The unprecedented preparation of dinuclear zinc(ii) complexes from 4-halido-2-[(3-cyclohexylaminopropylimino)methyl]phenol

Abstract

Three new centrosymmetric trinuclear nickel(II) and manganese(II) complexes, Ni[Ni(CH(3)COO)(CPA)](2) (1), Ni[Ni(CH(3)COO)(BPA)](2) (2), Mn[Mn(CH(3)COO)(BPA)](2) (3), where H(2)CPA = N,N'-bis(5-chlorosalicylidene)-1,3-propanediamine, H(2)BPA = N,N'-bis(5-bromosalicylidene)-1,3-propanediamine, and two new centrosymmetric dinuclear zinc(II) complexes, [Zn(2)(CMP)(2)] (4) and [Zn(2)(BMP)(2)] (5), where H(2)CMP = 4-chloro-2-{[3-(5-chloro-2-hydroxybenzyl)aminopropylimino]methyl}phenol, and H(2)BMP = 4-bromo-2-{[3-(5-bromo-2-hydroxybenzyl)aminopropylimino]methyl}phenol, have been prepared from the Schiff bases derived from 5-halido-substituted salicylaldehydes with N-hexylpropane-1,3-diamine under solvothermal conditions. The complexes have been characterised by elemental analysis, IR spectroscopy and single-crystal X-ray diffraction studies. The complexes 1, 2, and 3 crystallise in the monoclinic space group P2(1)/c with cell dimensions a = 9.347(1), b = 11.507(2), c = 18.539(2) Å, β = 93.774(2)°, Z = 2 (for 1), a = 9.111(4), b = 12.089(6), c = 18.724(8) Å, β = 92.117(7)°, Z = 2 (for 2), and a = 11.328(2), b = 22.468(5), c = 8.270(2) Å, β = 93.74(3)°, Z = 2 (for 3), while complexes 4 and 5 crystallise in the triclinic space group P1, with cell dimensions a = 7.483(1), b = 9.990(2), c = 12.155(2) Å, α = 75.27(3), β = 85.00(3), γ = 73.82(3)°, Z = 1 (for 4), and a = 7.008(1), b = 10.081(2), c = 13.095(3) Å, α = 100.62(3), β = 95.51(3), γ = 104.03(3)°, Z = 1 (for 5). It is interesting that the mono-Schiff bases 4-chloro-2-[(3-cyclohexylaminopropylimino)methyl]phenol (HCCP) and 4-bromo-2-[(3-cyclohexylaminopropylimino)methyl]phenol (HBCP) used to prepare the nickel(II) and manganese(II) complexes were transferred to bis-Schiff bases H(2)CPA and H(2)BPA in the complexes 1, 2, and 3, while the mono-Schiff bases HCCP and HBCP used to prepare the zinc(II) complexes were transferred to novel ligands H(2)CMP and H(2)BMP, bearing the unexpected, newly formed carbon-nitrogen single bond.

Solvolthermal synthesis, structure, and properties of a novel dinuclear zinc(II) complex

“…The Zn atom deviates from the least squares plane defined by the equatorial donor atoms by 0.100(2) Å. The coordinate bond lengths in the com plex are comparable to those reported in similar zinc(II) complexes [9,10] In the IR spectrum of [Zn 2 L 2 ], there exists a char acteristic N-H vibration at 3225 cm -1 . The strong ab sorption band at 1629 cm -1 can be attributed to the vi bration of the azomethine groups, ν(C=N).…”

“…It was found that the mono Schiff base ligand 4 chloro 2 [(3 cyclohexylami nopropylimino)methyl]phenol can be transformed to bis Schiff base ligand N,N' bis(5 chlorosalicylidene) 1,3 propanediamine under solvolthermal condition [8]. Then, they reported three interesting dinuclear zinc(II) complexes derived from mono Schiff bases bearing 2 [3 cyclohexylaminopropylimino]methyl]phe nol backbone under solvolthermal conditions [9,10]. It is interesting that the mono Schiff bases underwent structural transformation during the reactions.…”

“…In the presence of Zn 2+ ions, the reaction underwent a 1,3 hydride shift process [9,[15][16][17] can observe that the cyclohexyl groups of the Schiff bases can remove away only under solvolthermal con ditions.…”

Synthesis, Crystal Structure and Antimicrobial Activity of a Linear Trinuclear Nickel(II) Complex with Schiff Base Ligand

“…15 And also an acetate and phenolate bridged trinuclear nickel complex was prepared by nickel acetate with H 2 L under solvothermal condition. 16 Interestingly, the present complex was prepared by the reaction of the Schiff base ligand with nickel acetate in a 2:3 molar ratio under ambient condition. Crystals of the complex are stable in air at room temperature, soluble in DMF, DMSO, MeOH, EtOH and MeCN, insoluble in water.…”

The Construction of a Novel Bromido- and Azido-Bridged Dinuclear Copper(II) Complex Derived From 4-Chloro-2-[(2-hydroxyethylimino)methyl]phenol

“…As is well known, the halide and pseudohalide groups can link two or more metal atoms, yielding various polynuclear complexes. [4][5][6][7][8][9] To our knowledge, there are no bromido-bridged dinuclear copper complexes with Schiff bases derived from salicylaldehyde and its derivatives have been reported so far. In this study, a novel dinuclear Schiff base copper(II) complex with bromide and azide bridges, [Cu 2 Br 2 L 2 ]·[Cu 2 Br(N 3 )L 2 ]·H 2 O, where L is the deprotonated form of the Schiff base 4-chloro-2-[(2-hydroxyethylimino)methyl]phenol (HL; Scheme 1), was successfully prepared and characterized.…”