(<Emphasis Type="Italic">Z</Emphasis>)-diiodo(2-iodo-2-phenylvinyl)(phenyl)tellurium PhIC=CHTeI<Subscript>2</Subscript>Ph: Synthesis and complexing properties in a reaction with iron pentacarbonyl

Electrophilic addition of PhTeI₃ to phenylacetylene (PhC₂H) in boiling THF stereoselectively gave (Z)-diiodo(2-iodo-2-phenylvinyl)(phenyl)tellurium PhIC=CHTeI₂Ph (I). In a reaction with Fe(CO)₅, this complex easily eliminated two iodine atoms from tellurium to give PhTe-CH=CPhI. This ligand was coordinated to iron in a monodentate fashion through the Te atom in the resulting complex (CO)₃FeI₂(PhTeHC=CPhI) (II). The reaction also yielded the known complex Fe(CO)₄I₂ (III). The structures of complexes I–III were determined by X-ray diffraction analysis. The Fe-Te bond in structure II is substantially shortened.     

Crystal structures of polyphosphates MCs<Subscript>5</Subscript>(PO<Subscript>3</Subscript>)<Subscript>8</Subscript> (M = Pr,Eu, and Gd)

Crystals of double polyphosphates EuCs₅(PO₃)₈ (I) and GdCs₅(PO₃)₈ (II) have been studied by X-ray diffraction. The isostructural crystals of I and II are monoclinic, space group C2. Only unit cell parameters have been determined for the crystals of double Pr and Cs polyphosphate (III). This crystal is isostructural with earlier studied La₃Cs₁₅P₂₄O₇₂ · 6H₂O (IV). The crystals of compounds III and IV are triclinic, space group P1, Z = 1; a = 11.987(2) and 12.178(5) Å, b = 14.754(8) and 14.740(8) Å, c = 14.692(8) and 14.847(9) Å, α = 60.15(4)° and 60.87(5)°, β = 67.04(4)° and 66.35(4)°, γ = 78.76(3)° and 77.54(4)°, respectively. In compounds I and II, the polyphosphate anions exist as infinite chains. The M^IIIO₈ polyhedra are isolated from each other but share edges and faces with the CsO _n polyhedra.     

Crystal structures of <Emphasis Type="Italic">trans</Emphasis>-dichlorobis(ethylendiamine) rhodium(III) with univalent anions

The crystal structures of the compounds trans-[Rh(en)₂Cl₂]Cl₂ · H₅O₂ (I), trans-[Rh(en)₂Cl₂]ClO₄ (II), and trans-[Rh(en)₂Cl₂]ReO₄ (III) are determined. The crystal data are: I, a = 10.860(3) Å, b = 7.795(2) Å, c = 9.023(3) Å; β = 111.56(10)°, P2₁/c space group, Z = 4, d _x = 1.875 g/cm³; II, a = 6.593(2) Å, b = 8.309(3) Å, c = 11.922(4) Å, α = 83.55(10)°, β = 79.80(10)°, γ = 75.38(10)°, P \(\bar 1\) space group, Z = 2, d _x = 2.106 g/cm³; III, a = 6.533(2) Å, b = 16.391(4) Å, c = 12.411(3) Å; β = 98.30(10)°, P2₁/c space group, Z = 4, d _x = 2.749 g/cm³. The compounds are examined by IR spectroscopy and powder XRD. The solubility of the isolated crystalline phases in water decreases in the following order: trans-[Rh(en)₂Cl₂]Cl₂·H₅O₂ > trans-[Rh(en)₂Cl₂]ClO₄ > trans-[Rh(en)₂Cl₂]ReO₄.     

Synthesis and structure of silicon-containing <Emphasis Type="Italic">N</Emphasis>-methyland <Emphasis Type="Italic">N</Emphasis>-benzoylamides of diisopropylphosphoric acid

Diisopropyl N-benzoyl-N-(trimethylsilyl)phosphoramidate reacts with ClCH₂SiMe₂Cl under mild conditions to form diisopropyl N-benzoyl-N-[(chlorodimethylsilyl)methyl]phosphoramidate (III). Diisopropyl N-methyl-N-(trimethylsilyl)phosphoramidate with ClCH₂SiMe₂Cl affords an N-transsilylation product which does not rearrange into diisopropyl N-[(chlorodimethylsilyl)methyl]-N-methylphosphoramidate (XV) even under severe conditions (4 h, 130°C). Compound XV was prepared by the reaction of diisopropyl phosphorochloridate with N-[(methoxydimethylsilyl)methyl]-N-methylamine followed by treatment of diisopropyl N-[(methoxydimethylsilyl)methyl]-N-methylphosphoramidate with boron trichloride. Analysis of experimental and calculated ²⁹Si chemical shifts points to a five-coordinate silicon atom in compound III and a fourcoordinate silicon atom in compound XV. According to B3LYP calculations with due regard to solvent effects, compound III is an isomer with a C=O→Si bond. By variation of substituents at silicon, phosphorus, and carbonyl carbon atoms, chelate structures with either C=O→Si or P=O→Si dative bonds can be obtained.     

