Synthesis and structure of manganese(ii) coordination polymers with 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide: solvent and template effects

Russian Chemical Bulletin - New metal-organic frameworks [Mn(DMF)2(odabco)2](ClO4)2 · H2O (1), [Mn(H2O)2? (HCOO)2] · odabco (2), and [Mn(Hodabco)2(odabco)3](NO3)4 (3) were...     

4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane N,N′-dioxide tetrahydrate: Synthesis and crystal structure

N,N′-Substituted 2.2.2-cryptand, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane N,N′-dioxide, is synthesized by an unusual method. The X-ray diffraction crystal structure of its tetrahydrate (C₁₈H₃₆N₂O₈) · 4H₂O is studied (space group P $\bar 1$ , a = 8.040 Å, b = 11.883 Å, c = 14.451 Å, α = 65.78°, β = 81.10°, γ = 89.12°, Z = 2) by a direct method and refined by the least-squares method in the anisotropic approximation (R = 0.069 for 3244 independent reflections, CAD4 automated diffractometer, λMoK _α radiation). The macrocyclic molecule has exo-exo conformation with the two O atoms at the N atoms directed outside its cavity. A crystal of compound I contains hydrogen bonds formed by all H atoms of all water molecules; these H-bonds link the water molecule into zigzag-like complicated infinite chains.     

Sulfonylation of 1,4-Diazabicyclo[2.2.2]octane: Charge-Transfer Complex Triggered C−N Bond Cleavage

A novel charge-transfer complex triggered sulfonylation of 1,4-diazabicyclo[2.2.2]octane (DABCO) with mild reaction conditions has been developed. The formation of a charge-transfer complex between electron-withdrawing (hetero)aryl sulfonyl chloride and DABCO allows the synthesis of N-ethylated piperazine sulfonamide in good yields. The reaction has a high functional group tolerance. Spectroscopic studies confirmed the charge-transfer complex formation between sulfonyl chlorides and DABCO, which facilitates the C−N bond cleavage of DABCO.     

Diazabicycloalkanes with nitrogen atoms in bridgehead positions. 25. Influence of 3′-substituents on the direction of hydroxyethylation of benzo[b]-1,4-diazabicyclo[2.2.2]octenes

Substituents in the 3 and 6-positions of benzo[b]-1,4-diazabicyclo[2.2.2]octane are capable of influencing the reactivity of the nitrogen atoms in the hydroxyethylation reaction due to steric hindrances or anchimeric contribution. Depending on the reaction conditions and substituents in the aromatic ring of benzo[b]-1,4-diazabicyclo[2.2]octane, either mono- or bis-quaternary salts were obtained.For Communication 24, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 215–218, February, 1992.     

Formation of 3,4-diazabicyclo[4,3,0]non-2-ene and N,N′-azo-3-azabicyclo[3,3,0]octane by oxidation of an alicyclic hydrazine. influence ofpH on the diazene rearrangement

Summary 3,4-Diazabicyclo[4,3,0]non-2-ene and N,N-azo-3-azabicyclo[3,3,0]octane are the main products of the oxidation of N-amino-3-azabicyclo[3,3,0]octane by chloramine. The reaction leads to the transient formation of a saturated bicyclic aminonitrene (diazene). AtpH > 13, the diazene undergoes an intramolecular rearrangement to afford a hydrazone. AtpH < 9, a white solid is formed resulting from the dimerization of the molecular and protonated forms of the aminonitrene. At intermediatepH-values, a mixture of both species is obtained. They have been isolated and characterized by UV, GC/MS, IR, and¹H/¹³CNMR. A reaction mechanism is proposed.

