CATIONIC RUTHENIUM AND OSMIUM SYSTEMS V. CATIONIC OSMIUM(II) HYDRAZINE AND HYDRAZONE COMPLEXES DERIVED FROM THE POLYMER x (COD =CYCLO-OCTA-1,5-DIENE; x>/=2). THE CRYSTAL STRUCTURE OF t)2(NH2N:CMe2)2>2*(ACETONE)2

Article abstract of DOI:10.1016/0022-328X(85)87041-8

The polymer _x (1; COD=cycloocta-1,5-diene; x>/=2) and the appropiate hydrazine have been used to prepare the salts 2 (3) and PF6 (4).Treatment of 3 with t-butyl isocyanide produced mer-t)3(N2H4)3>2 (5) and trans-t)4(N2H4)2>2 (6) from refluxing ethanol and the hydrazone complex t)2(NH2N:CMe2)2>2 (7) from refluxing acetone.Reactions of 3 and L in acetone gave trans-2 (8).The crystal structure of t)2(NH2N:CMe2)2>2*(Acetone)2 (7) has been determined from three-dimensional X-ray counter data and refined to a final R (on F) of 0.090 based on 3014 reflections.The compound crystallizes in the monoclinic space group C2/c with four formula units in a cell of dimensions a 24.60(2), b 13.31(1), c 24.12(2) Angstroem and β 111.51(2) deg.The cation has a crystallographically imposed C² symmetry, with octahedral coordination of the osmium atom, assuming that the COD ligand occupies two adjacent coordination sites.Coordination of the mutually trans hydrazone ligands to the osmium atom is through the amino-N atoms rather than through the less basic, more sterically hindered, imino-N atoms.Revelant bond distances are: Os-N 2.19(2)(mean, Os-C(COD) 2.19(2) and 2.29(2), and Os-C(isocyanide) 1.93(2) (mean) Angstroem.