Coordination Compounds of Copper(II) Nitrate with Products of Aminotris(hydroxymethyl)methane Condensation with Salicyl- and 5-Nitrosalicylaldehydes: Synthesis and Crystal Structures

Abstract

Earlier [1], 3 d -element salts were found to react with the products of aminotris(hydroxymethyl)methane condensation with salicylaldehyde or its derivatives to give a variety of coordination compounds with fungicidal properties. Depending on the synthesis conditions and the nature of the starting reagents, mono-or polynuclear complexes can be obtained. Because only halides and acetates were used as starting salts, it was interesting to find out how the compositions and structures of the resulting coordination compounds would be affected by replacement of the above acid residues by the nitrate ion. In connection with this, we synthe-II ) and determined their crystal structures by X-ray diffraction analysis N OH HO HO OH N OH HO HO OH O 2 N ; (HL) (HL 1 )Abstract -The crystal structures of copper(II) nitrate complexes with 2-(2-hydroxybenzylideneamino)-2-hydroxymethylpropane-1,3-diol (HL) and 2-hydroxymethyl-2-(2-hydroxy-5-nitrobenzylideneamino)propane-1,3-diol (HL 1 ) were determined. The resulting complexes were formulated as [II ). The crystals of I are monoclinic, a = 17.809(4) Å, b = 30.549(6) Å, c = 18.962(4) Å, β = 115.36(3) ° , space group Cc , Z = 8, R = 0.0482. Complex I is composed of two independent three-dimensional µ 3 -oxo complexes; the coordination polyhedron of the copper atoms in both compounds is an elongated tetragonal bipyramid. The coordination polyhedron of the third Cu atom is a tetragonal pyramid. The bases of the pyramids are composed of the oxygen atoms of the phenol and alcohol OH groups, the imine N atom of ligand L, and µ 3 -oxo atoms. The phenol and water O atoms serve as the apices in both the tetragonal bipyramids. The crystals of II are triclinic, a = 6.062(1) Å, b = 7.701(2) Å, c = 16.162(3) Å, α = 88.15(3) ° , β = 84.94(3) ° , γ = 78.13(3) ° , space group P , Z = 2, R = 0.0272. Complex II is composed of polymer chains formed by coordination bonds between the copper atom and two O atoms of the amino alcohol in the azomethine of the neighboring complex connected to the initial one by translation along the x axis. These chains are linked through hydrogen bonds involving the oxygen atoms of the NO 2 groups. The benzene rings of the azomethine ligands of the adjoining complexes from different chains are antiparallel to each other. The coordination polyhedron of the central atom is an elongated tetragonal bipyramid. Its equatorial plane is formed by the phenol O atom, one of the alcohol O atoms, the N atom of ligand L 1 , and the O atom of the amino alcohol in the neighboring complex. The apices are the O atom of the water molecule and the O atom of the amino alcohol in the neighboring azomethine molecule. In complexes I and II , the outer-sphere nitrato group mainly serves to unite trimers and polymers in the crystal by means of hydrogen bonds.

Bis[1,3-dihydroxy-2-hydroxymethyl-2-(5-nitro-2-oxidobenzylideneamino)propane-κ3N,O,O′]nickel(II) pyridine solvate

“…1,3-Dihydroxy-2-hydroxymethyl-2-(2-hydroxy-5-nitrobenzylideneamino)propane was synthesized from tris(hydroxymethyl)aminomethane and 5-nitrosalicylaldehyde according a literature procedure (Chumakov et al, 2003(Chumakov et al, , 2005. This ligand (0.30 g, 1.11 mmol) was dissolved in ethanol (25 ml) and several drops of aqueous sodium hydroxide were added to raise the pH of the solution to about 8.5.…”

The coordination chemistry of tartronic acid with copper: magnetic studies of a quasi-equilateral tricopper triangle

“…There are a number of other trinuclear copper complexes in the literature. In three papers, the Cu 3 triangle has a µ 3oxo 21,22 or µ 3 -methoxo 23 ligand linking the square pyramidal copper centres. In the first two, the three planes containing the magnetic orbitals are roughly orthogonal, and the only one where magnetic measurements were reported, 21 shows only very weak antiferromagnetic coupling (−5 cm −1 ).…”

Structures and Magnetic Properties of an Antiferromagnetically Coupled Polymeric Copper(II) Complex and Ferromagnetically Coupled Hexanuclear Nickel(II) Clusters

“…The coordination versatility of the Schiff-base ligand (H 4 L3) (Figure ) toward transition metal ions − has prompted us to synthesize the related ‘double’-Schiff-base ligand H 7 L (Figure ) and explore its coordination chemistry. It is a potentially ennea-dentate, hepta-anionic ligand with a high degree of conformational flexibility and potential to coordinate in a convergent (directing formation of the dinuclear units) and divergent fashion (ability to extend coordination beyond the primary coordination mode, creating 1-dimensional chain, 2-dimensional sheet, or 3-dimensional structures utilizing one, two, or three protonated/deprotonated hydroxymethyl groups present in each side arm).…”