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Bildung von 3,4-Diazabicyclo[4,3,0]non-2-en und N,N-Azo-3-azabicyclo[3,3,0]oktan durch Oxidation eines alizyklischen Hydrazins. Einfluß despH-Wertes auf die Umlagerung von Diazenen

Zusammenfassung 3,4-Diazabicyclo[4,3,0]-non-2-en und N,N-Azo-3-azabicyclo[3,3,0]oktan sind die Hauptreaktionsprodukte der Oxidation von N-Amino-3-azabicyclo[3,3,0]oktan durch Chloramin. Die Interaktion führt übergangsweise zur Bildung eines gesättigten bizyklischen Aminonitrens (Diazens). Oberhalb despH-Wertes 13 lagert sich das Diazen intramolekular um und bildet ein Hydrazon. Unterhalb despH-Wertes 9 fällt ein weißer Niederschlag aus (Tetrazen), der von einer Dimerisierung zwischen for molekularen und protonierten Form von Aminonitren herrühren dürfte. Für die dazwischenliegenden Werte (9 <pH < 13) erhält man eine Mischung aus beiden Verbindungen. Sie wurden isoliert und mit Hilfe von UV, GC/MS, IR, und¹H/¹³C-NMR untersucht. Ein Reaktionsmechanismus wird vorgeschlagen.

     

CRYSTAL STRUCTURE OF COORDINATION COBALT(II) AND ZINC(II) POLYMERS WITH 1,4-DIAZABICYCLO[2.2.2]OCTANE N,N′-DIOXIDE

Journal of Structural Chemistry - Four cobalt(II) and zinc(II) cationic metal-organic frameworks (MOFs) based on bridging 1,4-diazabicyclo[2.2.2]octane N,N′-dioxide (odabco) are synthesized....     

Constructing porous lanthanide coordination polymers of 4,4′-bipyridine- N,N ′-dioxide templated by single- and double-Keggin anions

Three porous coordination polymers, {[Nd(dpdo)₂(H₂O)₅(CH₃OH)₂](PMo₁₂O₄₀)(CH₃OH)-(H₂O)₅} _n (1), {[Tb(dpdo)₄(H₂O)₃](PMo₁₂O₄₀)(H₂O)₂CH₃CN} _n (2) and {[Tb(dpdo)₄(H₂O)₃]H(SiMo₁₂O₄₀)(dpdo)_0.5(CH₃CN)_0.5(H₂O)₄} _n (3) (where dpdo is 4,4′-bipyridine-N,N′-dioxide), templated by single- or double-Keggin polyanions were synthesized and characterized by single crystal X-ray diffraction. The compounds exhibit three different 3D non-interwoven frameworks with large cavities occupied by the single- or double-Keggin-type anions. Thermogravimetric analyses suggest different stability for the three metal-organic frameworks. The SHG (second harmonic generation) efficiency of 1 confirms its noncentric framework.     

Synthesis of N- and N,N′-coordinated derivatives of 3,7-dithia-1,5-diazabicyclo[3.3.0]octanes and their fungicidal activity

Possibility of obtaining water-soluble N- and N,N′-coordinated adducts by reacting 3,7-dithia-1,5-diazabicyclo[3.3.0]octane with methyl iodide and Brønsted (HCl, HBr) and Lewis (AlCl₃) acids was examined. The fungicidal activity of 3,7-dithia-1,5-diazabicyclo[3.3.0]octane and its water-soluble adducts with hydrobromide and methyl iodide against a number of microscopic fungi affecting cultivated plants and various materials was studied.     

Synthesis,crystal structure and Raman spectra of [dabcoH2]CuICl3, [dabcoH2]3Cl4CuIICl4(DMSO) and Cu3Cl3(dabco)(DMSO) (dabco = 1,4-diazabicyclo [2.2.2] octane)

Dissolving elemental copper in a CCl₄–DMSO mixture in the presence of dabco (dabco = 1,4-diazabicyclo [2.2.2] octane) resulted in the formation of a compound with the composition [dabcoH₂][CuCl₃] featuring a univalent copper salt. This compound, composed of discrete dabcoH₂²⁺ cations and CuCl₃^2? anions, represents the first example of a copper(I) chloride derivative containing a doubly protonated [dabcoH₂]²⁺ unit, and a very rare example of the oxidative dissolving of copper in a CCl₄–DMSO mixture to give a Cu(I) compound. The addition of some drops of water to the initial reaction mixture led to the formation of the [dabcoH₂]₃Cl₄CuCl₄(DMSO). Three [dabcoH₂]²⁺ units and four Cl^? anions, bound via N–H…Cl hydrogen bonds, form a horseshoe-like cationic fragment. The divalent copper ion possesses a rather unusual pseudo-tetrahedral surrounding. The comproportionation reaction of CuCl₂·2H₂O and copper powder in the presence of dabco in DMSO results in the formation of the Cu₃Cl₃(dabco)(DMSO) complex. Copper and chlorine ions form unprecedented Cu₆Cl₆ cores, interconnected by neutral dabco linkers into infinite 2-D layers. All the compounds were characterized using the single-crystal X-ray diffraction technique and Raman spectroscopy.     

