X-ray crystal structure of di-μ-carbonyldicarbonyl-bis(η5-pentamethylcyclopentadienyl)diruthenium

An X-ray diffraction study of [(⁵-C₅Me₅)Ru(CO)(-CO)]₂ was performed, revealing its dimeric structure and centrosymmetrictrans conformation. The Ru-Ru bond length (2.758(1) Å) and the separation between the Ru atom and the plane of the ⁵-C₅Me₅ ligand (1.923 Å) are greater than those in the Cp analog and in the isostructural Cp and C₅Me₅ complexes of iron; this effect is due to the s inductive effect of the Me groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 543–544, March, 1994.     

Synthesis, crystal structure, and thermal properties of N,N′-di(diethoxythiophosphoryl)-1,4-phenylenediamine

The title compound N,N′-di(diethoxythiophosphoryl)-1,4-phenyl-enediamine was synthesized by the reaction of diethoxythiophosphoryl chloride with p-phenylenediamine and characterized by elemental analysis, IR, and ¹H NMR spectra. Its crystal structure was determined by X-ray diffraction analysis and the thermal property was studied by TG analysis. The relative molecular weight of the title compound is 412.42. The crystal structure belongs to the orthorhombic, Pbca space group, with a = 0.86936(16) nm, b = 1.2787(2) nm, c = 1.8897(3) nm, β = 90°, V = 2.1006(7) nm³, Z = 8, Dc = 1.304 g/cm³, μ(Mo Kα) = 0.425 mm⁻¹, F(000) = 872, S = 1.052, the final R = 0.0628 and wR = 0.1860 for 1852 observed reflections with I>2σ(I). The X-ray diffraction analysis demonstrates that the crystal structure is centrosymmetric. The weak N-H⋯S intramolecular hydrogen bonds were observed to link the molecules into sheets. The TG analysis shows that the title compound has good thermal stability and char forming capability and its fire retardation for polyacrylonitrile reveals that the compound is an excellent intumescent fire retardant. __________ Translated from Acta Chimica Sinica, 2007, 65(18): 2034–2038 [译自: 化学学报]     

Synthesis,crystal structure and photo-induced isomerization of [ N,N ′- bis (4-fluorobenzylidene) ethylenediamine]bromo(triphenylphosphine)copper(I) complex

Abstract

The electrochemical behavior of VOQ₂OH or [VOQ₂-OVOQ₂] (Q = 8-hydroxyquinohnate anion) has been investigated by cyclic voltammetry in acetonitnie solutions. Although both species exist simultaneously at every condition analyzed, they can be clearly differentiated by this method. The effect of trace amounts of water on the electrochemical behavior is also discussed.     

Synthesis and crystal structure of dinuclear nickel (Ⅱ) complex

The crystal structure of Ni(Ⅱ) complex with 3-hydroxyl-1, 5-diazacycloheptane-N, N'-diacetate was determined by X-ray diffraction method. Crystal data for Ni2 (C9H14N2O5)2·2H2O: monoclinic, space group P21/n, a = 1.1717(5), b = 0.9794(3), c = 1.2971(2) nm, β= 96.62(3), V= 1.4786(7) nm3, Dc = 1.377 g/cm3, Z = 2,μ=13.321 cm-1 (Mo-Kα), F(000)=640. The final R and Rw are 0.075 and 0.089 respectively. The Ni(Ⅱ) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(Ⅱ) atoms which are bridged by two O atoms. Every Ni(Ⅱ) is coordinated by two N atoms and four 0 atoms. The coordination polyhedron of the Ni(Ⅱ) ion is a distorted octahedron.     

Pyrazolate bridged ruthenium(I) complexes. A convenient synthesis of ruthenium(I) compounds. The X-ray structure of bis-μ-(3,5-dimethylpyrazolate)bis(tricarbonyl-ruthenium(I)) (RuRu)

RuCl₃·nH₂O reacts with carbon monoxide in boiling 2-methoxyethanol to give a solution which upon treatment with pyrazole-type ligands (HPz) in the presence of zinc and carbon monoxide yields the complexes [Ru(μ-Pz)(CO)₃]₂. This provides an easy high-yield route to ruthenium(I) complexes. In the crystal structure of [Ru(μ-dpmz)(CO)₃]₂ (dpmz = 3,5-dimethylpyrazolate) the Ru₂N₄ framework adopts a boat conformation with a RuRu distance of 2.705(2) Å.     

