26DC = pyridine‐2,6‐dicarboxylic acid], and one 2D lanthanide homometallic coordination polymer, [Ln(Py25DC)(ox)_0.5(H₂O)₂] [Ln = Tm ( 3 ); H₂Py25DC = pyridine‐2,5‐dicarboxylic acid; ox = oxalate], were synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single‐crystal X‐ray diffraction analysis. Both complexes 1 and 2 are isostructural and exhibit 3‐connected 2D heterometallic layer structures with the Schläfli symbol of (8² · 10), whereas complex 3 represents an extended 2D homometallic network structure with (4,4) topology.     

Synthesis,Structure and Raman Data of the New Binuclear Zirconium Complex [Ph4P]2[(ZrCl4Py)2O], with a Zr‐O‐Zr Bridge

The new Zirconium(IV) coordination compound [Ph₄P]₂[(ZrCl₄Py)₂O] (Ph = phenyl, Py = pyridine) was synthesized by dissolving ZrCl₄, [Ph₄P]Cl and a stoichiometric amount of NaOH/Na mixture in pyridine or pyridine/organic solvent mixtures. The title phase was obtained as colourless crystals. The crystal structure of [Ph₄P]₂[(ZrCl₄Py)₂O] was determined. It crystallizes monoclinic, P2₁/c, Z = 4, a = 13.412(2), b = 13.461(2), c = 16.442(3) Å, β = 102.72(1)°. The structure consists of isolated tetraphenylphosphonium cations and [(ZrCl₄Py)₂O]^2? complex anions. The centrosymmetric complex anion contains a linear Zr–O–Zr bridge. Each Zr atom is coordinated by one oxygen dianion, the N atom of one pyridine ring and four chloro ligands in a distorted octahedral geometry. The Raman spectrum of [Ph₄P]₂[(ZrCl₄Py)₂O] is also reported. Most of the observed frequencies can be assigned to vibrations of the tetraphenylphosphonium cations and the pyridine rings.     

2,6‐Bis[bis(2‐pyridiniomethyl)aminomethyl]‐4‐tert‐butylphenol dichloride diperchlorate hydrate

The title compound, C₃₆H₄₄N₆O⁴⁺·2Cl^?·2ClO₄^?·0.132H₂O, is shown to be protonated at all the pyridine N atoms; the two chloride ions are hydrogen bonded to three pyridine N atoms and to the phenolic O atom of the same cation [Cl?N = 3.045 (2)–3.131 (2) Å and Cl?O = 2.938 (2) Å], and the remaining pyridine N atom is hydrogen bonded to the phenolic O atom [N?O = 2.861 (2) Å]. The mean value of the C—N—C angle of the protonated pyridine rings is 123.4 (1)°, which is significantly larger than that found for unprotonated pyridine rings.     

Syntheses and Characterization of Three New Compounds Based on Terephthalate and 2‐(2‐Pyridin‐4‐yl‐vinyl)benzimidazole Ligands

Three new compounds based on H₂BDC and PyBImE [H₂BDC = 1,4‐benzenedicarboxylatic acid, PyBImE = 2‐(2‐pyridin‐4‐yl‐vinyl)benzimidazole], namely, [Co(PyBImE)(BDC)(H₂O)₂] ( 1 ), [Co(PyBImE)₂(HBDC)(BDC)_0.5] ( 2 ), and [(HPyBImE)⁺ · (BDC)²–_0.5 · (H₂BDC)_0.5] ( 3 ), were synthesized by hydrothermal methods and characterized by single‐crystal X‐ray diffraction. Compound 1 is a one‐dimensional chain bridged by terephthalate in a bis(monodentate) fashion. In the complex the nitrogen atom from N_BIm and the coordination water molecule complete the coordination sphere. In complex 2 , the dinuclear cobalt units are bridged by terephthalate in a bis(bidentate) fashion into a one‐dimensional chain, but different from complex 1 , the nitrogen atom from N_Py and the oxygen atom from hydrogenterephthalate complete the coordination sphere. Complex 3 is a co‐crystal with PyBImE and H₂BDC in a 1:1 ratio and the transfer of hydrogen atoms leads the complex into a salt. Interesting supramolecular structures are shown due to the hydrogen bonding as well as π ··· π interactions in the three complexes. Thermal and magnetic properties of 1 and 2 were also studied.     

