pi-complexes of copper(I) ionic salts: Synthesis and crystal structure of (4-allylthiosemicarbazide) (sulfamato)copper(I) and bis(4-allylthiosemicarbazide) (sulfato-O)dicopper(I)

Single crystals of [Cu(ATSC)]NH2SO3, (1) (ATSC 4-allylthiosemicarbazide) we re obtained by electrochemical synthesis using alternating current. Compoun d (1) crystallizes in P2(1)2(1)2(1) sp. gr., a=6.8284(2), b=9.3054(3), c= 1 6.1576(11) Angstrom, Z = 4. ATSC moiety acts as tetradentate ligand, chelat ing two symmetrically related copper atoms. The Cu atom possesses trigonal pyramidal coordination, formed by two sulphur atoms tone of them at the api cal position), nitrogen atom and C=C bond. Sulfamate anion is associated vi a hydrogen bonds. By slow hydrolysis of 1 crystals of [Cu-2(ATSC)(2)]SO4 (2 ) were obtained: P (1) over bar sp, gr., a = 9.526(2), b = 12.687(2), c = 1 4.7340(10) Angstrom, alpha = 95.119(10), beta = 89.903(12), gamma = 109.113 (14)degrees, Z = 4. The asymmetric unit of 2 contains two formula units, wh ich are related by pseudosymmetry via a glide plane a. One half of four ATS C molecules act as in 1, the rest as tridentate ligands, which coordinate t he two copper atoms in apical positions with sulfate anions. This Cu-S coor dination was to date unknown. The structure of the ATSC ligands contributes to the unexpected competitiveness of C=bond in the coordination sphere of Cu-I inspite of strong donor atoms.