Copper(I) halide complexes with n,n’-diallylthiomorpholinium chloride: synthesis and crystal structure

Abstract

By means of alternating current electrochemical technique, basing on ethanolic solutions of CuCl 2 ·2H 2 O or CuBr 2 and N,N’-diallylthiomorpholinium chloride, the two isostructural s-complexes of [C 4 H 8 NS(C 3 H 5 ) 2 Cu Hal 2 ] composition were obtained in a single crystal form and characterized by X-ray single crystal method: sp. gr. P 2 1 / c , Z = 4, Hal = Cl ( І ) – a = 7.7763(4), b = 13.1892(5), c = 13.1761(6) Å, β = 103.470(5)°, V = 1314.2(1) Å 3 , r calc. = 1.611 g/сm 3 , m (MoK a ) = 2.20 mm −1 , q max. = 28.8°, 10141 measured, 2659 used reflections, R ( F 2 ) = 0.032, S = 1.07; Hal = 1,04Br/0,96Cl ( ІІ ) – a = 7.9771(3), b = 13.2391(5), c = 13.1422(5) Å, β = 103.942(4), V = 1347.1(1) Å 3 , r calc. = 1.80 g/см 3 , m (MoK a ) = 5.02 mm −1 , q max. = 29.0°, 21269 measured, 2772 used reflections, R ( F 2 ) = 0.027, S = 1.08. In the crystal structure of the studied compounds, the trigonal-pyramidal coordination environment of Cu(I) includes sulfur atoms of the organic cation and three chloride anions (compound I ) or chloride/bromide mixture (compound II ). Atoms occupying position Hal (2) perform a bridging function and connect individual coordination polyhedrons into dimeric topological units {L 2 Cu 2 Hal 4 }. These dimers through hydrogen bonding are linked into a three-dimensional framework. None of the available allylic groups of the N,N’-diallylthiomorpholinium cation are coordinated to the copper(I) ion. In our opinion, this feature of the discussed crystal structure of [(C 4 H 8 NS(C 3 H 5 ) 2 )Cu Hal 2 ] compounds is explained by the influence of competition between the sulfur atom and the C=C bond of the allyl group of the cation during complexation in solution and the redistribution of electron density in the crystal structure of solid compounds due to hydrogen contacts C–H… Hal . Keywords : N,N’-diallylthiomorpholinium; copper(І); s-complexes; crystal structure.