Synthesis of Diorganotin Esters of 5-Bromonicotinic Acid: X-ray Crystal Structure of Polymeric 5-Bromonicotinatodiorganotin

Two types of diorganotins [R₂Sn(OCOC₅H₃N-3-Br-5)₂] _n and {[R₂Sn(OH₂)(OCOC₅H₃N-3-Br-5)₂]₂} _n (R= Me, n-Bu, Ph, n-Oc), are prepared from 5-Br-omonicotinic acid and diorganotin oxides. All the compounds, 1–8, are characterized by elemental analysis as well as IR and ¹H-NMR spectroscopy. The crystal structures of [R₂Sn(OCOC₅H₃N-3-Br-5)₂] _n (2) and {[R₂Sn(OH₂)(OCOC₅H₃N-3-Br-5)₂]₂} _n (8) were determined by single crystal X-ray diffraction. In compound 2, each carboxylate moiety of 5-Br-omonicotinic acid is involved in coordination to one Sn atom via two O-atoms, and the N-atom of one pyridine-ring coordinates to the neighboring Sn atom which leads to a polymeric chain. And the N-atom of the other pyridine-ring is dissociative. In compound 8, the compound proves to be dinuclear macrocyclic compounds with 5-Br-omonicotinic acid bridging the adjacent tin atoms with a 12-member ring. The hydrogen bonds ( ) are observed in the compound 8. These intermolecular hydrogen bonds form another ring, and lead to a polymeric chain in the lattice at the same time. An erratum to this article can be found at     

Hydrothermal Synthesis,Crystal Structure and Magnetic Properties of Lithium Manganese Complex of Benzene-Hexacarboxylic Acid (Mellitic Acid)

Abstract  

A new mellitate complex LiMn[C₆(COO)₆]_0.5(H₂O)₂ (1) has been synthesized by the reaction of mellitic acid and Mn(OAc)₂·4H₂O in the presence of LiOH·H₂O. 1 was characterized by the elemental analyses, IR spectra, TGA and the single crystal X-ray diffraction. X-ray crystal structural analysis revealed that the Li cation has a distorted tetrahedral geometry, coordinated by three carboxylic oxygen atoms and one water molecule. The Mn cation is coordinated to one water molecule and five carboxylic oxygen atoms in a slightly distorted octahedral coordination geometry. The mellitate anions behave as a bridging ligand and link six lithium ions and eight manganese ions repeatedly to form an interesting three-dimensional metal–organic coordination polymer. Variable-temperature magnetic susceptibility measurements indicate the presence of antiferromagnetic behavior.     

Syntheses and Characterization of 1D, 2D and 3D Organotin Polymers with Benzimidazole-5,6-dicarboxylic Acid and Trimethyltin Chloride

Three types of di- and trimethyltin(IV) polymers [Me₂Sn(C₉H₄N₂O₄)]_n · 4H₂O 1, [(Me₃Sn)₂(C₉H₄N₂O₄)]_n · H₂O 2 and [(Me₃Sn)₂(C₉H₄N₂O₄)]_n · CH₃OH 3 have been synthesized by the reaction of trimethyltin chloride with benzimidazole-5,6-dicarboxylic acid under three different experimental conditions. All the complexes were characterized by elemental analysis, IR, NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopy and X-ray crystallography diffraction analysis. The structure analyses reveal that complex 1 has a 1D helical chain in which benzimidazole-5,6-dicarboxylic acid act as a tetradentate (O,O-chelation) ligand coordinating to dimethyltin (IV) ions, two water molecules take part in the coordination giving seven-coordinated tin centers in the component. Complex 2 and 3 are 2D and 3D corrugated polymers in which the deprotoned acid as tetradentate ligand affords by three oxygen atoms and a nitrogen atom.     

