Reaction of <Emphasis Type="Italic">o</Emphasis>-aminophenol and <Emphasis Type="Italic">o</Emphasis>-aminobenzyl alcohol with palladium(II) bis(isocyanide) complexes

Reactions of palladium(II) bis-isocyanide complexes cis-[PdCl₂(CNR)₂] (R = 2,6-Me₂C₆H₃, 2-Me-6-ClC₆H₃) with an equimolar amount of chelating N,O-binucleophiles, 2-aminophenol and (2-aminophenyl)-methanol, in acetonitrile at room temperature in 24 h selectively afforded the corresponding open-chain monocarbene complexes. The complexation involved one isocyanide ligand and amino group of the aromatic amine. Neither bis(carbene) complexes (in the reactions with 4 equiv of the nucleophile under harsh conditions) nor C,O-chelate structures were detected. The isolated complexes were characterized by elemental analyses, IR, NMR, and mass spectra, and X-ray diffraction data.     

Mononuclear cobalt (III) complexes with <Emphasis Type="Italic">N</Emphasis>-salicylidene-2-hydroxy-5-bromobenzylamine and <Emphasis Type="Italic">N</Emphasis>-salicylidene-2-hydroxy-5-chlorobenzylamine

Cobalt (III) complexes with N-salicylidene-2-hydroxy-5-bromobenzylamine (H₂sbba) and N-salicylidene-2-hydroxy-5-chlorobenzylamine (H₂scba), [n-(C₄H₉)₄N][Co(sbba)₂] (I) and [n-(C₄H₉)₄N][Co(scba)₂] (II), were synthesized. The crystal structure of II was determined by the single-crystal X-ray diffraction method at 90 K confirming its crystallization in the monoclinic space group P2₁/n with a = 11.729(2) Å, b = 16.901(3) Å, c = 21.483(4) Å, β = 98.840(4)°, V = 4208.2(14) ų, D_x = 1.295 g cm^?3, and Z = 4. The R1 [I > 2σ(I)] and wR2 (all data) values of 0.0664 and 0.1920, respectively, for all 9521 independent reflections. The compound is composed of a tetra(n-butyl)ammonium cation and an octahedral cobalt(III) complex anion with two scba^2? ligands in a meridional fashion. The electronic spectral features of I and II are consistent with the octahedral cobalt(III) ion with an N₂O₄ donor set.     

Crystal structure of oxonium <Emphasis Type="Italic">trans</Emphasis>(O)-<Emphasis Type="Italic">cis</Emphasis>-(C)-dicyanobis(2-picolinato)cobaltate(III) hydrate: Two types of proton site

The trans(O)-cis(C)-bis(pyridine-2-carboxylato)dicyanocobaltate(III) ions, [Co(Pic)₂(CN)₂]^?, crystallize from acid medium with three water molecules per two crystallographically nonequivalent complexes whose charge is compensated by protons. One of the water molecules forms an oxonium ion (H₃O⁺) with a proton. The other two water molecules bound to each other through a short hydrogen bond O-H…O (2.403(2) Å) and thus forming (H₅O₂)⁺ cations is another proton site. The (H₃O)(H₅O₂)[Co(Pic)₂(CN)₂]₂ crystals are monoclinic: a = 10.7027(7) Å, b = 25.786(1) Å, c = 11.4865(8) Å, β = 91.411(9)°, Z = 4, space group P2₁/n.     

Crystal Structure of <Emphasis Type="Italic">DL</Emphasis>-Valinium Tetrafluoroantimonate(III) Monohydrate

The crystal structure of an antimony(III) fluoride complex of the composition (C₅H₁₂NO₂)SbF₄·H₂O (I) involving a cation of α-amino isovaleric acid (DL-valine, Val) is determined. Crystals are monoclinic: a = 12.2024(2) Å, b = 6.1636(1) Å, c = 15.5167(3) Å, Z = 4, space group P2₁/c. The structure is formed of DL-valinium (C₅H₁₂NO₂)⁺ cations, complex [SbF₄]_n^n? anions having a polymeric chain structure, and crystallization water molecules. The [SbF₄]_n^n? complex anions consist of trigonal SbF4E bipyramids joined together by asymmetric bridging Sb–F(3)···Sb bonds. The structural units are organized into a threedimensional framework via N–H···F, N–H···O, and O–H···F hydrogen bonds.     