Syntheses,Crystal Structures and Fluorescence of Cadmium(II) Coordination Polymers with Pyrazine-1,4-dioxide, 2-Methylpyrazine-1,4-dioxide and Thiocyanate as Mixed Bridge Ligands

1 INTRODUCTION For a long time much research interest has been focused on the coordination polymeric compounds because such new coordination polymers may afford new materials with useful properties, such as catalytic activity, micro-porosity, electrical conduc- tivity, non-linear optical activity, magnetic coupling behavior and so on[1, 2]. Thiocyanate anion as well as pyrazine-1,4-dioxide and its derivatives belongs to very useful bridge ligands and many complexes[3, 4] with one of them e…     

Structure influence of chiral 1,1′-biscarboline-N,N′-dioxide on the enantioselective allylation of aldehydes with allyltrichlorosilanes

A series of new axially chiral 1,1′-biscarboline-N,N′-dioxide Lewis base organocatalysts were examined in the asymmetric allylation of aldehydes with allyltrichlorosilane. The chiral catalysts (R)-1a–e bearing ester groups in 3,3′ position provided good yields of the homoallyl alcohols with excellent enantioselectivities up to 99% for a broad substrate scope that covers aliphatic, aromatic, heteroaromatic, and α,β-unsaturated aldehydes. Solvent effects on the conversion and enantioselectivity were elucidated, and CH₂Cl₂ proved to be the optimal solvent for the reactions. In addition, the allylation with crotyltrichlorosilane was explored and the result showed that anti-isomer was favored from (E)-crotyltrichlorosilane with complete diastereoselectivity.     

Preparation,crystal structure and luminescence of lanthanide coordination polymers with 2,2′-dimethyl-4,4′-bipyridine-N,N′-dioxide

Four coordination polymers of the bidentate ligand 2,2′-dimethyl-4,4′-bipyridine-N,N′-dioxide (L), [La(L)(NO₃)₃(H₂O)] _n (1), {[Gd₂(L)₃(NO₃)₆]·6H₂O} _n (2), {[Sm(L)₂(H₂O)₄]·3ClO₄·2L·4H₂O} _n (3) and {[Nd(L)₂(H₂O)₄]·3ClO₄·2L·4H₂O} _n (4) have been synthesized by the diffusing solvent mixture method. Results of X-ray diffraction analysis reveal that 1, with a Ln/L stoichiometry of 1:1, displays a rare 3-D three-fold interpenetrating diamondoid framework, while 2 has a Ln/L stoichiometry of 1:1.5 and exhibits a polycatenane network with a {8²,10} topology and large channels accommodated by water. Complexes 3 and 4, with Ln/L stoichiometry of 1:2, have 3-D two-fold interpenetrating diamondoid structures and large voids. Nonlinear optical property of 2 and luminescence of 3 were also investigated.     

Thermochemistry of 2,2′-dipyridil N-oxide and 2,2′-dipyridil N,N′-dioxide. The dissociation enthalpies of the N−O bonds

In this paper, the first, second and mean (N?O) bond dissociation enthalpies (BDEs) were derived from the standard (p° = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, ${\mathrm{\Delta }}_{\text{f}}{H}_{\text{m}}^{°}(\text{g})$, at T = 298.15 K, of 2,2′-dipyridil N-oxide and 2,2′-dipyridil N,N′-dioxide. These values were calculated from experimental thermodynamic parameters, namely from the standard (p° = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, ${\mathrm{\Delta }}_{\text{f}}{H}_{\text{m}}^{°}(\text{cr})$, at T = 298.15 K, obtained from the standard molar enthalpies of combustion, ${\mathrm{\Delta }}_{\text{c}}{H}_{\text{m}}^{°}$, measured by static bomb combustion calorimetry, and from the standard molar enthalpies of sublimation, at T = 298.15 K, determined from Knudsen mass-loss effusion method.     