Synthesis and Crystal Structures of Bis(1‐{(E)‐2‐pyridinylmethylidene}‐semicarbazone)iron(II) and ‐copper(II) Diperchlorate Monohydrates

The pyridine‐2‐carbaldehyde semicarbazone ligand (HL) reacts with iron(II) and copper(II) perchlorates in boiling ethanol to yield red‐violet [Fe^II(HL)₂](ClO₄)₂·H₂O ( 1 ) and light‐green crystals [Cu^II(HL)₂](ClO₄)₂·H₂O ( 2 ). The crystals are triclinic with the metal ions in an octahedral environment, coordinated to two nitrogen and one oxygen‐donor atom from HL. Electronic, magnetic and electrochemical properties are presented as well.     

Poly[[di‐μ2‐aqua‐di‐μ5‐croconato(2–)‐nickel(II)dipotassium(I)] tetra­hydrate]

In the title compound, {[K₂Ni(C₅O₅)₂(H₂O)₂]·4H₂O}_n, the Ni atom lies on an inversion centre. Two inversion‐related croconate [4,5‐dihydroxy‐4‐cyclo­pentene‐1,2,3‐trionate(2−)] ligands and an Ni^II ion form a near‐planar symmetrical [Ni(C₅O₅)₂]²⁻ moiety. The near‐square coordination centre of the moiety is then extended to an octa­hedral core by vertically bonding two water mol­ecules in the [Ni(C₅O₅)₂(H₂O)₂]²⁻ coordination anion. The crystal structure is characterized by a three‐dimensional network, involving strong K⋯O⋯K binding, K⋯O—Ni binding and hydrogen bonding.     

Transformations of the chameleon ligand 1,10‐phenanthroline‐5,6‐dione/diol: cis‐dichlorido(1,10‐phenanthroline‐5,6‐dione‐κ2N,N′)‐trans‐dipyridinecobalt(II) pyridine disolvate prepared from the diol

The title compound, [CoCl₂(C₅H₅N)₂(C₁₂H₆N₂O₂)]·2C₅H₅N, is a neutral Co^II complex with two chloride anions coordinated in a cis fashion, two pyridine ligands in trans positions and a chelating 1,10‐phenanthroline‐5,6‐dione ligand that completes the octahedral coordination geometry. Two pyridine solvent molecules reside in channels (about 7 × 4 Å wide; the closest atom–atom distance within the channel is 10 Å). The three‐dimensional structure supporting these channels is held together by C—H...Cl [3.466 (8)–3.670 (9) Å] and C—H...O [3.014 (9)–3.285 (8) Å] hydrogen bonds, and can be viewed as a CsCl or bcu (body‐centred cubic) net.     

Synthesis and Characterization of [Hg(sulfamethoxazolato)2]·2DMSO and[Cu2(μ‐CH3CO2)4(sulfamethoxazole)2]

