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Kristallstrukturen der [2.2.2]Cryptate [Cd(cryptand 222)][CdCl4] und [Hg(cryptand 222)][Hg2Cl6] mit achtfach koordinierten Metallionen

Pickardt, Joachim; Kühn, Britta

Inst. Chemie

Reactions of [2.2.2]cryptand, 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo-[8.8.8]hexacosane, (“cryptand 222”) with cadmium chloride and mercuric chloride yielded crystals of [Cd(cryptand 222)][CdCl4] (1) and [Hg(cryptand 222)][Hg2Cl6] (2). 1 crystallizes tetragonally, space group P42/n, Z = 4, a = 1239.8(2), c = 1801.2(8) pm; 2 is monoclinic, space group P2/n, Z = 2, a = 1060.3(3), b = 955.2(2), c = 1607.0(3) pm. and β = 108.85(2)°. In the cations of both complexes the metal ions are enclosed in the bicyclic ligand and show 8-coordination to its six oxygen and two nitrogen atoms, the coordination polyhedron is a distorted cube for 1 and a bicapped trigonal antiprism for 2. The anion of 2 is dimeric, the two mercury atoms are connected via chlorine bridges with Hg-Cl distances of 258 and 278 pm, the Hg-Cl bond lengths to the two terminal chloro ligands being shorter at 236 and 238 pm.