COPPER(I) CARBONYL AND COPPER(II) ACETATO COMPLEXES WITH 2,2'-DIPYRIDYLAMINE AND HALIDE ANIONS - CRYSTAL AND MOLECULAR-STRUCTURES OF CARBONYLCHLORO(2,2'-DIPYRIDYLAMINE)COPPER(I) AND ACETATOCHLORO(2,2'-DIPYRIDYLAMINE)COPPER(II)

Series of [Cu(I)dipyam(CO)X], [Cu(II)dipyam(CH3CO2)X] and [Cu-II(dipya m)(2)(CH3CO2)]X complexes (dipyam = 2,2'-dipyridylamine; X = Cl-, Br-, I-) were synthesized and the structures of the title compounds were d etermined by X-ray diffraction methods. Crystallographic details for c omplexes [Cu(II)dipyam(CO)CL] (1) and [Cu(II)dipyam(CH3CO2)Cl] (2) are as follows: complex 1, triclinic, space group <P(1)over bar> with a = 9.944(3), b = 9.450(3), c = 7.053(3) Angstrom, alpha = 69.50(2), beta = 91.81(2), gamma = 76.33(2)degrees, Z = 2; complex 2, triclinic, spa ce group <P(1)over bar> with a = 10.093(3), b = 9.098(3), c = 7.444(2) Angstrom, alpha = 106.24(2), beta = 96.91(2), gamma = 78.87(2)degrees , Z = 2. The dry carbonyl complexes are thermostable at 100 degrees C or more, but their formation was reversible in solution even at room t emperature. Thermal and chemical stabilities increase from the chloro to the iodo species. Among the acetato derivatives the chloro and brom o mono-dipyam complexes were easily formed, while the iodide gave pref erentially the bis-dipyam complex. Each series of the complexes gave v ery similar IR spectra in the range 3800-250 cm(-1). For the carbonyl derivatives the patterns of the far-IR 250-60 cm(-1) regions were show n and the v(Cu-X) frequencies assigned.