The reaction of hydrazine with copper (II) chloride in acidic aqueous solution has been shown to produce at least four distinct complexes. Hydrazine behaves as a reducing agent, leading to the white, diamagnetic copper (I) complex (N2H4)CuCl and the black paramagnetic mixed-valence tricopper(2I,II) complex (N2H5)2Cu3Cl6. Blue and green copper (II) complexes (N2H5)2CuCl,42H2O and (N2H5)CuCl3 are also formed. Infrared spectra establish the presence of coordinated hydrazinium ions in the blue, green, and black compounds. Structures are proposed for all of these materials on the basis of spectroscopic and magnetic measurements. Significant exchange interactions are present in the chloride-bridged linear-chain complex (N2H5)CuCl3. The structure of the complex (N2H5)CuCl3 has been determined from single-crystal X-ray counter data. The complex crystallizes in the orthorhombic space group Pnma with four molecules in a cell of dimensions a=14.439 (2), b=5.705 (1), and c=6.859 (1) υ. The structure has been refined by full-matrix least-squares techniques to a conventional R factor (oil F) of 0.042 using 538 independent observations. The entire formula unit (with the exception of some of the hydrogen atoms) is constrained to lie on a mirror plane. The structure consists of infinite chains of dichloro-bridged dimers, in which one chloride ligand serves to propagate the chain in both directions while the other two chloride ligands do not. Thus, one chloride ligand is coordinated to three copper atoms with an in-plane distance of 2.297 (1) υ and two out-of-plane separations of 2.8560 (5) υ, while the other two chloride ligands are each coordinated to only a single copper center with bond lengths of 2.280 (1) and 2.298 (2) υ. The Cu-Cu' separation and the bridging Cu-Cl-Cu' angle in the chain are 3.751 (1) υ and 92.79 (3)°, respectively. © 1979, American Chemical Society. All rights reserved.