Zinc(II) and copper(II) complexes of edampda2−: octahedral,trigonal bipyramidal and in between [edampda2−=N,N′-bis-(pyridylmethyl)ethylenediamine-N,N′-diacetate]

ZnII and CuII complexes of the ligand edampda2– [N,N-bis(pyridylmethyl)-ethylenediamine-N,N-diacetate] have been studied in solution by 1H n.m.r. and e.p.r. spectroscopies, respectively. [ZnII(edampda)] exists in solution in a major octahedral isomer (ca. 83%) in which the two carboxylate donors and two pyridylmethyl donors remain stereochemically rigid up to 333K at pD=6.0. The major octahedral complex has equivalent glycinato and pyridyl donors as shown by equivalent AB quartets for each type of chelate. By contrast, the [ZnII(edta)]2– analogue complex is known to have processes which rapidly equilibrate the coordinated carboxylates leading to coalesced, broad singlets instead of AB quartets down to 273K (freezing point of the sample). The minor [ZnII(edampda)] species has one pendant pyridylmethyl arm. The complex does not increase in abundance up to 333K via dissociation of the major species, suggesting that it possesses a different five-coordinate geometry (approximate trigonal bipyramid). The [CuII(edampda)] complex exhibits an e.p.r. spectrum that is intermediate between rhombic or tetragonal CuII complexes (near D4h) and the reversed-e.p.r. type of trigonal bipyramidal CuII complexes (ca. D3h). The single g value of 2.079 for gg>2.03 identifies the [CuII(edampda)] complex as distorted toward trigonal bipyramidal whereas its [CuII(edtaH2)(H2O)] analogue is known to be distorted toward square pyramidal. A binuclear CuI complex of edampda2– is formed only as a transient, and it rapidly disproportionates into [CuII(edampda)] and Cu metal. A mononuclear [CuI(edampda)]– complex persists for up to 8 h, but is oxidized within 3 min by O2 to the CuII complex. [CuII(edampda)] oxidizes to CuIII with a highly irreversible wave on glassy-carbon at +1.09V compared to the [NiII/III(edampda)] wave at +1.32V.     

Synthesis of Macroheterocycles by Reaction of N,N′-(1,4-Phenylene)bis[N′-(4,4-diethoxybutyl)urea] with Resorcinol and Its Derivatives

An efficient procedure has been developed for the synthesis of macroheterocycles by acid-catalyzed reaction of N,N′-(1,4-phenylene)bis[N′-(4,4-diethoxybutyl)urea] with resorcinol, 2-methylresorcinol, and pyrogallol. The structure of the isolated compounds was proved by spectral methods.

     

Computer-aided structure-affinity relationships in a set of piperazine and 3,8-diazabicyclo[3.2.1]octane derivatives binding to the μ-opioid receptor

Summary Molecular modeling studies were carried out on a set of piperazine and 3,8-diazabicyclo[3.2.1]octane derivatives with the aim to highlight the main factors modulating their affinity for the -opioid receptor. Structure-affinity relationships were developed with the aid of molecular mechanics and semiempirical quantum-mechanics methods. According to our proposed pharmacodynamic model, the binding to the -receptor is promoted by the following physico-chemical features: the presence of hydrocarbon fragments on the nitrogen ring frame capable of interacting with one of two hypothesized hydrophobic receptor pockets; a correct orientation of an N-propionyl side chain so as to avoid a sterically hindered region of the receptor; the possibility of accepting a hydrogen bond from a receptor site complementary to the morphine phenol oxygen.     