Synthesis,crystal structure,and antibacterial activity of oxovanadium(V) complexes derived from <Emphasis Type="Italic">N</Emphasis>'-[1-(5-fluoro-2-hydroxyphenyl)methylidene]nicotinohydrazide and <Emphasis Type="Italic">N</Emphasis>'-(5-fluoro-2-hydroxybenzylidene)-2-hydroxynaphthylhydrazide

Two new oxovanadium(V) complexes, [VOL¹(OCH₃)(CH₃OH)] (I) and [VOL²(OCH₃)] (II), where L¹ and L² are the di-anionic form of N'-[1-(5-fluoro-2-hydroxyphenyl)methylidene]nicotinohydrazide and N'-(5-fluoro-2-hydroxybenzylidene)-2-hydroxynaphthylhydrazide, respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination (CIF files CCDC nos. 891852 (I), 891853 (II)). The crystal of I is monoclinic: space group P2₁/c, a = 8.061(1), b = 15.293(2), c = 13.471(2) Å, ß = 92.595(2)°, V = 1658.8(4) ų, Z = 4. The crystal of II is monoclinic: space group P2₁/n, a = 7.4454(9), b = 8.0833(9), c = 28.906(2) Å, ß = 92.644(2)°, V = 1737.8(3) ų, Z = 4. The V atom in I is in an octahedral coordination, and that in II is in a square-pyramidal coordination. The antibacterial activity of the compounds against various bacteria was assayed.     

Synthesis and crystal structures of tetraacetylethylenediamine and <Emphasis Type="Italic">N</Emphasis>-(2-ammoniumethyl)carbamate

Two ethylenediamine derivatives—N-(2-ammoniumethyl)carbamate HN(COO^?)CH₂CH₂N⁺H₃ (I) and tetraacetylethylenediamine (H₃CC(O))₂NCH₂CH₂N(C(O)CH₃)₂ (II) (synthesized for the first time)—have been synthesized and characterized by X-ray crystallography. Compounds I and II are isolated as minor admixtures upon an attempt to synthesize ethylenediamine complexes of lanthanum and neodymium nitrates, respectively. The crystals of I and II are monoclinic: a = 7.778 Å, b = 8.060 Å, c = 7.568 Å, β = 95.73°, Z = 4, space group P2₁/c (I); a = 5.946, b = 10.255, c = 9.343 Å, β = 95.72°, Z = 2, space group P2₁/c (II). The bond lengths and bond angles lie within the corresponding standard values. Compounds I and II have different conformations of the N-C-C-N ethylenediamine moiety: gauche in I and trans in II, and the corresponding torsion angles are equal to 66.6° and 180°, respectively.     

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.     

Synthesis,Structure, and Magnetic Properties of a Twist Linear Tetranuclear Co<Stack><Subscript>2</Subscript><Superscript>III</Superscript></Stack>Ln<Stack><Subscript>2</Subscript><Superscript>III</Superscript></Stack> Complexes

A series of twist linear tetranuclear 3d–4f Co ₂ ^III Ln ₂ ^III [Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5)] complexes have been prepared under solvothermal conditions and structurally characterized with Schiff-base ligand 2-(((2-hydroxy-3-methoxyphenyl)methylene)amino)-2-(hydroxymethyl)-1,3-propanediol (H₄L). The two central Co ions are linked by two alkoxyl oxygen atoms, and one Ln ion lying above and the other below the Co–Co dimer, form a twist linear array. The magnetic susceptibility studies reveal antiferromagnetic or ferromagnetic behaviour, whilst dynamic magnetic studies indicate no slow magnetic relaxation for these complexes.     

