Komplexe 17-gliedriger Dibenzo-Makrocyclen mit N3O2- bzw. N3S2-Donorzentren Strukturen von [Zn(′N3O2′)Cl]2ZnCl4 und [Hg(′N3S2′)Br2] / Complexes of 17-Membered Dibenzo Macrocycles with N3O2 or N3S2 Donor Sets Crystal and Molecular Structures of [Zn(′N3O2′)Cl]2ZnCl4 and [Hg(′N3S2′)Br2]

Abstract

The macrocyclic complexes [Zn(′N3O2')Cl]2ZnCl4 (1) und [Hg(′N3S2')Br2] (2) have been prepared and their crystal structures determined. Zn(II) is incorporated into the macrocyclic cavity of the ′N3O2′ ligand and primarly coordinated to the three nitrogen donors of the macrocycle and to a chloride ion. Weaker interactions occur with the oxygen donors of the macrocycle. The Zn—O distances are 296,4(5) and 322,4(6) pm. In complex 2 Hg(II) lies outside the macrocyclic cavity. The donor set comprises two secondary amine nitrogen atoms and a thioether sulfur atom of the macrocycle, and two bromide anions. The coordination polyhedron can be described as a trigonal bipyramid. The conformational behaviour of the ′N3O2′ and the ′N3S2′ ligands within these and other complexes is discussed. ′N3O2′ and ′N3S2′ are 17-membered dibenzo macrocycles. Crystal data for [Zn(′N3O2')Cl]2ZnCl4 (1): monoclinic, space group C2/c, a = 2864(4), b = 951.0(2), c = 1986(4) pm, β = 118.5(1)°, Z = 4, 2499 reflections, R = 0.0581; [Hg(′N3S2′)Br2] (2): monoclinic, space group P21/c, a = 887.0(2), b = 1307.6(3), c = 2002.3(4) pm, β = 94.13(3)°, Z = 4,3123 reflections, R = 0.072.