PREPARATION, CHARACTERIZATION AND CRYSTAL-STRUCTURE OF [NI(BPY)(3)][FE(CN)(5)(NO)]3H(2)O AND ONE-DIMENSIONAL CYANO-BRIDGE [NI(EN)(2)FE(CN)(5)(NO)]H2O

Two new double complexes [Ni(bpy)(3)][Fe(CN)(5)(NO)]3H(2)O (1) and [Ni (en)(2)Fe(CN)(5)(NO)]H2O (2) have been isolated from the reactions of the mixture of NiCl2 . 6H(2)O and Na-2[Fe(CN)(5)(NO)] in water, with b ipyridine (bpy) and ethylenediammine (en) in ethanol, respectively, an d have been characterized by X-ray analysis, IR, EPR, Mossbauer spectr oscopy and magnetic measurements. Crystallographic data for 1 and 2 ar e as follows: 1: triclinic, P (1) over bar, a=10.752(4), b=13.321(3), c=13.791(5) Angstrom, alpha=79.834(25), beta=81.39(3), gamma=72.93(3)d egrees, Z=2; 2: triclinic, P (1) over bar, a=8.622(16), b=8.832(3), c= 12.417(3) Angstrom, alpha=94.81(3), beta=92.322(19), gamma=112.820(23) degrees, Z=2. The bond angles of Fe-N-O are nearly linear for 1 (178.3 (4)degrees) and 2 (179.4(3)degrees). The structure of 1 consists of a double complex of a cation [Ni(bpy)(3)](2+) and an anion [Fe(CN)(5)(NO )](2-). The structure of 2 consists of a one-dimensional polymeric cha in -Ni(en)(2)-NC-Fe(CN)(3)(NO)-CN-Ni(en)(2)- in which the Ni(II) and F e(II) centers are linked by two CN groups. Cryomagnetic investigations (4-300 K) reveal a paramagnetic behavior for 1 and the presence of a one-dimensional Heisenberg weak antiferromagnetic chain with J=-0.47 c m(-1) for 2. EPR spectra observed at ambient temperature for the Ni(II ) ions in both complexes are also reported.