Synthesis,crystal structures,and catalytic property of dioxomolybdenum(VI) complexes with hydrazone ligands derived from 3,5-Di-<Emphasis Type="Italic">tert</Emphasis>-butylsalicylaldehyde

Two new dioxomolybdenum(VI) complexes, [MoO₂L¹(MeOH)] (I) and [MoO₂L²] (II), where L¹ and L² are the anionic forms of N'-(2-hydroxy-3,5-di-tert-butylbenzylidene)-4-methoxybenzohydrazide and 2-amino-N'-(2-hydroxy-3,5-di-tert-butylbenzylidene)benzohydrazide, respectively, have been synthesized and characterized by elemental analysis, FT-IR spectra, and single crystal X-ray determination (CF files CCDC nos. 1448089 (I), 1487063 (II)). The crystal of I is monoclinic: space group P21/n, a = 7.353(1), b = 24.758(3), c = 13.891(2) Å, β = 101.013(2)°, V = 2482.3(6) Å3, Z = 4, R ₁ = 0.0848, wR ₂ = 0.2050. The crystal of II is monoclinic: space group P2₁/c, a = 6.752(1), b = 16.947(1), c = 19.510(1) Å, β = 96.891(2)°, V = 2216.5(4) Å3, Z = 4, R ₁ = 0.0670, wR ₂ = 0.1638. The Mo atom in complex I is in octahedral coordination, with three donor atoms of the hydrazone ligand, two oxo groups, and one methanol O atom. The Mo atom in complex II is in square pyramidal coordination, with three donor atoms of the hydrazone ligand, and two oxo groups. The complexes have interesting catalytic properties for sulfoxidation reactions.     

X-ray study of rhodium(III) sulfates

Compounds with compositions [Rh(H₂O)₆]₂(SO₄)₃·4H₂O (I), (H₃O)[Rh(H₂O)₆](SO₄)₂ (II), [Rh(H₂O)₅OH](SO₄)·0.5H₂O (III), and [Rh(H₂O)₆]₂(SO₄)·(H₂SO₄) _x ·5H₂O (IV) have been studied. The crystal structures of II, III, and IV were determined. All compounds crystallized in the monoclinic crystal system. Crystal data for II: a = 7.279(2) Å, b = 10.512(7) Å, c = 15.806(3) Å, β = 96.71(3)°, space group P2₁/n, Z = 2, d _calc = 2.334 g/cm³; III: a = 20.433(4) Å, b = 7.820(2) c = 11.215(2) Å, β = 114.14(1)°, space group C2/c, Z = 8, d _calc = 2.559 g/cm³; IV: a = 6.2250(4 Å), b = 27.0270(12) Å, c = 7.2674(5) Å, β = 97.04(3)°, space group P2₁/c, Z = 4, d _calc = 2.143 g/cm³. The compounds were studied by IR spectroscopy and powder X-ray diffraction. All of the isolated crystalline phases are sparingly soluble in ethanol and well soluble in water.     

Synthesis and crystal structures of Schiff base oxovanadium(V) complexes [VO(Bhm)(OCH<Subscript>3</Subscript>)(CH<Subscript>3</Subscript>OH)] and [VO<Subscript>2</Subscript>(Bpp)]

Compound [VO(acac)₂] reacts with the Schiff bases N′-(5-bromo-2-hydroxybenzylidene)-2-hydroxy-3-methylbenzohydrazide (H₂Bhm) and 4-bromo-2-[(2-piperidin-1-ylethylimino)methyl]phenol (HBpp) in absolute methanol to give the oxovanadium(V) complexes [VO(Bhm)(OCH₃)(CH₃OH)] (I) and [VO₂(Bpp)] (II), respectively. Both complexes were characterized by elemental analysis, IR spectra, and single-crystal X-ray determination. The crystal of I crystallizes in the triclinic space group \(P\bar 1\) with a = 7.625(2), b = 11.240(3), c = 12.156(4) Å, α = 77.404(5)°, β = 75.770(4)°, γ = 79.922(5)°, V = 977.4(5) ų, Z = 2. The crystal of II crystallizes in the monoclinic space group P2/c with a = 26.760(3), b = 6.655(1), c = 17.570(2) Å, β = 100.335(2)°, V = 3078.2(7) ų, Z = 8. The V atom in I is in an octahedral coordination, and those in II are intervenient between square pyramidal and trigonal bipyramidal coordination.     

