Synthesis and Study of Heterometallic Co–Bi Compounds Based on Ethylenediaminetetraacetic Acid. Crystal and Molecular Structures of [Co(DH)2(o-NH2C6H4CH3)2]2[Bi2(μ-Edta)2(H2O)2] · 10H2O (DH2 is dimethylglyoxime)

Compounds of the [Co(DH)₂A₂](BiEdta) · 6H₂O type (where DH is the monodeprotonated dimethylglyoxime ^–ON=C(CH₃)–(CH₃)C=NOH; A is the o-, m-, or p-toluidine; and Edta is the ethylenediaminetetraacetate(4–) ion) were synthesized and studied. The composition and structures of the complexes were determined from their UV and ¹H NMR spectra and from X-ray diffraction data. The isomer [Co(DH)₂(o-NH₂C₆H₄CH₃)₂]₂[Bi₂(μ-Edta)₂(H₂O)₂] · 10H₂O was structurally characterized using X-ray diffraction analysis. The crystals are triclinic: a = 12.153(2) Å, b = 12.824(3) Å, c = 16.215(3) Å, α = 67.73(3)°, β = 86.18(3)°, γ = 66.96(3)°, space group P $\overline 1$ , ρ(calcd) = 1.719 g/cm³, Z = 4. The structure is composed of complex binuclear [Bi₂(μ-Edta)₂(H₂O)₂]^2– anions, [Co(DH)₂(o-NH₂C₆H₄CH₃)₂]⁺ cations, and molecules of crystallization water. The Edta^4– anion chelates with the Bi atom in a hexadentate manner (N₂O₄); the fifth O atom functions as a bridging ligand. The bismuth coordination polyhedron can be regarded as a strongly distorted antiprism. In the octahedral cation, the Co(III) atom coordinates four N atoms of two DH ligands (average Co–N 1.897 Å) and two N atoms of two o-toluidine molecules (Co–N 2.023 Å). Thermolysis of the complexes studied was found to proceed in several successive steps, namely, the deaquation, deamination, and pyrolysis of the ligands.     

Reaction of 5-Substituted 2-(3-Chloropropanoylamino)benzophenone syn- and anti-Oximes with Sodium Hydroxide

Treatment of syn-oximes of 5-substituted 2-(3-chloropropanoylamino)benzophenones with equimolar amount of sodium hydroxide results in formation of syn-oximes of 5-substituted 2-propenoylamino-benzophenones. The corresponding anti isomers under the same conditions give a mixture of anti-oximes of 5-substituted 2-(propenoylamino)benzophenones and 18-membered 11,22-disubstituted 7,8,18,19-tetrahydrodibenzo[d,m][1,10,2,6,11,15]dioxatetraazacyclooctadecine-6,17(5H,16H)-diones.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 969–977.Original Russian Text Copyright © 2005 by Andronati, Simonov, Pavlovskii, Kulikov, Gdanec, Mazepa.     

Copper(II) Cyanoacetate Polymer: Synthesis and Structure

A new copper carboxylate polymer with cyanoacetate anion as a ligand was synthesized and studied using X-ray diffraction, IR, and EPR spectroscopy. The crystal is tetragonal: a= 14.702(2) Å, c= 13.470(3) Å, Z= 8, space group I4₁/a, and R= 0.0634. The copper atoms in the centrosymmetric dimeric fragment have a square-pyramidal surrounding with the CuO₄N coordination core and are joined through four bidentate bridging anions of cyanoacetic acid Cu(1)"–O(1A) 1.931(4) Å, Cu(1)"–O(1B) 1.926(4) Å, Cu(1)–O(2B) 2.018(3) Å, Cu(1)–O(2A) 2.036(4) Å, and Cu(1)–N(1A)" 2.206(5) Å). The Cu···Cu" distance in the dimer is 2.709 Å. The copper atom is extended from the mean equatorial plane toward the axial nitrogen atom by 0.23 Å. EPR data confirm strong antiferromagnetic interaction (2J –275 cm^–1) between the copper(II) ions of the dimeric fragment, whereas the interaction between the dimers is significantly weaker (J< 0.3 cm^–1).