Synthesis and crystal structure of one-dimensional azide-bridged Mn(III) polymer [Mn(Sal2-1,2Pn)(N3)] n (Sal2-1,2Pn = N,N′-bis(salicylidene)-1,2-propanediamine)

The new one-dimensional azide-bridged manganese(III) polymer, [Mn(Sal₂-1,2Pn)(N₃)] _n (I), where Sal₂-1,2 Pn = N, N,N′-bis(salicylidene)-1,2-propanediamine, was prepared from a reaction mixture containing Sal₂-1,2 Pn, MnCl₂ · 2H₂O and NaN₃ (2: 1: 8 molar ratio) in methanol-chloroform (v/v 2: 1) and has been characterized by elemental analyses, FT-IR spectroscopy, and X-ray single-crystal diffraction. In the structure of I, Mn³⁺ ion is in a distorted octahedral geometry with an obvious Jahn-Teller distortion. The quadridentate Schiff-base ligand Sal₂-1,2Pn is located in the equatorial plane. The azide ion acts as an end-to-end bridge to form the one-dimensional manganese(III) polymer.     

Solvent-free synthesis and crystal structures of s-cis and s-trans N,N′-bis(2-hydroxycyclohexyl)ethane-1,2-diamine

The symmetrical amino alcohol synthesis via ring opening of cyclohexene oxide with ethylendiamine is illustrated by synthesis and characterization of β-amino alcohols s-cis-(SSSS)-cy₂en (1) and s-trans-(SSRR)-cy₂en (2) (cy₂en = N,N′-bis(2-hydroxycyclohexyl)ethane-1,2-diamine) in one step and with high yield. The reaction was carried out in a microwave reactor under solvent-free conditions. These products were characterized by IR and Raman spectroscopy, elemental analysis, thermal methods (TGA, DTG and DTA), mass spectrometry and ¹H and ¹³C NMR spectroscopy. The crystal structures of 1 and 2 were determined by single crystal X-ray structural analysis, followed by DFT calculations. Intramolecular hydrogen bond was observed in 1 with C ₂ symmetry, but not in 2 with C _i symmetry. The nature of intramolecular hydrogen bond in 1 has been investigated by AIM and NBO analyses. The molecules in 1 are linked into an infinite chain along the [001] direction, giving rise to R ₄ ⁴ (8) graph-set motif, while the molecules in 2 are linked into a 2D network in the bc plane, giving rise to R ₂ ² (10) and R ₃ ³ (12) motifs. The protonation equilibria of 1 and 2 have been studied by pH-potentiometry, with pK ₁ 9.01 and pK ₂ 5.50 determined for 1 and pK ₁ 8.58 and pK ₂ 5.26 determined for 2.     

Bis(μ3-barbiturato−O,O,O′)-(μ2-aqua)- aqua-barium(II): crystal structure,spectroscopic and thermal properties

A polymeric coordination compound, [Ba(H₂O) ₂(Hba)₂] (1) (H₂ba – barbituric acid, C₄H₄N₂O₃), was obtained. The structure of 1 was solved using powder X-ray diffraction methods. The Ba²⁺ ion in 1 formed a three-capped trigonal prism. The BaO₉ polyhedra, connected with each other by the edges and faces, formed a chain. Several 4- and 12-membered cycles due to the bridging μ₂-H₂O and bridging μ₃-Hba^– also formed implementing a 3-D polymer structure. The structures of 1 and other thiobarbiturate complexes were compared. The replacement of a S atom by an O atom in the heterocyclic ligand Htba^? (thiobarbiturate ion) of the compound Ba(H₂O)₂(Htba)₂ resulted in changes of the coordination number Ba(II) and supramolecular structure. The intermolecular hydrogen bonds O–H?O and N–H?O formed a 3-D net where pronounced 2-D layers of Hba^– ions could be found. A new topological net in 1 was observed. The IR and thermal stability were investigated.     

Synthesis and crystal structure of the equimolar complex of copper(I) cyanide with 3,3′-[ethane-1,2-diylbis(oxy)]dipropanenitrile

Complex [Cu(CN)(NC(CH₂)₂O(CH₂)₂O(CH₂)₂CN))] is obtained by the heating of copper(I) cyanide with 3,3′-[ethane-1,2-diylbis(oxy)]dipropanenitrile (DPN) followed by slow cooling. The X-ray diffraction analysis shows that the crystals are monoclinic, space group C2/c, a = 12.183(2), b = 10.667(2), c = 8.4700(13) Å, β = 92.444(10)°, V = 1099.7(3) ų, Z = 4. The structure is built of infinite zigzag fragments [Cu(CN)(DPN)] _n . The tetrahedral environment of the copper atom includes two cyano groups of the ligand and two cyano groups of the inorganic fragment.     