Synthesis of oxo derivatives of <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">p</Emphasis>-tolysulfonyl)hexahydrocycloalka[<Emphasis Type="Italic">b</Emphasis>]indoles

Hydroxymercuration-demercuration of N-p-tolysulfonyl-4,4a,9,9a-tetrahydro-3H-carbazoles and N-p-tolyl(or methyl)sulfonyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles leads to the formation of the corresponding N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-2-ols and N-p-tolyl(or methyl)sulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indol-2-ols. The latter are oxidized to 2-oxo derivatives with potassium dichromate. The oxidation of 2-methoxy-8-methyl-N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-ol under analogous conditions gives 2-methoxy-8-methyl-N-p-tolysulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-one.     

Complexes of some tervalent metals with <Emphasis Type="Italic">N</Emphasis>-alkyl(benzyl)nitrozohydroxylamine derivatives

Twenty two new complexes of some tervalent metals (aluminum, chromium, iron, and lanthanides) with nitrozohydroxylamine N-alkyl(benzyl) derivatives ML₃^m · nH₂O, (m = 1?5) were synthesized and isolated in a crystalline state. The crystal and molecular structures of the iron(III) complex with N-(2-fluorobenzyl)-N-nitrozohydroxylamine were determined by X-ray diffraction. An octahedral coordination of the central ion and a bidentate chelating coordination of the organic ligand were established. The spectral criteria of coordination of nitrozohydroxylamine alkyl(benzyl) derivatives were determined, and the complexation processes in solutions were studied.     

Conformations and properties of <Emphasis Type="Italic">O</Emphasis>-Alkyl-<Emphasis Type="Italic">S</Emphasis>-(2-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dialkylamino)-ethylmethylthiophosphonates

Conformers of the biologically active compounds CH₃P(O)(OR)(SCH₂CH₂NR ₂ ^′ ), where (I) R = i-C₄H₉, R′ = C₂H₅ and (II) R = C₂H₅, R′ = i-C₃H₇, are calculated within the AM1 level of theory. The elongated and twisted forms with maximum and minimum distances between a nitrogen atom and those of a phosphorus tetrahedron, respectively, and bearing a syn and anti oriented alkoxy group relative to a phosphoryl oxygen, are studied. It is found that the differences between the energy, electronic, and geometric parameters of these forms are apparent in differences between their properties, e.g., the ability to participate in complexation and protonation, reactions that to some extent simulate the interaction between a substance and a biological object.     

New binuclear <Emphasis Type="Italic">bis</Emphasis>(2,4,6,8-tetramethyl-2,4,6,8-tetraazobicyclo(3.3.0)octane-3,7-dione-<Emphasis Type="Italic">O,O</Emphasis>')-tetraaqua-hexakis(nitrato-<Emphasis Type="Italic">O,O</Emphasis>')-disamarium(III) complex: Synthesis and crystal structure

The centrosymmetric binuclear complex of samarium(III) nitrate with bicyclic biscarbamide 2,4,6,8-tetramethyl-2,4,6,8-tetraazabicyclo(3.3.0)octane-3,7-dione, or mebicar (Mk) namely, [Sm(C₈H₁₄N₄O₂)(H₂O)₂(NO₃)₃]₂ (I) has been synthesized. Its crystal structure has been characterized (CIF file CCDC no. 1451436). Crystals of complex I are triclinic, space group P1 a = 9.8661(2) Å, b = 10.2913(3) Å, c = 10.9629(3) Å, α = 74.475(2)°, β = 67.802(2)°, γ = 67.570(2)°, V = 942.68(5) ų, ρcalcd = 2.01028 g/cm³, and Z = 1. The samarium atom is coordinated by the two oxygen atoms of two Mk molecules bonded via the symmetry center, three bidentate nitrate anions, and two water molecules. The coordination number of the samarium atom is 10, the coordination polyhedron of the metal atom is a decahedron and the Sm…Sm distance is 9.7904(4) Å.     