Tin(IV) Polymers: Part 1. Synthesis of Diorganotin Esters of Thiosalicylic Acid: X-ray Crystal Structure of Polymeric Thiosalicylatodiorganotin

Thiosalicylatodiorganotin, [R₂Sn(O₂CC₆H₄S)]_n, (R=Me (1), n-Bu (2), Ph (3), 3-Cl–PhCH₂ (4)), are prepared from thiosalicylic acid and diorganotin chlorides. All the compounds, 1–4, are characterized by elemental analysis as well as IR and ¹H-NMR spectroscopy. X-ray crystallographic analysis of the 2 and 4 shows that the structures are polymeric with neighboring diorganotin centers being linked by one O-atom of the carboxylate ligands. The carboxylate moiety is involved in coordination to one Sn atom via one O-atom while the other O-atom coordinates to the neighboring Sn atom. The mercaptotropone sulfur atom is bonded to the central Sn atom thereby establishing that Sn is five-coordinate and exists in a trigonal bipyramidal geometry.     

Synthesis of Triorganostannate Esters of Dicarboxylic Acids: X-ray Crystal Structure of Polymeric Triethylammonium 2,5-Thiophenedicarboxylatotriphenylstannate

The triethylammonium 2,5-thiophenedicarboxylatotriorganostannates, [(C₂H₅)₃ NH]-[R₃Sn((O₂C)₂C₄H₂S)] (R = Me (1), n-Bu (2), Ph (3), PhCH₂ (4)), have been prepared from triethylamine, 2,5-thiophenedicarboxylic acid and triorganotin chloride. All the compounds, 1–4, have been characterized by elemental, IR and ¹H-NMR analyses. An X-ray analysis of the R = phenyl compound shows that the structure is polymeric with neighboring triorganotin centers being linked by dicarboxylate ligands. Each carboxylate moiety is involved in coordination to a Sn atom via one O atom only showing that the Sn atoms are five-coordinate and exist in trigonal bipyramidal geometries. Moreover, the ammonium nitrogen is hydrogen bonded to the carbonyl oxygen.     

Synthesis, characterization and biological activity of dimethyltin dicarboxylates containing germanium

A series of diorganotin dicarboxylates of the general formula (CH₃)₂Sn(OCOCHR³CHR²GeR¹)₂ where R¹=(C₆H₅)₃, (P-CH₃C₆H₄)3, N(CH₂CH₂O)₃, R²=C₆H₅, H, CH₃, P-CH₃OC₆H₄, P-ClC₆H₄, P-CH₃C₆H₄, R³=CH₃ and H, have been synthesized by the reaction of dimethyltin oxide with germanium substituted propionic acid in 1:2 molar ratio in toluene. The H₂O formed was removed azeotropically using a Dean and Stark apparatus. All the compounds have been characterized by IR, multinuclear (¹H, ¹³C, ¹¹⁹Sn) NMR, mass and Mössbauer spectroscopies. All compounds were found to have potential activity against bacteria.     

Synthesis,crystal structure and desulfurization properties of zig-zag 1D coordination polymer of copper(II) containing 4-methoxybenzoic acid ligand

ABSTRACT

Combustion of fuels containing organosulfur compounds has resulted in the emission of sulfur oxides (SO_x) into the atmosphere, therefore, causing serious environmental and health hazards. Herein, slightly distorted octahedral zig-zag 1D coordination polymer of copper(II) [Cu(4-mba)₂(H₂O)₃] was synthesized by reacting copper sulfate pentahydrate with a carboxylate-containing ligand (H-4mba?=?4-methoxybenzoic acid) and employed for sulfur compound uptake. The ligand coordinates to the copper(II) atom via two pairs of deprotonated ligating atoms (carboxylate oxygens) and two water molecules. Structural characterization also reveals that interplay of O–H···O, N–H···O, C-H···O and C–H···π interactions between lattice and coordinated water and ligands significantly contribute to the crystal packing leading to the formation and strengthening of three-dimensional supramolecular assembly. The complex, [Cu(4-mba)₂(H₂O)₃], show potential for desulfurization of fuel with an observed adsorption capacity of 9.6?mg/g at 32°C for 6?h. DFT calculations further revealed a transfer of electron sulfur-containing compounds and the complex, [Cu(4-mba)₂(H₂O)₃], thus leading to a stronger pi–pi interaction.     

