The reaction of ethanolic solutions of CuX 2 (X=NO 3 - , ClO 4 - ), with bidentate amine, 2,2'-bipyridyl (bipy) and ammonium thiocyanate, leads to the high-yield formation of {catena-[Cu(bipy)(μ N , S -NCS) 2 ]} (1) and [Cu(NCS)(bipy) 2 ]ClO 4 . 1/2CH 3 CN (2). The crystal structure of 1 and 2 were determined. Complex 1 crystallises in the monoclinic system, space group C2/c with a=8.125(4) 9, b=15.557(6) 9, c=10.536(3) 9, β=95.32(3) o and Z=4. The crystal structure consists of neutral Cu(NCS) 2 (bipy) units which are bridged by sulfur atoms of the thiocyanate groups to yield a 1D chain. Complex 2 crystallises in the monoclinic system, space group C2/c with a=12.694(4) 9, b=25.007(11) 9, c=15.479(11) 9, β=106.85(4) o and Z=8. The crystal structure consists of a [Cu(NCS)(bipy) 2 ] + cation, ClO 4 - anion and CH 3 CN. The cations show a quasi-trigonal bipyramidal coordination. A variable temperature magnetic susceptibility study was performed on 1 at a temperature range of 2-300 K. The compound shows a very weak antiferromagnetic coupling (J=-0.13 cm - 1 ) and the magnetic susceptibility data were analysed by the expression for the magnetic susceptibility of isotropically coupled S=1/2 ions in antiferromagnetic chains. The single crystal EPR spectra of 2 presents rhombic g values and the direction of the highest g value lies in the equatorial plane near the Cu-N e q direction; therefore, this is a distorted trigonal bipyramidal structure.