Synthesis and structure of bischelate gallium complexes (dpp-bian)Ga(acac) and (dpp-bian)Ga(2,2´-bipy) (dpp-bian is 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene)

A reaction of digallane [(dpp-bian)Ga—Ga(dpp-bian)] (1) (dpp-bian is the 1,2-bis[(2,6-disopropylphenyl)imino]acenaphthene) with one equivalent of I₂ leads to oxidation of (dpp-bian)^2– in compound 1 to (dpp-bian)–and gives [(dpp-bian)GaI—GaI(dpp-bian)] (2). In the reaction of compound 2 with two equivalents of (acac)Na, not only exchange of the iodide and acetylacetonate ions takes place, but also a transfer of electrons from the metal—metal bond to dpp-bian with the formation of the complex [(dpp-bian)Ga(acac)] (3), in which the dpp-bian ligand is a dianion. A reaction of digallane 1 with 2,2´-bipyridyl at 200 °C in toluene in a sealed tube leads to the reduction of 2,2´-bipyridyl and gives the complex [(dpp-bian)Ga(bipy)] (4), which contains two different chelate redox-active ligands. The new compounds were characterized by IR (3, 4), NMR (3), and ESR spectra (4), the structures of both derivatives were established by X-ray diffraction.     

Synthesis and crystal structure of (E)-[(2-cyclohexenyl) vinyl]triaryltin

(E)-[(2-Cyclohexenyl)vinyl]triaryltin (aryl=phenyl, p-tolyl) were synthesized and characterized by elemental analysis, IR, 1H NMR spectroscopy. The crystal structure of (E)-[(2-cyclohexenyl)vinyl]triphenyltin was also determined by the X-ray diffraction. Experiments show that this compound has the conjugated system, which makes it have possible bioactivity and anti-tumor activity.     

Copper(II) halide complexes of aminopyridines: Syntheses,structures and magnetic properties of [(5CAP)2CuX2] and [(5BAP)nCuX2] (X = Cl,Br)

Abstract

Reaction of 2-amino-5-halopyridine molecules with Cu(II) halides in the solid state via mechanochemical techniques produced four coordination complexes, (5BAP)₂CuBr₂ (2a), (5BAP)₂CuCl₂ (3), (5CAP)₂CuCl₂ (4), (5CAP)₂CuBr₂ (5) [5BAP?=?2-amino-5-bromopyridine; 5CAP?=?2-amino-5-chloropyridine]. In all compounds, the 5BAP or 5CAP ligands are coordinated to the Cu(II) ion through the pyridine N atom along with two halide ions. Compounds 2 and 3 crystallized in the P-1 and P2₁/c space groups, respectively. Temperature dependent magnetic susceptibility data for 2 were fit to the antiferromagnetic rectangle model (J?=?–4.5(2) K; α?=?0.89(17)), while the data for 3 were fit to the uniform chain model (J?=?–4.20(6) K), indicating a significant difference in the interchain interactions. Both 4 and 5 crystallize with the 5CAP ligands in the syn-conformation in the space groups I2/a and P21/n, respectively. Compound 4 formed the expected dimeric structure via bridging chloride ions and the magnetic data were successfully fit to the dimer model (J?=?–2.57(5) K), while 5 unexpectedly formed a structural chain via Br…Br contacts which exhibits very weak antiferromagnetic interactions. An intermediate structure, (5BAP)(H₂O)CuBr₂ (1), was prepared and characterized via mechanochemical methods along with an isomer of (5BAP)₂CuBr₂ (2b).     

