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Complex formation of metal salts with macrocyclic polyethers in aprotic organic solvents: crystal structures of the molecular complex [MeCN·Mg·15C5(μ2-Cl)CuCl3] and the ionic complexes [(MeCN)2·Mg·15C5][Cu2Cl6], {[(MeCN)2·Mg·15C5][Cu3Cl8]} , [(H2O)2·Mg·15C5][CuCl4]·H2O and {[(H2O)2·Cu3Cl8][Mg·(H2O)6]·[2(15C5)]·H2O

1992; Elsevier BV; Volume: 11; Issue: 15 Linguagem: Inglês

10.1016/s0277-5387(00)83742-0

1873-3719

T. B. Rubtsova, O.K. Kireeva, Boris M. Bulychev, N.P. Streltsova, V.K. Belsky, Б. П. Тарасов,

Layered Double Hydroxides Synthesis and Applications

Abstract Interaction of anhydrous MgCl2 and CuCl2 in acetonitrile in the presence of 15C5 leads to the formation of the molecular complex [MeCN·Mg· 15C5·(μ2-Cl)CuCl3] (I) and the ionic complexes [(MeCN)2·Mg·15C5][Cu2Cl6] (II) and {[(MeCN)2·Mg·15C5]·[Cu3Cl8]}n (III). In all three compounds the magnesium is in the inner cavity of the macrocycle and its polyhedron is a pentagonal bipyramid with five oxygens in the equatorial plane and nitrogen and chlorine (I) or two nitrogens (II,III) in apical positions. The anion[Cu3Cl8]2− is polymeric. On hydration of I–III by water vapour acetonitrile is replaced and the fragment with the intracavital metal is partially or completely cleaved. The compounds thus formed are CuCl2·2H2O, {[(H2O)2·Mg·15C5][CuCl4]H2O} (IV), {[(H2O)2·Cu3Cl8][Mg(H2O)6]·2(15C5)]· H2O}n (V) and {CuCl2·(H2O)2·15C5}n (Va). Magnesium in IV is intracavital, while in V and Va the crown ether is in the second coordination sphere. Both compounds are chain polymers with structural units linked by hydrogen bonds. The structural, thermal and spectrophotometric data indicate that the heterometallic crown compounds of this type are characterized by a higher stability compared with homometallic CuCl2 complexes.