Synthesis,crystal structure and reactivity of trans-diaquo N,N′-ethylenebis-(3-methoxysalicylideneiminato)chromium(III)

A new chromium(III) Schiff base complex, [Cr(3-methoxysalen)(H₂O)₂]ClO₄, where salen=N,N-ethylenebis- (salicylideneimine), has been synthesized and characterized by spectroscopic techniques. Single crystal X-ray data reveals that the complex assumes a trans-diaquo structure with formulation [Cr(C₁₈H₂₂N₂O₆)]ClO₄ but, unlike in Cr (salen)(H₂O)₂ ⁺, the two trans-water molecules are equidistant from Cr^III. The effect of the substituent on the phenyl ring in respect of redox reactivity has been investigated. The kinetics of the oxidation of [Cr(Schiff base)- (H₂O)₂]ClO₄, where Schiff base=salen, (1) and 3-OMe-salen, (2) by PhOI has been studied. The bimolecular rate constant for the formation of the O=Cr^v Schiff base in case of (2) was four times faster than that of (1). The introduction of the OMe group substituent on the phenyl ring influences not only the structure and crystal packing, but also the reactivity of the complex and the electronic environment around the metal ion.     

Crystal structure of diaquatetrakis (μ-2,6-dichlorobenzoato-o,o′)dicopper(II)

Summary A new copper(II) complex of the formula [Cu(C₇H₃O₂Cl₂)₂·H₂O]₂ crystallizes in the triclinic system (space group P ). The cell parameters area=7.267(3),b=10.687(3),c= 10.934(3) Å, =99.88(3), =96.25(3), =94.78(3)°,V=827.1(5)ų,Z=1,D _c=1.853(1), andD _m=1.85 Mg/m³. The two copper atoms in the molecule are held together by the four carboxylate groups of the organic ligands, and each copper atom is further bonded to a water molecule, resulting in a square pyramidal geometry. The Cu-O(carboxylate) distances are in the range of 1.955(2)-1.975(2)Å, and Cu-O(water) and Cu-Cu distances are 2.166(2) and 2.605(1)Å, respectively.

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Kristallstruktur von Diaquatetrakis(-2,6-dichlorobenzoato-o,o)dikupfer(II)

Zusammenfassung Ein neuer Kupfer(II)-Komplex mit der Formel [Cu(C₇H₃O₂Cl₂)₂·H₂O]₂ kristallisiert im triklinen System (Raumgruppe P ) mit den Zellparameterna=7.267(3),b=10.678(3),c=10.934(3)Å, =99.88(3), =96.25(3), =94.78(3)°,V=827.1(5)ų,Z=1,D _c=1.853(1) undD _m=1.85 Mg/m³. Die beiden Kupferatome im Molekül werden von den vier Carboxylatgruppen der organischen Liganden zusammengehalten. Jedes Kupferatom ist zusätzlich an ein Wassermolekül gebunden, woraus eine quadratisch pyramidale Geometrie resultiert. Die Cu-O(Carboxylat)-Abstände liegen in einem Bereich von 1.955(2)–1.975(2)Å; die Cu-O(Wasser)- und Cu-Cu-Abstände betragen jeweils 2.166(2) und 2.605(1)Å.

     

Synthesis,acid-base and complexing properties of N,N,N′,N′-tetrakis(O-butylhydroxyphosphorylmethyl)-1,2-diaminoethane

Russian Journal of General Chemistry - A method of synthesis of organophosphorus analog of ethylenediaminetetraacetic acid (a common complexon),...     

Mononuclear copper(I) complexes with triphenylphosphine and N,N′-disubstituted thioureas: synthesis,characterization, and biological evaluation

Abstract

Twelve new complexes, of the general formula CuCl(TPP)₂Tu^1–12 (Tu?=?thiourea), were synthesized by the reaction of CuCl(TPP)₃ (TPP?=?triphenylphosphine) and various N,N′-disubstituted thioureas. The structures of the synthesized complexes were characterized by different techniques such as Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy (¹H, ¹³C, ³¹P, and ¹⁹F), and the representative complexes (1, 2 and 12) were analyzed via single crystal X-ray diffraction. The single crystal X-ray analysis revealed that copper(I) is coordinated with chlorine, two TPP, and the thiourea ligands through the sulfur atom in a mononuclear distorted tetrahedral mode. The compounds were tested for antibacterial, antifungal, cytotoxicity, antileishmanial, and antioxidant activities. The results showed that the synthesized complexes are significantly more active than the free ligands and the commercial reference compounds. The high biological activities of the complexes versus free ligands can be attributed to the copper(I) chloride complexation with thiourea ligands. The synthesized complexes were also evaluated, both experimentally and theoretically, for DNA binding studies. The UV-visible spectroscopic and molecular docking studies demonstrated that the complexes are conjugating with DNA through a groove binding mode.     

