NITROSAMINE COMPLEXES OF SBCL5 AND CUCL2

Dialkylnitrosamines form 1:1 complexes with SbCl5 (colourless) and CuC l2 (reddish brown). Me2NNOSbCl5 (1) crystallizes in the monoclinic spa ce group P2(1)/n with a = 8.860(2), b = 13.150(3), c = 9.540(2) Angstr om, beta = 92.58(3)degrees and Z = 4. The components are joined by a O -Sb bond and the complex is isostructural to that of dimethylformamide Me2NCHOSbCl5. The N-sitrosopiperidine CuCl2 complex (6) crystallizes in the monoclinic space group P2(1)/c with a = 6.5294(2), b = 16.7236( 3), c = 8.5990(2) Angstrom, beta = 112.210(1)degrees and Z = 4. As in the case of the known dimethylnitrosamine CuCl2 complex (5) the struct ure consists of infinite doubly chlorobridged CuCl2 chains to both sid es of which nitrosamine molecules are coordinated both by the O atom a nd the N atom of their nitroso group. While the nitroso groups of the dimethylnitrosamine molecules point in the same direction at either si de of the chain resulting in a uniform CuCl4ON array in 5, the nitroso piperidine molecules at the two sides of the chain are arranged in opp osite directions resulting in alternating CuCl4O2 and CuCl4N2 arrays i n 6. In the latter coordination the Jahn-Teller distortion results in an elongation of the CuN2 axis, while in the former an elongation of t wo of the CuCl bonds is noted. (C) 1998 Elsevier Science S.A.