Structural studies of nickel(II) complexes with 1-<Emphasis Type="Italic">tert</Emphasis>-butylimidazole-2-thione and 3-phenyl-5-methyl-pyrazole ligands

The nickel(II) complexes dichlorobis(1-tert-butylimidazole-2-thione)nickel(II) [Ni(tm ^t-Bu)₂Cl₂] (1), dinitratobis(1-tert-butylimidazole-2-thione)nickel(II) [Ni(tm ^t-Bu)₂(NO₃)₂] (2), dichloro-bis(3-phenyl-5-methyl-pyrazole)(1-tert-butylimidazole-2-thione)nickel(II) [Ni(pz^Ph,MeH)₂(tm ^t-Bu)Cl₂] (3) and dinitratobis(3-phenyl-5-methyl-pyrazole)(1-tert-butylimidazole-2-thione)nickel(II) [Ni(pz^Ph,MeH)₂(tm ^t-Bu)(NO₃)₂] (4) have been synthesized and studied. The single crystal X-ray diffraction analysis was carried out for 1 and 4 {Bruker Kappa Apex-II CCD diffractometer, MoK _α radiation}. Crystal data for 1: monoclinic C2/c, a = 16.949(2) Å, b = 8.6647(10) Å, c = 15.461(3) Å, β = 117.662(4)°, V = 2011.1(5) ų, Z = 4, D _calc = 1.460 g/cm³. Crystal data for 4: triclinic P-1, a = 9.9775(7) Å, b = 11.2254(8) Å, c = 14.8068(10) Å, α = 75.401(4)°, β = 87.422(4)°, γ = 74.874(4)°, V = 1548.86(19) ų, Z = 2, D _calc = 1.405 g/cm³. Coordination core of complex 1 adopts distorted tetrahedral geometry whereas core 4 has distorted octahedral geometry. The bonded nitrates are of two types coordinating as monodentate and bidentate ligands.     

Syntheses and crystal structures of [Bi(DMSO)<Subscript>8</Subscript>][Fe(NCS)<Subscript>6</Subscript>] and [Al(DMSO)<Subscript>6</Subscript>][Al(NCS)<Subscript>6</Subscript>]

New complexes of composition [Bi(DMSO)₈][Fe(NCS)₆] (1) and [Al(DMSO)₆][Al(NCS)₆] (2) have been prepared, and an octahedral hexarodanoaluminate anion has been structurally characterized for the first time. Crystals of compound 1 are triclinic, space group \(P\bar 1\), a = 11.2368(4) Å, b = 11.4063(4) Å, c = 21.0711(9) Å, α = 92.9520(10)°, β = 99.9430(10)°, γ = 111.9290(10)°, V = 2447.69(16) ų, Z = 2, ρ_calc = 1.680 g/cm³, R ₁ = 0.0564; crystals of compound 2 are cubic, space group \(Pa\bar 3\), a = 15.8201(4) Å, V = 3959.39(17) ų, Z = 4, ρ_calc = 1.462 g/cm³, R ₁ = 0.0475. The bismuth coordination polyhedron BiO₈ in compound 1 is a distorted square antiprism with broken square faces (Bi-O, 2.368-2.582 Å). In the structure of 2, the cation disordered in a complex manner has an octahedral configuration (Al-O, 1.888(11)-1.912(11) Å).     

Co(II) and Ni(II) complexes incorporating <Emphasis Type="Italic">N</Emphasis>-acetimidoylacetamidine ligand: Synthesis and structures

Two new square planar complexes with the formula Co(L)₂ · CH₃OH (1) and Ni(L)₂ · CH₃OH (2) (HL = HN{C(Me)=NH}₂ = N-acetimidoylacetamidine) have been synthesized by solvothermal reactions in methanol/acetonitrile. N-acetimidoylacetamidine ligand was derived from the self-condensation reaction of acetonitrile, and the reaction was promoted by the cooperation of M(II) (M = Co in 1 and M = Ni in 2) with diphenylcarbazide. 1 and 2 are characterized by single crystal X-ray diffraction, elemental analysis and infrared spectrum. Both complexes crystallize in the monoclinic space group P2₁/c with a = 9.329(6) Å, b = 11.494(7) Å, c = 13.040(8) Å, β = 92.945(11)°, V = 1396.3(16) ų and Z = 4 for 1, and a = 9.323(4)Å, b = 11.512(5) Å, c = 13.020(6)Å, β = 92.819(7)°, V = 1395.7(10)ų and Z = 4 for 2.     

