INTERACTION OF 7-TETRACYANO-3,5-DIHYDRO-3,5-DIIMINOPYRROLIZINIDE) METAL-COMPLEXES WITH PHENAZINE AND DERIVATIVES - CRYSTAL-STRUCTURES OF ADDITION-COMPOUNDS OF THE NICKEL(II) COMPLEX WITH PHENAZINE AND 5,10-DIMETHYL-5,10-DIHYDROPHENAZINE

The charge-transfer compounds of the electron-acceptor moiety [NiL2] ( L = 7-tetracyano-3,5-dihydro-3,5-diiminopyrrolizinide) and the electro n-donating phenazine derivatives [phenazine (phz), 5,10-dimethyl-5,10- dihydrophenazine (dmphz) and N-methylphenazinium cation (mphz+)] have been synthesized and characterized. The X-ray crystal structures of [N iL2].2phz.2MeCN 1a and [NiL2].dmphz.2MeCN 1b have been determined. Bot h compounds are monoclinic, mixed-stacked compounds, with planar accep tor and donor moieties alternating along the c axis [1 a: space group P2(1)/n, a = 14.687(l), b = 21.364(2), c = 7.8208(6) angstrom, beta = 110.958(6)-degrees, Z = 2; 1b: space group P2(1)/c, a = 12.975(5), b = 19.838(7), c = 7.651(3) angstrom, beta = 106.05(2)-degrees, Z = 2]. W hile 1a, as expected, does not show any solid-state collective propert y, 1b is a semiconductor (single crystal p = 3.6 x 10(3) OMEGA cm at r oom temperature; E(a) = 0.28 eV); its degree of ionicity gradually inc reases, on lowering the temperature, from zero to a small amount corre sponding to an effective magnetic moment (mu(eff)) = of 0.28 mu(B) per molecular formula. The cobalt derivative [CoL2].dmphz.2MeCN has also been synthesized and characterized, which is isomorphous and isostruct ural with the nickel analogue, and qualitatively behaves likewise (sin gle crystal p = 4.2 x 10(5) OMEGA cm at room temperature; E(a) = 0.26 eV); its magnetic measurements show a high-spin metal configuration (S = 3/2, mu(eff) = 4.13 mu(B)). The N-methylphenazinium (mphz+) derivat ive, isolated as [NiL2].-.mphz+-2MeOH, is assumed to be a mixed-stacke d radical anion salt from magnetic (mu(eff) = 1.72 mu(B)) and electric al (powder rho = 5.5 x 10(6) OMEGA cm at room temperature, E(a) = 0.43 eV) measurements.