Crystal and molecular structure of <Emphasis Type="Italic">tris</Emphasis>(<Emphasis Type="Italic">m</Emphasis>-chlorophenyl)phosphine selenide

The crystal and molecular structure of tris(m-chlorophenyl)phosphine selenide, C₁₈H₁₂Cl₃PSe (I), was investigated by X-ray diffraction (XRD) analysis. The trigonal rhombohedral structure of I (space group \(R\overline 3 c\), a = 14.110(2) Å, c = 32.360(4) Å, Z = 12) was solved by direct methods and refined by least squares in an anisotropic approximation (R = 0.029) for 1319 averaged measured reflections (CAD-4 automatic diffractometer, λCuK_α).     

Binuclear copper(II) complexes with acyldihydrazones of <Emphasis Type="Italic">N</Emphasis>-benzenesulfonyl-<Emphasis Type="Italic">L</Emphasis>-aspartic acid

The structure and the EPR spectra of copper(II) coordination compounds with acyldihydrazones of N-benzenesulfonyl-L-aspartic acid and salicylaldehyde (2-hydroxyacetophenone) were described. The compounds were studied by chemical and thermal analyses, IR spectroscopy, and EPR. The molecular and crystal structures of copper(II) complexes with N-benzenesulfonyl-L-aspartic acid bis(salicylidene)hydrazone (H₄L¹) [Cu₂L¹ · 2Py] · 1.5 H₂O was determined by X-ray diffraction. The crystals are triclinic: a = 10.4714(4) Å, b = 12.9702(5) Å, c = 14.6187(9) Å, α = 104.763(2)°, β = 93.082(2)°, γ = 111.4240(10)°, space group P \(\bar 1\), Z = 2. The binuclear complexes containing copper cations whose coordination polyhedra are connected by an aliphatic spacer (Cu...Cu, 8.669 Å) are additionally linked by phenoxy bridges (Cu...Cu, 3.398 Å). The EPR spectra of these compounds in solutions exhibit an isotropic signal of seven HFS lines due to two equivalent copper ions with the spin Hamiltonian parameters g = 2.115?2.120, a _Cu = (35.5?38.0) × 10^?4 cm^?1, which is indicative of weak exchange interactions between the paramagnetic sites.     

Crystal structure of hexakis-(<Emphasis Type="Italic">N</Emphasis>-methylthiourea) bismuth(III) triperchlorate

A bismuth(III) complex of N-methylthiourea (Mtu, C₂H₆N₂S) [Bi(C₂H₆N₂S)₆](ClO₄)₃ has been synthesized, and its crystal structure has been determined. The structure is built of octahedral Bi(Mtu) ₆ ³⁺ cations and ClO ₄ ^? anions. Sulfur atoms are coordinated to bismuth(III) (at axis 2) at octahedron vertices (Bi-S, 2.7670(8), 2.8142(8), and 2.8315(8) Å); angles SBiS vary from 82.26(3)° to 96.13(2)°. The presence of amino groups and oxygen atoms in the structure results in the emergence of numerous hydrogen bonds (HBs). All H atoms of amino groups are involved in HBs; one of them is bound to the sulfur atom. One of the oxygen atoms of ClO ₄ ^? anions does not participate in HBs.     

Crystal Structure,Spectroscopic and Magnetic Properties of <Emphasis Type="Italic">Trans</Emphasis>-Difluoro-(1,4,8,11-Tetraazaundecane)Chromium(III) Aquatrichlorozincate

A new complex salt trans-[CrF₂(2,3,2-tet)][ZnCl₃(H₂O)] (2,3,2-tet is 1,4,8,11-tetraazaundecane), is prepared and its structure is determined by single crystal X-ray diffraction using synchrotron data at 100 K. The complex crystallizes in the space group P2₁/c of the monoclinic system with two mononuclear formula units in a cell with dimensions a = 5.6360(11) Å, b = 17.120(3) Å, c = 17.020(3) Å, and β = 94.38(3)°. The chromium(III) ion is coordinated by four N atoms of the 2,3,2-tet ligand in the equatorial plane and two F atoms in a trans axial arrangement, displaying a slightly distorted octahedral geometry. The mean Cr–N(2,3,2-tet) and Cr–F bond distances are 2.0772(11) Å and 1.8930(8) Å, respectively. The crystal packing is stabilized by hydrogen bonding interactions between N–H groups of the 2,3,2-tet, O–H groups of the anion, the F atom, and the Cl atom of the anion. The FT-infrared, UV-visible spectra, and magnetic properties are also described.     