Rosenmund-Braun Reaction Products 4′,5′-Dicyanobenzo-15-crown-5 and 4′,5′-Dicyanobenzo-15-crown-5,4′-cyano-5′-cyano(bromo)benzo-15-crown-5 Hydrates: Spectroscopic Properties and Crystal Structure

The products of 4′,5′-dibromobenzo-15-crown-5 (I) cyanation by the Rosenmund-Braun reaction are studied by the ¹H NMR and IR spectroscopy methods. X-ray diffraction analysis of two isolated products, i.e., di(4′,5′-dicyanobenzo-15-crown-5) 1.6 hydrate {(CN)₂B15C5}₂ · 1.6H₂O (IIa) and 4′,5′-dicyanobenzo-15-crown-5,4′-cyano-5′-cyano(bromo)benzo-15-crown-5 dihydrate (CN)_3.85Br_0.15(B15C5)₂ · 2H₂O (III) is performed. Crystals IIa are monoclinic, a = 15.882(2) Å, b = 11.412(2) Å, c = 18.484(3) Å, β = 100.717(3)°, V = 3291.7(9) ų, Z = 4, space group P2₁/c, R = 0.0746 for 4775 reflections with I > 2σ(I). Crystals III are monoclinic, a = 15.956(3) Å, b = 11.425(2) Å, c = 18.865(4) Å, β = 99.32(3)°, V = 3394(1) ų, Z = 4, space group _P2₁/_{c, R} = 0.0692 for 2070 reflections with I > 2σ(I). Compounds IIa and III have similar structures with two crystallographically independent molecules in each (A and B in IIa; C and D in III). Four of the five O atoms of a macrocycle in molecules A and C form hydrogen bonds with the water molecules. The latter molecules lie above and below the cycle plane at a distance of ～2 Å from this plane. The A and C molecules have identical conformations (TTG TTG TTG TTG TTC) that differ from those of molecules B (TTG TGG STT SSG TTC) and D (TTC TSG STT SSG TTC).     

Synthesis,characterization, crystal structures,and antimicrobial activity of cobalt(II) and iron(III) complexes derived from N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide

A new cobalt(II,III) complex, [Co^IIIL₂]₂[Co ₂ ^II (HL)₂(OH₂)₂(CH₃OH)₂] ? 2H₂O (I) and a new iron(III) complex, [Fe^III(HL)₂](NO₃) (II), where L^2– and HL^– are the dianionic and monoanionic form of N'-(2-hydroxybenzylidene)-3-methylbenzohydrazide, respectively, have been prepared and characterized by elemental analyses, infrared and UV-Vis spectroscopy and single-cyrstal X-ray diffraction (CIF files CCDC nos. 1417971 (I), 1417979 (II)). Complex I crystallizes in the monoclinic space group P2₁/n with unit cell dimensions a = 16.1665(9), b = 14.5692(8), c = 19.086(1) Å, β = 96.347(1)°, V = 4467.9(4) ų, Z = 2, R ₁ = 0.0521, and wR ₂ = 0.1411. Complex II crystallizes in the orthorhombic space group Pbcn with unit cell dimensions a = 12.475(1), b = 12.202(1), c = 18.859(2) Å, V = 2870.8(4) ų, Z = 4, R ₁ = 0.0796, and wR ₂ = 0.1981. The metal atoms in the complexes are in octahedral coordination. Crystals of the complexes are stabilized by hydrogen bonds. The efficiency of the aroylhydrazone and the two complexes was evaluated against B. subtilis, S. aureus, E. coli, P. fluorescence, C. albicans and A. niger, with the complexes demonstrating enhanced activity relatively to the free ligand.     

Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.     

Copper(II) coordination compounds with 8-quinolinaldehyde semicarbazone: Synthesis and structure

A series of compounds of the general formula Cu(HL)X₂ · nH₂O (compound I, X = ClO₄, n = 3; compound II, X = NO₃, n = 2; compound III, X = Cl, n = 0.5; compound IV, X = 1/2SO₄, n = 0) is isolated by the reactions of the copper(II) salts with quinolinaldehyde semicarbazone (HL). Regardless of the reactant ratio, only the compounds with a metal to ligand mole ratio of 1: 1 are formed, where the organic reactant is coordinated in the molecular form. The X-ray diffraction analyses of the [Cu(HL)(NO₃)(H₂O)](NO₃) · H₂O (II) and [Cu(HL)Cl₂] · 0.5H₂O(III) compounds show their substantially different organizations of the molecular structures depending on the specifics of the acido ligand. An ionic structure with one NO ₃ ^? anion incorporated into the inner coordination sphere of the metal as a bidentate chelate ligand is observed in compound II. Molecular tetragonal pyramidal complexes associated into a dimer due to the bridging function of one coordinated Cl^? anion are formed in structure III. The coordination polyhedron of the copper atom in structures II and III is an asymmetrically extended tetragonal bipyramid. The CuClCu angle equal to 90° and the distance between two planes in compound III equal to 2.978 Å determine the insignificant antiferromagnetic interaction in this compound (g = 2.1, J = ?2.5 cm^?1).     

