| Popis: |
The nickel(II) and copper(II) complexes of meso-3,6,6,9-tetramethyl-4,8-diazaundecane-2,10-dione dioxime (meso-HM-PAO) have an intramolecular hydrogen bond between cis oxime groups. [Cu(meso-HM-PAO-H)(H2O)](NCS) crystallizes in space group P21/n with a = 7.692(1), b = 12.028(2), c=20.235(3) A, β=93.03(1)°, Z = 4 and Dc=1.46 g/cm3. The final R value for this complex was 0.034 for 2223 observed reflections with I ≥ 2.5σ (I). The Cu(II) coordination is a distorted square pyramid. The Cu(II) ion is five-coorinated with the diazadioxime N atoms equatorial and water O atom axial. The Cu(II) is 0.12 A from the equatorial plane towards the hydrate. The equatorial Cu-N distances span a narrow range, 1.953(3)-1.999(3) A. The axial Cu-O distance is 2.314(3) A. The thiocyanate group is almost linear. The intramolecular O O hydrogen bond length is 2.479(4) A. [Ni(meso-HM-PAO-H)](ClO4) crystallizes in space group P21/c with a = 14.774(3), b = 12.752(3), c = 20.035(4) A, β = 92.94(3)°, Z = 8 and Dc = 1.51 g/cm3. The final R value for the complex was 0.053 for 4794 observed reflections with F ≥ 4σ (F). The coordination about Ni(II) is a slightly distorted square plane. The Ni(II) ion is 0.0673(7) A from the best plane of the four donor nitrogen atoms away from the perchlorate ion. The Ni-N distances span a narrow range 1.863(4)-1.927(4) A. There are two molecules per asymmetrical unit resulting in eight molecules being packed in an unit cell; they are bound together by van der Waals interactions. The O-H O bonds of these complexes give characteristic infrared absorptions as well as chemical shift of the 1H NMR signal (Ni complex). |
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