[Hg(sulfamethoxazolato)₂]·2DMSO ( 1 ) and [Cu₂(CH₃COO)₄(sulfa‐methoxazole)₂] ( 2 ) can be obtained by the reaction of sulfamethoxazole with mercury acetate or copper acetate in methanol. The structures of the two complexes were characterized by single crystal X—ray diffractometry. Compound 1 consists of sulfamethoxazolato ligands bridging the metal ions building an unidimensional chain. Two solvent dimethylsulfoxide molecules are involved via N‐H···O hydrogen bridges. The mercury atom shows a linear primary coordination arrangement formed by two trans deprotonated sulfonamidic nitrogen atoms. The overall coordination around the metal atom may be regarded as a strongly distorted octahedron when the interactions of mercury with four sulfonamidic oxygen atoms [bond distances of 2.761(4) Å—2.971(4) Å] are also considered to build an equatorial plane and the N1 and N1′ atoms [bond distance of 2.037(5) Å] occupy the apical positions. Compound 2 is a dinuclear complex in which the copper ions are bridged by four syn‐syn acetate ligands which are related by a symmetry centre located in the centre of the complex. Each copper atom presents a nearly octahedral coordination where the equatorial plane is formed by four oxygen atoms and an isoxazolic nitrogen atom and the second copper atom occupy the apical positions.     

Pyridin‐Komplexe von Seltenerd‐Trichloriden. Synthese und Kristallstrukturen von [YCl3(Py)4] und [LnCl3(Py)4] · 0,5 Py mit Ln = La und Er

Pyridine Complexes of Rare Earth Element Trichlorides. Syntheses and Crystal Structures of [YCl₃(py)₄] and [LnCl₃(py)₄] · 0.5 py with Ln = La and Er The pyridine complexes [YCl₃(py)₄] ( 1 ), [LaCl₃(py)₄] · 0.5 py ( 2 · 0.5 py), and [ErCl₃(py)₄] · 0.5 py ( 3 · 0.5 py) have been prepared from the diacetone‐alcohol complexes [LnCl₃(DAA)₂] or directly from the metal trichlorides with excess pyridine to give colourless, only sparingly moisture sensitive crystals. They were characterized by IR spectroscopy and by crystal structure determinations. 1 : Space group Pbca, Z = 16, lattice dimensions at –80 °C: a = 1647.4(1), b = 1743.1(1), c = 3190.5(1) pm, R₁ = 0.031. 2 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 978.9(1), b = 1704.5(1), c = 1589.5(1) pm, β = 103.61(1)°, R₁ = 0.0281. 3 · 0,5 Py: Space group P2₁/n, Z = 4, lattice dimensions at –80 °C: a = 970.1(1), b = 1706.4(1), c = 1566.1(1) pm, β = 103.46(1)°, R₁ = 0.0232. All complexes realize monomeric molecular structures with the metal atom in a distorted pentagonal‐bipyramidal coordination. One of the chlorine atoms and the four pyridine molecules are in the equatorial plane.     

Crystal Structure and Ethylene Oligomerization Catalytic Activity of {2-Carbethoxy-6-[1-[（2,6-diethylphenyl）imino]ethyl]pyridine}CoCl2

The unsymmetric precursor ethyl 6-acetylpyridine-2-carboxylate （4） was synthesized from 2,6-dimethylpyridine （1）. On the basis of this precursor, a new mono（imino）pyridine ligand （5） and the corresponding Co（Ⅱ） complex {2-carbethoxy-6-[1-[（2,6-diethylphenyl）imino]ethyl]pyridine}CoCl2 （6） were prepared. The crystal structure of complex indicates that the 2-carbethoxy-6-iminopyridine is coordinated to the cobalt as a tridentate ligand using [N, N, O] atoms, and the coordination geometry of the central cobalt is a distorted trigonal bipyramid, with the pyridyl nitrogen atom and the two chlorine atoms forming the equatorial plane. Being applied to the ethylene oligomedzation, this cobalt complex shows catalytic activity of 1.820× 10^4 g/mol-Cooh at 101325 Pa of ethylene at 15.5℃ for 1 h, when 1000 equiv, of methylaluminoxane （MAO） is employed as the cocatalyst.     