The conformational spaces of dinaphthyl ketones,dinaphthyl thioketones,and dinaphthyl diazomethanes: 1-substituted naphthalenes versus 2-substituted naphthalenes

1,1′-Dinaphthyl ketone (15), 1,2′-dinaphthyl ketone (18), 2,2′-dinaphthyl ketone (19), 1,1′-dinaphthyl thioketone (16), 1,2′-dinaphthyl thioketone (20), 2,2′-dinaphthyl thioketone (21), 1,1′-dinaphthyldiazomethane (17), 1,2′-dinaphthyldiazomethane (22), and 2,2′-dinaphthyldiazomethane (23) have been synthesized. Ketone 15 has been prepared from di(1-naphthyl)methanol; ketone 18 has been prepared by a Friedel–Crafts acylation of naphthalene with 2-naphthoyl chloride; ketone 19 has been prepared by a Grignard reaction of 2-naphthylmagnesium bromide with 2-naphthoyl chloride. Thioketones 16, 20, and 21 have been prepared by reactions of the corresponding ketones 15, 18, and 19 with Lawesson’s reagent. The diazomethane derivatives 17, 22, and 23 have been prepared by the HgO oxidation of the respective hydrazones 25, 27, and 28 (prepared from the respective thioketones 16, 20, and 21). The crystal and molecular structures of ketones 15, 18, and 19 and of thioketone 16 have been determined. A variety of conformations in the crystal structures is noted: 1Z,1′Z (15), 1E,1′Z (16), 1E,2′E (18), 2Z,2′Z (19). The NMR experiments have demonstrated the downfield shifts of the protons peri to the carbonyl and the thiocarbonyl groups in 15, 16, and 18, but not in 20. A systematic DFT study (B3LYP/6-31G(d)) of the conformational spaces of 15–23 and their ¹H and ¹³C NMR chemical shifts has been performed. In each series of constitutional isomers, the order of stabilities is 2,2′-(NA)₂C=X > 1,2′-(NA)₂C=X > 1,1′-(NA)₂C=X. The decrease in the stabilities of 1-naphthyl derivatives relative to 2-naphthyl derivatives is attributed to the increased overcrowding and the increased twist angles in 1-naphthyl derivatives. The increased stabilization of E-conformations with the increase of the radius of a heteroatom at C⁹ due to the steric reasons is noted. The DFT calculations satisfactorily describe the X-ray conformations of 15, 16, 18, and 19.     

Cobalt(II) and nickel(II) cloride complexes with 4,5-(<Emphasis Type="Italic">n</Emphasis>-pyridylethylene)-dithio-1,3-dithiol-2-thiones (<Emphasis Type="Italic">n</Emphasis> = 2, 4)

The NiCl₂ and CoCl₂ complexes with 4,5-(2-pyridylethylene)-dithio-1,3-dithiol-2-thione (L¹) and 4,5-(4-pyridylethylene)-dithio-1,3-dithiol-2-thione (L²) were described. The L¹ ligand shows bidentate coordination through the pyridyl N atoms and the thiol S atoms in a tetrahedral [CoCl₂(L¹)] complex (I) and in an octahedral [NiCl₂(L¹)₂](MeCN)₂ complex (II). The L² ligand exhibits monodentate coordination through the pyridyl N atom in tetrahedral complexes [CoCl₂(L²)₂ (III) and [NiCl₂(L²)₂] (IV). Complexes I, III, IV in crystal state are octahedral due to extra coordination of the thione S atoms or the chloride bridges responsible for the polymeric structure. The structure of the complex II · CH₂Cl₂ was determined by X-ray diffraction analysis. The crystals are monoclinic, space group P2₁/c, a = 11.895(2) Å, b = 13.374(3) Å, c = 21.873(4) Å, β = 95.30(3)°, Z = 2. The Ni atom has quasi-tetrahedral surrounding due to two chloride ions and two L¹ ligands coordinated through the pyridyl N atoms and the thiol S atoms.