Cooperative Effect of 3,3′,4,4′-Benzophenonetetracarboxylic Acid and 1,10-Phenanthroline under Solvothermal Conditions to Afford Two Novel Zinc(II) and Cadmium(II) Complexes

Rational self-assembly of a flexible ligand 3,3′,4,4′-benzophenonetetracarboxylic acid and d¹⁰ transition metal salts in the presence of rigid bidentate ligand 1,10-phenanthroline yields two novel helical coordination polymers with different structural motifs; i.e., [Zn(H₂bbtc)(phen)₂ · 2H₂O] _n (1) and [Cd₂(bbtc)(phen)₄ · 2.25H₂O] _n (2) (H₄bbtc = 3,3′,4,4′-benzophenonetetracarboxylic acid, phen = 1,10-phenanthroline), under solvothermal condition. One is hydrogen bonded and π–π stacked together into a network, and the other is a covalently coordinated 3D framework. The coordination polymers were characterized by FT-IR, UV/VIS and fluorescent spectroscopy, single crystal X-ray diffraction, elemental analysis and differential thermal analysis/thermogravimetry (DTA/TG). The most intriguing structural feature is that each complex exhibits novel helical-spaced chains by reason of two different ligands coordinating to the metal centers. Additionally, compounds 1 and 2 showed good fluorescence properties compared to the free ligands.     

Synthesis and structure of a novel tetranuclear 32-membered macrocycle of triphenyltin complex with pyridine-4-carboxylic acid N-oxide

The 32-membered stereoregular triphenyltin macrocycle: [Ph₃Sn (OCOC₅H₄NO)]₄·3(CH₂Cl₂) has been synthesized by the reaction of triphenyltin chloride with pyridine-4-carboxylic acid N-oxide. The complex was characterized by elemental analysis, FT-IR, NMR (¹H, ¹¹⁹Sn) spectra and X-ray crystallography. Single crystal X-ray diffraction data reveal that the complex is highly symmetrical tetranuclear cyclic complex with the ligand pyridine-4-carboxylic acid N-oxide bridging the adjacent tin atoms. All four tin atoms are five-coordinated resulting in trigonal bipyramidal geometry. And the complex showed good thermal stability and high antitumor activity.     

Extraction of Lanthanides(III), U(VI), and Th(IV) from Nitric Acid Solutions with 1,5-N,N'-Bis[(diphenylphosphoryl)acetylamino]pentanes

Novel polyfunctional neutral organophosphorus ligands, namely 1,5-N,N'-bis[(diphenylphosphoryl)acetyl(alkyl)amino]pentanes [Ph₂P(O)CH₂C(O)NR]₂(CH₂)₅ (Ia, R = C₆H₁₃; Ib, R = CH₃), were studied as extractants for Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, and U from nitric acid solutions. The effect of both HNO₃ concentration in the aqueous phase and that of the extractant in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes was determined by the slope analysis method. Compared with the related bisaminopentane [Ph2P(O)CH₂C(O)NH]₂(CH₂)₅ (Ic), the replacement of hydrogen atoms at the amide nitrogens by alkyl radicals (compounds Ia,b) leads to an increase of metal ions extraction. Bis-CMPO ligands Ia-c were found to possess higher extraction efficiency towards U(VI), Th(IV), and Ln(III) than their monophosphorylated analogue Ph₂P(O)CH₂C(O)N(C₄H₉)₂.     