Synthesis and One-dimensional Structure of Cobalt(Ⅱ) Complex [(NaOC_2H_5)CoL_2]_n

IntroductionCobaltis one of the essential trace elements inthe human body,and is often used as a spectralprobe in structural studies on metal proteins[1] .Moreover,extensive literature reports on infinitepolymeric chains with various transition metal ionsindicate the most common route to obtaining cate-na- complexes,thatis,polydentate ligands are usedas bridges between metallic units[2— 13 ] .Althoughnumerous transition metal complexes have been ob-tained in this way[2 ,3 ,7— 9] ,few charact…     

Hydroamination of alkynes with aromatic amines catalyzed by digallane (dpp-bian)Ga—Ga(dpp-bian)

Digallane (dpp-bian)Ga—Ga(dpp-bian) (1) (dpp-bian is the 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene) catalyzes the addition of 4-chloroaniline to some terminal alkynes RC≡CH (R = Buⁿ, Ph, 4-MeC₆H₄). The reaction orders in each of the substrates were found for the reaction of phenylacetylene with 4-chloroaniline catalyzed by compound 1. The reaction of compound 1 with phenylacetylene in a molar ratio of 1: 10 led to 1-[N-(2,6-diisopropylphenyl)imino]-2-(1-phenylethylidene)acenaphthene (5) and the compound [C₁₂H₆(NC₆H₃Pr₂ ⁱ)(PhC=CH₂)(PhC=CH)]Ga(C≡CPh)₂ (6). The reaction of digallane 1 with phenylacetylene and aniline in a stoichiometric ratio of 1: 2: 2 gave bis-anilide (dpp-bian)-Ga[N(H)Ph]₂ (7) in 40% yield. The compound (PhC≡C)₃Ga·THF (9) was obtained by the reaction of three equivalents of sodium phenylacetylide (prepared in situ from phenylacetylene and sodium) with one equivalent of GaCl₃ in tetrahydrofuran. Compounds 5—7 and 9 were characterized by IR spectroscopy, ¹H NMR spectroscopy was used to characterize products 5, 6, and 9, whereas EPR spectroscopy was used for amide 7. The structures of compounds 5—7 and 9 were determined by single crystal X-ray diffraction analysis.     

Probing the aromaticity of the [(H(t)Ac)3(μ2-H)6], [(H(t)Th)3(μ2-H)6],(+), and [(H(t)Pa)3(μ2-H)6] clusters

In this study we report about the aromaticity of the prototypical [(H(t)Ac)(3)(μ(2)-H)(6)], [(H(t)Th)(3)(μ(2)-H)(6)](+), and [(H(t)Pa)(3)(μ(2)-H)(6)] clusters via two magnetic criteria: nucleus-independent chemical shifts (NICS) and the magnetically induced current density. All-electron density functional theory calculations were carried out using the two-component zeroth-order regular approach and the four-component Dirac-Coulomb Hamiltonian, including scalar and spin-orbit relativistic effects. Four-component current density maps and the integration of induced ring-current susceptibilities clearly show that the clusters [(H(t)Ac)(3)(μ(2)-H)(6)] and [(H(t)Th)(3)(μ(2)-H)(6)](+) are non-aromatic whereas [(H(t)Pa)(3)(μ(2)-H)(6)] is anti-aromatic. However, for the thorium cluster we find a discrepancy between the current density plots and the classification through the NICS index. Our results also demonstrate the increasing influence of f orbitals, on bonding and magnetic properties, with increasing atomic number in these clusters. We think that the enhanced electron mobility in [(H(t)Pa)(3)(μ(2)-H)(6)] is due the significant 5f character of its valence shell. Also the participation of f orbitals in bonding is the reason why the protactinium cluster has the shortest bond lengths of the three clusters. This study provides another example showing that the magnetically induced current density approach can give more reliable results than the NICS index.     

