Syntheses and properties of cis-diacidophthalocyaninato (2-)thallates(III); Crystal structure of tetra(n-butyl)ammonium cis-dinitrito(O,O ')- and cis-dichlorophthalocyaninato (2-) thallate (III)

Blue green cis-diacidophthalocyaninato(2-)thallate(III), (cis)[Tl(X)(2)pc(2 -)](-) (X = Cl, ONO', NCO) is prepared from iodophthalocyaninato(2-)thalliu m(III) and the corresponding tetra(n-butyl)ammonium salt, ((Bu4N)-Bu-n)X in dichloromethane, and isolated as ((Bu4N)-Bu-n)(cis)[Tl(X)(2)pc(2-)]. ((Bu4 N)-Bu-n)(cis)[Tl(ONO')(2)pc(2-)] (1) and ((Bu4N)-Bu-n)(cis)[Tl(X)(2)pc(2-)] 0,5(C2H5)(2)O (2) crystallize in the monoclinic space group P2(l)/n with c ell parameters for 1: a = 14.496(2) Angstrom, b = 17.293(5) Angstrom, c = 1 8.293(2) Angstrom, beta = 98.76(1)degrees resp. for 2: a = 13.146(1) Angstr om, b = 14.204(5) Angstrom, c = 24.900(3) Angstrom, beta = 93.88(1)degrees; Z = 4. In 1, the octa-coordinated Tl atom is surrounded by four isoindole- N atoms (N-iso) and four O atoms of the bidental nitrito(O,O') ligands in a distorted antiprism. The Tl-N-iso distances vary between 2.257(3) and 2.31 2(3) Angstrom, the Tl-O distances between 2.408(3) and 2.562(3) Angstrom. I n 2, the hexa-coordinated Tl atom ligates four N-iso atoms and two Cl atoms in a typical cis-arrangement. The average Tl-N-iso distance is 2.276 Angst rom, the average Tl-Cl distance is 2.550 Angstrom. In 1 and 2, the Tl atom is directed out of the centre of the (N-iso)(4) plane (Ct(N)) towards the a cido ligands (d(Tl-Ct(N)) = 1.144(1) Angstrom in 1, 1.116(2) Angstrom in 2) , and the phthalocyaninato ligand is concavely distorted. The vertical disp lacements of the periphereal C atoms amounts up to 0.82 Angstrom. The optic al and vibrational spectra as well as the electrochemical properties are di scussed.