Synthesis and crystal structure of the Copper(I) chloride pi-complex with diallyl sulfide, 2CuCl center dot(C3H5)(2)S

The crystals of the 2CuCl . (C3H5)(2)S pi-complex were prepared by ac elect rochemical synthesis and studied by X-ray diffraction analysis (a single-cr ystal DARCh automated diffractometer, MoKalpha radiation, 2 theta(max) = 42 degrees). The compound crystallizes in the monoclinic system, space group P2(1), a = 14.048(9), b = 9.576(4), c = 7.440(4) Angstrom, alpha = 102.16(4 )degrees, rho(calcd) = 2.119(4) g/cm(3), Z = 2 for the composition 2CuCl . (C3H5)(2)S. The copper and chlorine atoms form eight-membered cyclic Cu4Cl4 fragments that, due to the bridging function of one of the diallyl sulfide (DAS) molecules, are associated into infinite double helices along the 2(1 ) axis. The distorted tetrahedral environments of the Cu(1), Cu(2), and Cu( 3) atoms differ in composition (2Cl + 2S, 3Cl + S, and 2Cl + S + C=C, respe ctively), while the Cu(4) atom has the trigonal environment (2Cl + C=C). In both DAS molecules, the S atom functions as bridge relative to Cu(I). Howe ver, only one ligand molecule is coordinated to the metal atom through the C=C bonds of both allyl groups. The structure of the compound differs subst antially from the structure of the previously studied pi-complex 5CuBr . 2D AS.