Syntheses and crystal structures of [Ni(IIP)2] and [Cu2(PMP)2(μ1,1-N3)2] · MeOH (IIP = 2-iminomethyl-4,6-diiodophenolate, PMP = 2-[(2-phenylaminoethylimino)methyl]phenolate)

A new centrosymmetric mononuclear nickel(II) complex, [Ni(IIP)₂] (I), and a new end-on azido-bridged dinuclear copper(II) complex, [Cu₂(PMP)₂(μ_1,1-N₃)₂] · MeOH (II) (IIP = 2-iminomethyl-4,6-diiodophenolate, PMP = 2-[(2-phenylaminoethylimino)methyl]phenolate), have been prepared from similar tridentate Schiff bases derived from N-phenylethane-1,2-diamine with 3,5-diiodosalicylaldehyde and salicylaldehyde, respectively. The complexes were characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. Complex I crystallizes in the monoclinic space group P2₁/c with unit cell dimensions a = 4.936(1), b = 11.779(3), c = 15.789(4) Å, β = 90.722(3)°, V = 918.0(4) ų, Z = 2, R ₁ = 0.0267, and wR ₂ = 0.0546. Complex II crystallizes in the orthorhombic space group Pna2₁ with unit cell dimensions a = 23.370(2), b = 12.210(1), c = 11.438(1) Å, V = 3263.8(5) ų, Z = 4, R ₁ = 0.0461, and wR ₂ = 0.0891. The Ni atom in I is in a square planar coordination, and the Cu atoms in II are in square pyramidal coordination.     

Synthesis and crystal structure of Cs2[(UO2)2(C2O4)3] and Cs2[UO2(C3H2O4)2] · H2O

Cs₂[(UO₂)₂(C₂O₄)₃] (I) and Cs₂[UO₂(C₃H₂O₄)₂] · H₂O (II) have been synthesized and studied by X-ray diffraction. The crystals of complexes I and II are monoclinic: a = 8.1453(2) Å, b = 8.9831(2) Å, c = 11.3897(4) Å, β = 104.0950(10)°, V = 808.29(4) ų, space group P2₁/n, Z = 2, and R ₁ = 0.0255 for I and a = 9.6998(2) Å, b = 17.8686(3) Å, c = 8.2074(2) Å, β = 97.5780(10)°, V = 1410.10(5) ų, space group P2₁/c, Z = 4, and R ₁ = 0.0287 for II. The uranium-containing structural units of complexes I and II are [(UO₂)₂(C₂O₄)₃]^2? chains and [UO₂(C₃H₂O₄)₂] ₂ ^4? dimers, which belong to the AK _0.5 ⁰² T¹¹ and AT¹¹B⁰¹ crystallochemical groups (A = UO ₂ ²⁺ , K⁰² and T¹¹ = C₂O ₄ ^2? , T¹¹ and B⁰¹ = C₃H₂O ₄ ^2? ) of uranyl complexes.     

N,N′-methylenedipyridinium Pt(II) and Pt(IV) hybrid salts: synthesis, crystal and molecular structures of [(C5H5N)2CH2] · [PtCl4] and [(C5H5N)2CH2] · [PtCl6]

The highly insoluble organic-inorganic hybrid ionic compounds N,N??-methylenedipyridinium tetrachloroplatinate(II) [(C₅H₅N)₂CH₂] · [PtCl₄] and N,N??-methylenedipyridinium hexachloroplatinate(IV) [(C₅H₅N)₂CH₂] · [PtCl₆] were obtained by the treatment of N,N??-methylenedipyridinium dichloride monohydrate [(C₅H₅N)₂CH₂]Cl₂ · H₂O with K₂[PtCl₄] or (NH₄)₂[PtCl₆], respectively, in an aqueous solution. Both complexes were isolated, purified, characterised by elemental analysis, and their molecular structures were confirmed by powder X-ray diffraction. The crystal structure of both compounds consists of separated discrete dications [(C₅H₅N)₂CH₂]²⁺ and anions [PtCl _n ]^2? (n = 4 or 6). As anticipated, the dications formed a butterfly shape consisting of two pyridine rings bound to the methylene group via their N atoms, while the Pt centre had a square planar geometry in [(C₅H₅N)₂CH₂] · [PtCl₄] and an octahedral coordination in [(C₅H₅N)₂CH₂] · [PtCl₆]. Interestingly, both crystal structures are stabilised by intermolecular C-H??Cl non-standard hydrogen bonds, ??-?? ring interactions between two pyridine rings of adjacent dications, and also by Cl-?? interactions.     