Untersuchungen zur Darstellung des Phosphorsäurefluoridpyridiniumbetains,Py · PO2F (Py = Pyridin)

Studies on the Preparation of the Phosphoric Acid Fluoride Pyridinium Betaine, Py · PO₂F (Py = Pyridine) Under anhydrous reaction conditions phosphoric acid chloride betaine, Py · PO₂Cl ( I ), does not react with NaF or NaSO₂F to the corresponding fluorine compound Py · PO₂F ( II ). Reaction between AsF₃ and I gives rise to the formation of compound II which is detectable by N.M.R. In an excess of pyridine POCl₂F reacts with P₄O₁₀ to a mixture of I and II which are difficult to be separated. In a preparatively simple way II can be obtained by sulfur-oxygen exchange in liquid SO₂ starting from dithiophosphoric acid fluoride betaine Py · PS₂F.     

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.     

Tris[N‐(4‐fluorophenyl)pyridine‐2‐carboxamidato‐κ2N,N′]cobalt(III) trihydrate: a novel meridional complex

The title complex, [Co(C₁₂H₈FN₂O)₃]·3H₂O, has been synthesized for the first time. The complex comprises three bidentate ligands containing the pyridine‐2‐carbox­amide stem. The distorted octahedral coordination around the Co atom is formed via the pyridine (py) N atom and the deprotonated amide N atom of each ligand, with the three pyridine rings in a meridional arrangement. For each ligand, the pyridine ring and the carbonyl group are nearly coplanar, with torsion angles in the range 0.4 (3)–4.8 (4)°. The Co—N_py distances [1.9258 (16)–1.9656 (17) Å] are shorter than the corresponding Co—N_amide distances [1.9372 (17)–1.9873 (15) Å]. In addition, the Co—N_py distances are closely related to the magnitudes of the chelate angles, a shorter Co—N_py distance corresponding to a larger angle. Five intermolecular hydrogen bonds, involving carbonyl O atoms of the ligands and lattice water mol­ecules, lead to the formation of a mesh structure.     

fac‐Bromo­tri­carbonyl­[2‐(2‐pyridylmethyl)‐2,3‐di­hydro‐1H‐isoindol‐1‐one]­rhenium(I) methanol solvate

The structure of the title compound, fac‐[ReBr(C₁₄H₁₂N₂O)(CO)₃]·CH₄O, consists of neutral mononuclear mol­ecular units of distorted octahedral geometry, with the three carbonyl donors in a facial orientation. The remaining coordination sites are occupied by the Br atom, the pyridine N atom and the ketone O‐atom donor of the ligand. The mol­ecules pack in stacks of antiparallel tapes, with a network of classical (O—H⋯Br) and non‐classical (C—H⋯O) hydrogen bonds between the methanol solvent mol­ecule and the complex mol­ecule.     

Crystallographic report: [(Pyridine)(1,2‐bis(2‐pyrazinecarboxamido)‐4,5‐dimethylbenzene)zinc(II)] monohydrate

The N₄ donor ligand, Me₂bpzb^2? and a pyridine molecule are coordinated to the Zinc(II) so that the coordination geometry closely resembles a square‐pyramidal environment with a nitrogen atom of the pyridine ligand occupying the apical position. Copyright © 2003 John Wiley & Sons, Ltd.     

Koordinationspolymere 1, 2‐Dithiooxalato‐ und 1, 2‐Dithioquadratato‐Komplexe. Synthese und Strukturen von [BaCr2(bipy)2(1, 2‐dtox)4(H2O)2], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)2(H2O)2]·2H2O und [H3O][H5O2][Cu(cyclam)]3[Cu2(1, 2‐dtsq)3]2