New catecholate complexes of triphenylantimony(V) based on 6-iminomethyl-3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butylpyrocatechols N-functionalized by the aniline or phenol group

The following new triphenylantimony(V) catecholate complexes bearing the protonated imine group are synthesized from the new sterically hindered 3,5-di-tert-butylpyrocatechols (6-(CH=N-o-(C₆H₄–NH₂))-3,5-Cat)H₂ (H₂L¹) and (6-(CH=N-o-(C₆H₄–OH))-3,5-Cat)H₂ (H₂L²) containing in position 6 the iminomethyl group bonded to the aniline or phenol substituent: (6-(CH=NH⁺-o-(C₆H₄–NH₂))-3,5-Cat)SbPh₃X (X = Br (I), OMe (III)) and (6-(CH=NH⁺-o-(C₆H₄–OH))-3,5-Cat)SbPh₃X (X = Br (II), OMe (IV)). The molecular structure of complex III · CH ₃ OH in the crystalline state is determined by X-ray diffraction analysis (CIF file CCDC no. 1554694). The electrochemical properties of complexes III and IV are studied by cyclic voltammetry.     

Structure of hexaaquamagnesium (II) bis(4-<Emphasis Type="Italic">p</Emphasis>-aminobenzenesulfamido-2,6-dimethoxypyrimidinate) pentahydrate

The X-ray analysis of a single crystal of Mg(C₁₂H₁₃N₄O₄S)₂·11H₂O, where (C₁₂H₁₃N₄O₄S)^? is the anion of 4-p-aminobenzenesulfamido-2,6-dimethoxypyrimidine (sulfadimethoxine) is carried out. Unit cell parameters are: a = 19.753(4) Å, b = 34.031(7) Å, c = 13.859(3) Å; β = 125.37(3)°, C2/c, Z = 8, R(F) = 0.042. The structure is built of [Mg(OH₂)₆]²⁺, (C₁₂H₁₃N₄O₄S)^?, and water molecules and corresponds to the formula [Mg(OH₂)₆](C₁₂H₁₃N₄O₄S)₂·5H₂O. The IR bands of ν_asymSO₂ and ν_symSO₂ are bathochromically shifted as a result of their participation in hydrogen bonding, and not because of any direct coordination of sulfadimethoxinate anion to the complexing atom through oxygen.     

System vanadium alkoxy compound-<Emphasis Type="Italic">tert</Emphasis>-butyl hydroperoxide-oxidant of hydrocarbon C-H bonds

Vanadium alkoxy compounds [(t-BuO)₄V, (t-BuO)₃VO] react with tert-butyl hydroperoxide (C₆H₆, 20°C) to liberate oxygen, partly in the singlet form, and to form alkoxyl and peroxyl radicals via the intermediacy of vanadium peroxides and trioxide. These systems are capable of oxidizing hydrocarbon C-H bonds. The process is radical in nature and involves formation of carbon-centered radicals and their reaction with oxygen generated in the systems. Vanadium-containing peroxides, too, take part in the oxidation reaction.     

Recyclization of 1,3-dialkyl-6-nitro-1<Emphasis Type="Italic">H</Emphasis>-imidazo[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridine-2,5(3<Emphasis Type="Italic">H</Emphasis>,4<Emphasis Type="Italic">H</Emphasis>)-diones into imidazole derivatives

Treatment of 5-amino-1,3-dialkyl-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones with sodium nitrite in aqueous HCl gave 1,3-dialkyl-1H-imidazo[4,5-b]pyridine-2,5(3H,4H)-diones which were nitrated with potassium nitrate in sulfuric acid to 6-nitro derivatives, and the latter underwent recyclization into 4-amino-1,3-dialkyl-5-(1H-pyrazol-5-yl)-2,3-dihydro-1H-imidazol-2-ones by the action of hydrazine hydrate.     