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O

The title complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O (C18H34Cl2CuN2O14S2) (tssb = taurine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3)nm, α = 103.800(4), β = 95.030(4), γ = 104.416(4)°, Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, μ = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are positioned diagonally on a plane.     

Crystal and Molecular Structure of Mo_2[(μ_2-S)SCNEt_2]_2(S_2CNEt_2)_2

Crystal structure of the title complex was determined by X-ray diffraction method. It crystallizes in space group P21/n with cell dimensions:α=10. 041(5) , b=10. 719(4) , c= 1. 5671(6) nm, β=104. 36(3)°. The structure was solved by Patterson method. The final residual factor is R=0. 050.     

On the configuration of open chain α-sulfonyl carbonions: X-ray crystal structure of [(phenylsulfonyl)isopropyllithium-diglyme]2 and [(α-phenylsulfonyl)-α-(methyl)benzyllithium-diglyme]2

The solid state structure of [(phenylsulfonyl)isopropyllithium- diglyme]2 (2d) and of [(α-phenylsulfonyl)-α-(methyl)benzyllithium-diglyme]₂ (2e) is described. Whereas in dialkyl substituted 2d the anionic C-atom is strongly pyramidalized it is almost planar in phenyl substituted 2e. A rationalization of this observation is proposed within the MO model for α-sulfonyl carbanions.     

Syntheses and molecular structures of organo-tellurium(IV) halides trans-[(Ph2Te)(μ-Cl)2]n,cis-[(Ph2Te)(μ-Cl)2]n, [(p-MeC6H4)2TeBr2], and [{(p-MeC6H4)2TeBr}2(μ-O)]

Abstract

Treatment of Ph₂Te with aqueous hydrogen chloride under air in refluxing THF gave trans-[(Ph₂Te)(μ-Cl)₂]_n (1), whereas interaction of Ph₂Te with ammonium chloride under similar condition afforded cis-[(Ph₂Te)(μ-Cl)₂]_n (2). Reaction of (p-MeC₆H₄)₂Te and bromine in refluxing THF resulted in formation of a discrete complex [(p-MeC₆H₄)₂TeBr₂] (3) with a step-like tetrameric structure, which further reacted with sodium hydroxide in refluxing THF to give a dinuclear tellurium oxide [{(p-Me-C₆H₄)₂TeBr}₂(μ-O)] (4) with a bridging oxygen atom. Complexes 1–4 have been spectroscopically characterized and their crystal structures have been established by X-ray crystallography.     

Synthesis and crystal structure of bis[(18-crown-6)potassium] bis(μ2-bromo)tetrabromodicopper(II)

A new complex bis[(18-crown-6)potassium] bis(μ₂-bromo)tetrabromodicopper(II), [{K(18-crown-6)}₂Cu₂Br₆] (I), is synthesized and studied by X-ray diffraction analysis (space group P2₁/n, a = 9.137 Å, b = 34.860 Å, c = 13.414 Å, β = 99.53°, Z = 4). The structure is solved by a direct method and refined by the fullmatrix least-squares method in the anisotropic approximation to R = 0.083 for 5850 independent reflections (CAD-4 automated diffractometer, λMoK _α radiation). Complex molecule I consists of the central binuclear anion [Cu₂Br₆]^2? and two peripheral cations K(18-crown-6)]⁺ of the host-guest type bound to the [Cu₂Br₆]^2? anion through two and one K-Br coordination bonds. In the [Cu₂Br₆]^2? anion, the coordination polyhedra of two Cu atoms can be described as strongly flattened tetrahedra. In two [K(18-crown-6)]⁺ fragments, the coordination polyhedra of their K⁺ cations (coordination numbers 8 and 7) are distorted hexagonal pyramids with a base of six O atoms of the 18-crown-6 ligand and a bifurcated or ordinary vertex: the Br atoms of the [Cu₂Br₆]^2? anion. Two 18-crown-6 ligands have a standard crown conformation.     