Synthesis and magnetic properties of copper(II)-MII-copper(II) trinuclear complexes with N,N′-bis(2-aminoethyl)oxamidocopper(II) [M = Co and Ni]

Summary Two novel trinuclear complexes were prepared, namely [Cu₂(oxae)₂(H₂O)₂M] (ClO₄)₂, [oxae = N,N-bis(2-aminoethyl) oxamido dianion; M = Co and Ni]. Based on elemental analyses, conductivity measurements and i.r. spectra, the complexes are proposed to have extended oxamidobridged structures. The magnetic susceptibility of [Cu₂-(oxae) ₂(H₂O)₂Co](ClO₄)₂ were measured over the 4–300 K range and the observed data were successfully simulated by an equation based on the spin Hamiltonian, =–2J(₁·₂·₂·₃). The exchange integral, J, was found to be equal to –29.2 cm^–1, indicating an antiferromagnetic spin-exchange interaction between the adjacent metal ions.     

Thermochemistry of Cu(II) and Ni(II) complexes with N,N-di-n-butyl-N′-thenoylthiourea and N,N-di-iso-butyl-N′-thenoylthiourea

Two substituted N-acylthioureas and the respective Ni(II) and Cu(II) complexes were synthesized, namely: N,N-di-n-butyl-N′-thenoylthiourea (Hnbtu); N,N-di-iso-butyl-N′-thenoylthiourea (Hibtu); bis[N,N-di-n-butyl-N′-thenoylthioureato]nickel(II), [Ni(nbtu)₂]; bis[N,N-di-n-butyl-N′-thenoylthioureato]copper(II), [Cu(nbtu)₂]; bis[N,N-di-iso-butyl-N′-thenoylthioureato]nickel(II), [Ni(ibtu)₂]; bis[N,N-di-iso-butyl-N′-thenoylthioureato]copper(II), [Cu(ibtu)₂]. The standard (p^° = 0.1 MPa) molar enthalpies of formation and sublimation of the two N-acylthioureas were measured, at T = 298.15 K, by rotating-bomb combustion calorimetry and Calvet microcalorimetry, respectively. The standard (p^° = 0.1 MPa) molar enthalpies of formation of the Ni(II) and Cu(II) complexes were determined, at T = 298.15 K, by high precision solution–reaction calorimetry. From the results obtained, the enthalpies of hypothetical metal–ligand and metal–metal exchange reactions, in the gaseous phase, were derived, thus allowing a discussion of the gaseous phase energetic difference between the complexation of Ni(II) and Cu(II) to 1,3-ligand systems with (S,O) ligator atoms.     

Iodoplumbate(Ⅱ)-based Hybrid Templated by 1,4-Diazabicyclo[2.2.2]octane Derivative:Structure,Photocurrent Response Behavior and Photocatalytic Activity for the Degradation of Organic Dye

A new iodoplumbate/organic hybrid,[(Et_2DABCO)_2(Pb_3I_(11))(H3 O)]n(1,Et_2DABCO = N,N?-diethyl-1,4-diazabicyclo[2.2.2] octane) has been synthesized using solution method.According to X-ray diffraction structural analysis,the unique(Pb_3I_(11))_n~(5n-) chain in 1 is constructed from face-and edge-sharing PbI_6 octahedra,which is templated by(Et_2DABCO)~(2+) dication possessing both rigidity and flexibility.C–H···I hydrogen bonds contribute to the structure extending from 1D chains to a 3D network.Its energy band gap of 2.64 eV indicates its broad-gap semiconductor nature.It exhibits both photocurrent response property and photocatalytic activity for the degradation of rhodamine B.     

Dinuclear Nickel(II) and Zinc(II) Complexes of 2,6-[N,N′-bis(2-hydroxyphenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol

Abstract

The symmetric 'end-off' compartmental proligand 2,6-[N,N′-bis(2-hydroxy-phenylmethyl)-N,N′-bis(2-pyridylmethyl)aminomethyl]-4-methylphenol (H₃L) has been used to generate homodinuclear nickel(II) and zinc(II) complexes. The crystal structures of the complexes reveal that the di-nickel(II) complex is donor asymmetric and the di-zinc(II) complex is coordination number asymmetric. In both complexes non-coordinated acetic acid molecules are tightly hydrogen-bonded to the pendant phenols of the ligand generating a double acid salt of the type[CH₃COO…H…L…H…OOCCH₃]^3? in the dinickel complex and a single acid salt of the type [CH₃COO…H…L]^3? in the dizinc complex. In both cases the ligand periphery has been extended to provide a supraligand in which the donor potential of the original ligand has been enhanced.