Synthesis,Crystal Structure and DNA Interaction of a Novel Three-Nuclear Cobalt(II) Complex with Schiff Base Derived from 4-Chloroanthranilic Acid and 2,4-Dihydroxybenzaldehyde

A novel transition metal coordination polymer [Co₃(C₁₄H₈NO₄Cl)₄(CH₃OH)₄·4CH₃OH]_n with Schiff base (C₁₄H₈NO₄Cl: 4-chloroanthranilic acid- 2,4-dihydroxybenzaldehyde) was synthesized using 4-chloroanthranilic acid, 2,4-dihydroxybenzaldehyde and cobalt(II) acetate as source, and its structure was characterized by IR spectroscopy, elemental analysis, ¹H NMR and single crystal X-ray diffraction. X-ray crystallography shows that every cobalt atom is six-coordinated. Two cobalt atoms on the two sides are respective coordinated with two nitrogen atoms from –C=N–, two carboxylic oxygen atoms and two hydroxyl oxygen atoms in different ligands, while the cobalt atom in the middle links two ligands on the side through two carboxylic oxygen atoms and coordinates with four oxygen atoms of methanol, forming a three-nuclear Co(II) complex. The complex forms a two-dimensional layer structure through O–H···O intermolecular hydrogen bonds. The interaction of the Co(II) complex with calf-thymus DNA (CT-DNA) was investigated by UV absorption spectroscopy, fluorescence emission spectroscopy, viscosity and cyclic voltammetry. All measurements revealed that the Co(II) complex binds to DNA via a intercalative mode.     

Divalent metal complexes of formylhydrazine: Syntheses and crystal structures of M(CH4N2O)2(H2O)2·2NO3 (M = Zn,Co)

The syntheses and crystal structures of Zn(CH₄N₂O)₂(H₂O)₂·2(NO₃) (1) and Co(CH₄N₂O)₂(H₂O)₂·2(NO₃) (2), the first well-characterised metal complexes of formylhydrazine (fh), are described. In both compounds, the fh acts as an N,O-bidentate ligand in a centrosymmetric [M(fh)₂(H₂O)₂]²⁺ cation, with charge balance supplied by nitrate counter ions. The packing for the two compounds are quite different: in 1, chains of [Zn(fh)₂(H₂O)₂]²⁺ units are seen in the triclinic unit cell, whereas in the monoclinic structure of 2, sheets of cations occur. This might arise because the conformations of the five-membered chelate rings for the ligands are slightly different, with that for 2 showing a greater degree of puckering.     

Experimental study of the structure of laminar premixed flames of ethanol/methane/oxygen/argon

The structures of three laminar premixed stoichiometric flames at low pressure (6.7 kPa): a pure methane flame, a pure ethanol flame, and a methane flame doped by 30% of ethanol, have been investigated and compared. The results consist of mole fraction profiles of CH₄, C₂H₅OH, O₂, Ar, CO, CO₂, H₂O, H₂, C₂H₆, C₂H₄, C₂H₂, C₃H₈, C₃H₆, CH₃-C CH (propyne), CH₂ C CH₂ (allene), CH₂O, and CH₃HCO, measured as a function of the height above the burner by probe sampling followed by on-line gas chromatography analyses. Flame temperature profiles have been also obtained by using a PtRh thermocouple. The similarities and differences between the three flames have been analyzed. The results show that, in these three flames, the mole fraction of the intermediates with two carbon atoms is much larger than that of the species with three carbon atoms. In general, the mole fraction of all intermediate species in the pure ethanol flame is the largest, followed by the doped flame, and finally the pure methane flame.     