Reactions of arylsulfinyl chlorides and <Emphasis Type="Italic">N</Emphasis>-(arylsulfonyl)arylsulfinimidoyl chlorides with <Emphasis Type="Italic">p</Emphasis>-aminophenols

In reactions of arylsulfinyl chlorides and N-(arylsulfonyl)arylsulfinimidoyl chlorides with p-aminophenols formed N-arylthio-1,4-benzoquinone imines, evidently through a stage of N-arylsulfinyl-4-aminophenols and N-(N-arylsulfonyl)arylsulfinylimidoyl-4-aminophenols that under the reaction conditions eliminate respectively H₂O and ArSO₂NH₂.     

Some Transformations of 2-(Chloromethyl)-5,5-dimethyl-5,6-dihydrobenzo[<Emphasis Type="Italic">h</Emphasis>]quinazolin-4(3<Emphasis Type="Italic">H</Emphasis>)-one

The condensation of 1-amino-3,3-dimethyl-3,4-dihydronaphthalene-2-carbonitrile with chloroacetyl chloride afforded chloro-N-(2-cyano-3,3-dimethyl-3,4-dihydronaphthalen-1-yl)acetamide which underwent cyclization to 2-(chloromethyl)-5,5-dimethyl-5,6-dihydrobenzo[h]quinazolin-4(3H)-one. The latter reacted with various nucleophiles (alkali metal alkoxides, piperazine, 2-sulfanylethanol) to give 2-(alkoxymethyl)-, 2-(piperazin-1-ylmethyl)-, and 2-{[(2-hydroxyethyl)sulfanyl]methyl}-5,5-dimethyl-5,6-dihydrobenzo[h]quinazolin- 4(3H)-ones. The condensation of 2-(chloromethyl)benzo[h]quinazoline with 2-thioxo derivatives of quinazoline and benzo[h]quinazolines led to the formation of bis-quinazolines in which 5,5-dimethyl-5,6- dihydrobenzo[h]quinazolin-4(3H)-one fragment is linked to quinazoline or benzo[h]quinazoline system through a CH₂S bridge.     

Crystal structure of <Emphasis Type="Italic">tris</Emphasis>-(dipivaloylmethanato) (ethylendiamine)yttrium(III)

The structure of a mixed-ligand complex tris-(dipivaloylmethanato)(ethylendiamine)yttrium(III) [Y(en)(dpm)₃] is studied at 150(2) K by single crystal XRD. The crystallographic data for C₃₅H₆₅N₂O₆Y are as follows: space group P2₁/c, a = 10.3771(3) Å, b = 26.3566(8) Å, c = 14.8412(4) Å, β = 100.385(2)°, V = 3992.6(2) ų, Z = 4. The structure is molecular. The coordination environment of yttrium atoms is square antiprismatic; the Y–О distances are 2.2597(13)-2.3760(12) Å and Y–N distances are 2.5381(16) Å and 2.5499(17) Å.     

Synthesis and X-ray study of 6<Emphasis Type="Italic">H</Emphasis>-chromeno[3,4-<Emphasis Type="Italic">e</Emphasis>][1,3,4]triazolo[2,3-<Emphasis Type="Italic">a</Emphasis>]pyrimidine

2-Dimethylamino methylenechromanone 1 reacted with 4H-1,2,4-triazol-3-amine in acetic acid to give only one isolated product which was identified by X-ray study as 6H-chromeno[3,4-e][1,3,4]triazolo[2,3-a]-pyrimidine. The molecular structure of 3, C₁₂H₈N₄O, was determined to be monoclinic, P2₁/c, a = 16.3875(5), b = 8.8378(3), c = 13.8392(5) Å, β = 101.190(1)°, V = 1966.22(11) ų, Z = 8.