Coordination Polymeric 1, 2‐Dithiooxalato and 1, 2‐Dithiosquarato Complexes. Syntheses and Structures of [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂], [Ni(cyclam)(1, 2‐dtsq)]·2DMF, [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H2₂, and [H₃O][H₅O₂][Cu(cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ 1, 2‐Dithioxalate and 1, 2‐dithiosquarate ions have a pair of soft and hard donor centers and thus are suited for the formation of coordination polymeric complexes containing soft and hard metal ions. The structures of four compounds with building blocks containing these ligands are reported: In [BaCr₂(bipy)₂(1, 2‐dtox)₄(H₂O)₂] Barium ions and pairs of Cr(bipy)(1, 2‐dtox)₂ complexes form linear chains by the bisbidentate coordination of the dithiooxalate ligands towards Ba²⁺ and Cr³⁺. In [Ni(cyclam)(1, 2‐dtsq)]·2DMF short NÖH···O hydrogen bonds link the NiS₂N₄‐octahedra with C_2v‐symmetry to an infinite chain. In [Ni(cyclam)Mn(1, 2‐dtsq)₂(H₂O)₂]·2H₂O the 1, 2‐dithiosquarato ligand shows a rare example of S‐coordination towards manganese(II). The sulfur atoms of cis‐MnO₂S₄‐polyedra are weakly coordinated towards the axial sites of square‐planar NiN₄‐centers, thus forming a zig‐zag‐chain of Mn···Ni···Mn···Ni polyhedra. [H₃O][H₅O₂][Cu (cyclam)]₃[Cu₂(1, 2‐dtsq)₃]₂ contains square planar [Cu^II(cyclam)]²⁺ ions and dinuclear [Cu^I₂(1, 2‐dtsq)₃]^4— ions. Here each copper atom is trigonally planar coordinated by S‐donor atoms of the ligands. The Cu…Cu distance is 2.861(4)Å.     

Bis[1‐(2‐hydroxyethyl)‐4,10‐diazapyrazolo[4,3‐b]fluoren‐5(1H)‐one thiosemicarbazonato]zinc(II) dimethylformamide trisolvate monohydrate

In the title Schiff base complex, [Zn(C₁₅H₁₂N₇OS)₂]·3C₃H₇NO·H₂O, each Zn^II atom is six‐coordinated in a distorted octahedral environment by two ligands acting in a tridentate chelating mode through two N atoms and one S atom. The coordination mode of the ligand is nearly planar. There are three dimethylformamide molecules and one water molecule solvating the complex. The coordination behavior of the ligand is compared with that of related ligands in similar complexes.     

Coordination Centres of Purine Nucleotides: Adenosine‐5′‐diphosphate and Adenosine‐5′‐triphosphate in their Reactions with Nickel(II), Cobalt(II) and Tetramines

Interactions between the nucleotides: adenosine‐5′‐diphosphate (ADP) and adenosine‐5′‐triphosphate (ATP) with Ni^II and Co^II ions, as well as with spermine (Spm) and 1,11‐diamine‐4,8‐diazaundecane (3,3,3‐tet) are the subject of this study. Composition and stability constants of mixed complexes thus formed have been determined on the basis of the potentiometric measurements, whereas interaction centres in ligands have been identified by VIS and NMR spectral parameter analysis. Mixed tetraprotonated complexes with Ni^II, i.e. Ni(ADP)H₄(Spm), Ni(ATP)H₄(Spm), Ni(ADP)H₄(3,3,3‐tet) and Ni(ATP)H₄(333‐tet), are identified as ML·······L′ type adducts, in which the main coordination centre is the nucleotide nitrogen N(1) or N(7) donor atom, and the fully protonated polyamine is engaged in noncovalent interactions with nucleotide phosphate group oxygen atoms. Ni(ADP)H₂(Spm), Ni(ATP)H₂(Spm), Ni(ADP)H₂(3,3,3‐tet) and Ni(ATP)H₂(3,3,3‐tet) complexes represent the {N3} coordination type In diprotonated mixed complexes of Ni^II with spermine are weak noncovalent interligand interactions, providing an additional stabilising effect. Formation of ML·······L′ type molecular complexes has been observed in systems with Co^II: Co(ADP)H₄(Spm), Co(ATP)H₄(Spm), Co(ADP)H₄(3,3,3‐tet) and Co(ATP)H₄(3,3,3‐tet), in which the N(7) atom and oxygen atoms of the phosphate group are involved in coordination and the fully protonated polyamine is engaged in noncovalent interactions with the nucleotide N(1).