Hydrosilylation Synthesis of New Ferrocenylene Copolymers Containing Carbosilylene,Carbosiloxy and Cyclopentadienyliron Dicarbonyl Bridges

Bifunctional organometallic silicon precursor monomers and substrates FC(SiMe₂H)₂ (1) [FC = (η⁵-C₅H₄)Fe(η⁵-C₅H₄)]; FC(SiMe₂(CH₂)_xCH=CH₂)₂ [x = 0 (2), 1 (3)], [η⁵-C₅H₄-SiMe₂(CH₂)_xCH=CH₂)]Fe(CO)₂SiMe₂(CH₂)_xCH=CH₂ x = 0 (4), 1 (5) and (η⁵-C₅H₄-SiMe₂H)Fe(CO)₂SiMe₂H (6) have been used to make a series of new iron containing polymers via hydrosilylation reactions. In addition to the vinyl- and allyl-containing substrates 2, 3, 4 and 5 the organosilicon compounds [CH₂=CHSiMe₂]₂O, 1,4-(H₂C=CH-SiMe₂)₂C₆H₄ and (HC≡CH–SiMe₂)₂O were also used as substrates for the hydrosilylation reaction. The reactions between the various SiH and CH=CH₂ and C≡C functionalities were performed in the presence of Pt(0) catalyst and resulted in regioselective (β-isomer and β-(E) isomer) products as determined by NMR spectroscopy. Molecular weights of all the polymers were determined by Gel Permeation Chromatography, which revealed oligomeric materials with narrow polydispersity. Cyclic voltammetric studies of exhibited single reversible redox processes due to the Fe(II)/Fe(III) couple when present, and irreversible oxidation for the presence of any Fp Fe atom. This article is dedicated to Professor Astruc.     

Clicking not cooking: Functionalization of 2,2′:6′,2″-terpyridines by diol–boric acid interactions

A diol–boric acid condensation is a simple type of CLICK reaction that can be applied to give a family of related ligands. It is exemplified by the reaction of 4′-(3,4-dihydroxyphenyl)-2,2′:6′,2″-terpyridine (1) with naphthalene-1-boronic acid. The single crystal structures of 1^.MeOH and [Fe(1)₂][BF₄]₂? 4H₂O?0.2CH₃CN are presented.     

Tuning the valence of 3,3-di(1H-tetrazol-5-yl)pentanedioic acid: Solvothermal synthesis of Eu(III) and bimetallic Eu(III)/Cu(II) compounds

3,3-Di(1H-tetrazol-5-yl)pentanedioic acid (H₄dtzpda) with four acidic hydrogen atoms can display different valence when reacted with different metal ions. Solvothermal reactions of H₄dtapda with Eu(NO₃)₃·6H₂O or Eu(NO₃)₃·6H₂O/Cu(NO₃)₂·6H₂O afford [Eu(Hdtzpda)(H₂O)₄]·4H₂O (1) and [Eu₂Cu(dtzpda)₂(H₂O)₁₀]·6H₂O (2), respectively, where only three acidic hydrogen atoms of H₄dtzpda are deprotonated in compound 1 while all the four acidic ones are deprotonated in compound 2. In compound 1, Hdtzpda^3 − acts as a pentadentate ligand to bridge Eu(III) centers via the oxygen atoms of the carboxylate group while in compound 2, dtzpda^4 − is a hepadentate one via not only the oxygen atoms of the carboxylate group but also the nitrogen atoms of the tetrazole rings. The luminescence properties of the two compounds in the solid state show both intraligand and characteristic peaks of Eu^3 + at room temperature.     

Acid gas adsorption on zeolite SSZ-13: Equilibrium and dynamic behavior for natural gas applications

In developing new adsorption separation processes, it is necessary to study both the equilibrium and dynamic adsorption properties of potential materials. Experimental determination of isotherms and dynamic breakthrough properties aid in the development of modeling new adsorption systems toward process development. Here, the equilibrium adsorption properties of a small-pore zeolite, Na-SSZ-13, are studied for its natural gas separation potential. Using volumetric, gravimetric, and dynamic column breakthrough adsorption techniques, the adsorption properties of CO₂, CH₄, C₂H₆, H₂S, and H₂O are determined. High-pressure breakthrough experiments demonstrate the mixed gas separation performance of Na-SSZ-13 in mixtures containing CO₂, CH₄, C₂H₆, and H₂S. Simulations of these breakthrough experiments show that ideal adsorbed solution theory adequately describes the mixed gas adsorption modeling for this zeolite. In gas mixtures containing both CO₂ and H₂S, there is an observed acid gas reaction that results in elution of carbonyl sulfide, COS.     

