Manganese(II) Complexes containing the Tridentate Ligands 2,6-Bispyridine, L1, or 2,6-Bispyridine, L2. The Molecular Structures of Five-co-ordinate 1> and the Zinc Analogue 1>

Article abstract of DOI:10.1039/DT9900003161

Reactions of equimolar ratios of MnX2*4H2O (X = Cl or Br) and the tridentate ligands 2,6-bis<1-(phenylimino)ethyl>pyridine (L¹) or 2,6-bis<1-(4-methoxyphenylimino)ethyl>pyridine (L²) afford the five-co-ordinate complexes 1> and 2>.The complex 1>, as the monobenzene solvate, crystallises in the space group P2₁2₁2₁ with a = 8.761(3), b = 17.032(5), c = 17.453(5) Angstroem, and Z = 4.The distorted trigonal-bipyramidal geometry around manganese involves a trigonal plane with angles close to 120 deg comprising both bromines and the pyridyl nitrogen of L¹.However, strain induced by this ligand reduces the axial NMnN angle to 142.8 deg.The Mn-N(pyridyl) bond is markedly shorter than the axial Mn-N(imino) bonds.For comparison, the structure of 1>, as the 1.5MeCN solvate, has been determined.This complex crystallises in the triclinic space group P1/ with a = 8.977(3), b = 12.585(5), c = 22.297(6), α = 90.99(3), β = 98.27(2), γ = 94.33(3) deg, and Z = 4.The two independent molecules of 1> in the asymmetric unit are geometrically identical within the limits of experimental error, with bond lengths and angles differing less than twice the estimated standard deviations.The distorted trigonal-bipyramidal geometry and bond length and angle variations are similar to those of the manganese complex.Reactions of Mn(ClO4)2*6H2O with 2 equivalents of L¹ or L² produce the cations 12>²⁺ and 22>²⁺ isolated as the perchlorates.The two ligands of the octahedral cations are co-ordinated in a meridional manner.

Full text of DOI:10.1039/DT9900003161

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