Synthesis and X-ray diffraction study of K4[(UO2)2(C2O4)3(NCS)2] · 4H2O

Single crystals of K₄[(UO₂)₂(C₂O₄)₃(NCS)₂] · 4H₂O(I) have been synthesized and studied by X-ray diffraction. The crystals are monoclinic with the unit cell parameters a = 8.0226(7) Å, b = 14.9493(11) Å, c = 11.1670(9) Å, β = 98.299(3)°, space group P2₁/n, Z = 2, V = 1325.26(19) ų, R = 0.0186. The main structural units of the crystals of structure I are discrete binuclear groups [(UO₂)₂(C₂O₄)₃(NCS)₂]^4? belonging to the crystal-chemical group A₂K⁰²B ₂ ⁰¹ M ₂ ¹ (A =UO ₂ ²⁺ , K⁰² =C₂O ₄ ^2? , B⁰¹ =C₂O ₄ ^2? , M¹ = NCS^?) of the uranyl complexes. The uranium-containing complexes are linked into a three-dimensional framework through the potassium ions and a system of hydrogen bonds involving the outer-sphere water molecules.     

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)_2]·2[(H_3O)Cl]·4H_2O

1 INTRODUCTION The complexes of amino acid Schiff base have attracted considerable attention because of their bio- activities[1, 2]. Taurine is a special amino acid in be- ings, and recently the complexes of taurine conden- sation salicylaldehyde Schiff …     

Synthesis and structure of [(μ4-succinato)hexadecaphenyltetraantimony] triiodide solvate with benzene [(Ph4Sb)2O2CCH2CH2CO2(Ph4Sb)2][I3]2 · 4PhH

Russian Journal of Coordination Chemistry - The reaction of bis(tetraphenylantimony) succinate with iodine in benzene affords [(μ4-succinato) hexadecaphenyltetraantimony] triiodide solvate...     

Synthesis of Five-coordinated Anionic Tin(Ⅳ) Complexes and Crystal Structure of [(I-Pr)2NH2][PhSn(μ2-SCH2COO)2]

Four new five-coordinated anionic tin(Ⅳ) complexes with a form of [RnNH4-n][PhSn(μ2-SCH2COO)2] were synthesized via the reaction of mercaptoacetic acid with phenyltin trichloride in the presence of different organic bases and characterized by means of IR, 1H NMR and MS spectroscopies. The crystal structure of [(i-Pr)2NH2][PhSn(μ2-SCH2COO)2] was determined by X-ray diffraction. In the crystal structure, the tin atom is five-coordinated and exists in trigonal bipyramid geometry with cell parameters a=1.1766(11) nm, b=1.3144(14) nm, c=1.3336(15) nm, β=90° and Z=4.     

Synthesis and structure of (NH4)2[(UO2)2(C2O4)(CH3COO)4] · 2H2O

Single crystals of (NH₄)₂[(UO₂)₂C₂O₄(CH₃COO)₄] · 2H₂O have been synthesized and studied. The compound crystallizes in the orthorhombic system with the unit cell parameters a = 6.9225(14) Å, b = 12.327(3) Å, c = 14.619(3) Å, space group Immm, Z = 2, and V = 1247.6(5) ų. The main structural units of the crystals are the isle binuclear groups [(UO₂)₂C₂O₄(CH₃COO)₄]^2? belonging to the crystal-chemical group A₂K⁰²B ₄ ⁰¹ (A = UO ₂ ²⁺ , K⁰² = C₂O ₄ ^2? , B⁰¹ = CH₃COO^?) of the uranyl complexes. The uranium-containing groups are linked into a three-dimensional framework due to electrostatic interaction with the ammonium cations and through a system of hydrogen bonds involving atoms of the water molecules, oxalate and acetate ions, and ammonium and uranyl cations.