Synthesis and Structural Characterization of Three New Tetraorganodistannoxanes

An efficient method was developed for the preparation of three tetraorganodistannoxane complexes, (C₂H₅)₈Sn₄Cl₂(CH₃O)₂O₂ (1), (CH₃)₈Sn₄(C₃H₄N₃S)₂(CH₃O)₂O₂ (2) and (C₄H₉)₈Sn₄(C₃H₄N₃S)₂(CH₃O)₂O₂ (3). All prepared complexes were characterized by infrared, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopes and elemental analysis. The molecular structure of a representative complex (1) was determined by single-crystal X-ray diffraction. Results showed that 1 is a tetranuclear, centrosymmetric dimeric, and contains two endo-cyclic five-coordinated tin atoms and two exo-cyclic five-coordinated tin atoms. Compound 1 lies about a center of inversion and the tetranuclear molecule features a three-ring-staircase Sn₄O₄ core. The asymmetric unit of 1 contains two independent Sn(IV) atoms and a 2D infinite rigid chain structure forms via C–H···Cl interactions between tetranuclear units.     

Solvent Control Over Structural Diversity of Two Copper (II) Complexes Based on Polyaromatic Acid Ligand

Abstract  

A new bipod polyaromatic acid ligand H₂bcm (H₂bcm = {2, 4-bis [(2′-carboxyphenoxy) methyl]-1,3,5-trimethylbenzene}) is prepared and its two novel binuclear coordination compounds, [Cu₂(bcm)₂(CH₃OH)₂]·2CH₃OH (1) and [Cu₂(bcm)₂(CH₃CH₂OH)₂]·2CH₃CH₂OH (2), have been synthesized with copper acetate and H₂bcm ligand in methanol solvent and ethanol solvent respectively, and characterized by the element analysis, IR, TGA and single crystal X-ray diffraction. The results of structural analysis indicate that 1 crystallizes in the triclinic system with space group P1, while 2 crystallizes in the monoclinic system with space group P2₁ /c. Furthermore, 1 adopts μ ₂ -COO⁻ and syn–syn coordination mode with Cu (II)···Cu (II) separation of 2.5868(11) ? and forms 1D zigzag chain structure by O···O interactions. The coordination of 2 is similar to that of 1 except that ethanol molecules are coordinated instead of methanol molecules with Cu (II)···Cu (II) separation of 2.5973(13) ?. Two-dimensional network structures of 1 and 2 are formed through π–π interactions.     

A New Series Lanthanide-2,6-Pyridinedicarboxylic Acid Complexes Containing Low Dimensionality: Synthesis,Structure and Photoluminescent Properties

Abstract  

Based on the 2,6-pyridinedicarboxylate acid ligand, ten lanthanide complexes with formula, (Hdipa)₃[Ln(L)₃] (Ln = Eu [1], Gd [2], Nd [3], Tb [4], Ce [5], Sm [6], Pr [7], Dy [8] and Er [9]) and [Nd(L)(HL)(H₂O)₂]·4H₂O (10), (where H₂L = 2,6-pyridinedicarboxylic acid and dipa = N-(1-methylethyl)-2-propanamine) have been prepared by different synthetic methods. Structural analyses reveal that complexes 1–3 are isomorphous, zero-dimensional structures, which are further connected to 3D H-bonding networks via extensive intermolecular hydrogen bonds. In the structures of these complexes, the dipa plays a key role in balancing electric charge. For complex 10, the 1D Ln–O–C–O–Ln polymeric chains are linked into a stable 3D H-bonding framework through numerous intermolecular and intramolecular hydrogen bonds. The luminescent properties of complexes 1, 4, 6 and 8 were investigated in detail.