Crystal structure and magnetic properties of catena-μ-(pyrazine-N,N′)bis[(p-nitrobenzoyl)trifluoroacetonato-O,O′]copper(II)

The X-ray crystal structure, variable-temperature magnetic susceptibilities and e.s.r. spectra are reported for the title complex. The complex crystallises as infinite chains in which the copper(II)-β-diketonate units are bridged axially by ambidentate pyrazine ligands with a Cu⋯Cu separation of 7.6700(2) Å. The magnetic susceptibility measurements in the range 5–325 K are consistent with the ferromagnetic intrachain exchange. The S=1/2 Heisenberg ferromagnetic linear chain analysis results in magnetic parameters of g=2.12 and J/k=0.6 K.     

Crystal structure of bis(triphenylphosphine) bis(N,N′-dibutylthiourea)silver(I) nitrate

A mixed-ligand silver(I) complex of triphenylphosphine and N,N′-dibutylthiourea (Dbtu), [Ag(Ph₃P)₂(Dbtu)₂]NO₃, is prepared and its structure in the solid state is determined by X-ray crystallography. X-ray structure of this complex shows that it is mononuclear with the silver atom coordinated by two PPh₃ and two dibutylthiourea ligands adopting a distorted tetrahedral geometry. The crystal structure shows the formation of 1-D chains through intermolecular hydrogen bonding interactions between N-H of Dbtu and nitrate ions. The new complex is also characterized by IR and NMR (¹H and ³¹P) spectroscopy. The spectroscopic data are discussed in terms of the nature of bonding. A similar mixedligand complex is also prepared for tetramethylthiourea (Tmtu), but the structure of the resulting compound shows that it is a bis(phosphine) complex, [Ag(PPh₃)₂NO₃] rather than a mixed-ligand complex.     

Synthesis and crystal structure of cyclotris-(4,4′-thiodiphenylene ketone)

The side reaction of macrocyclization that occurs during the synthesis of poly-(1,4-phenylenesulfide ketone) by polycondensation of a 4,4-dihalobenzophenone with sodium sulfide was studied. It was found that the major product of this reaction is a cyclic trimer, cyclotris-(4,4"-thiodiphenylene ketone) (1). Despite the fact that ketone bridges are more rigid than sulfide bridges, the yield of the macrocycle is rather high, as it is in the synthesis of poly-(1,4-phenylenesulfide), and reaches 20% under high dilution conditions. The structure of 1 was investigated by X-ray diffraction analysis (R = 0.069 on 3138 reflections). Macrocycle 1 is strongly flattened in the crystal; the conformation observed is determined by the packing, since stereochemical analysis indicates high flexibility of the macrocycle. The solvate acetone molecules incorporated in the crystal are disordered, nevertheless, they are strongly fixed in the cavities and channels of the crystal structure.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1460–1466, August, 1994.     

Synthesis and crystal structure of a trinuclear copper(II) complex derived from N,N′-Bis(4-methoxysalicylidene)-1,3-pentanediamine

A trinuclear copper(II) complex [Cu₃Cl₂L₂], where L is the dianionic form of N,N′-bis(4-methoxysalicylidene)-1,3-pentanediamine, has been synthesized and characterized by means of spectroscopic methods and single crystal X-ray structure determination. The complex crystallizes in the orthorhombic space group Pnma with unit cell dimensions a = 15.301(2), b = 23.226(2), c = 12.089(1)Å, V = 4296.2(8) ų, Z = 4, R ₁ = 0.0682, and wR ₂ = 0.1590. The molecule of the complex possesses a crystallographic mirror plane symmetry with the mirror plane passes through the three Cu atoms and the two Cl atoms. The two terminal Cu atoms adopt distorted square pyramidal coordination, and the middle one adopts square planar coordination. The intramolecular Cu…Cu distances are 2.900(1) and 2.916(1) Å. The complex was tested for its antibacterial activity to assess its inhibiting potential.