Crystals of the novel title arsenic(III)-phthalocyanine complex, [As(C32H16N8)]2[As2I8] or [AsPc]2[As2I8], where Pc is the phthalocyaninate(2-) macrocycle, have been obtained from the reaction of pure powdered arsenic with phthalonitrile under oxidizing conditions (iodine vapour) at 463 K. The crystals are formed by separate but interacting [AsPc]+ cations and centrosymmetric [As2I8]2- anions. The As atom of the [AsPc]+ ion is bonded to the four isoindole N atoms of the Pc macrocycle and lies 0.762 (1) A out of their plane. The anionic part of the complex consists of two [AsI4]- units joined together into a centrosymmetric [As2I8]2- counter-ion. The arrangement of oppositely charged moieties, viz. [AsPc]+ and [As2I8]2-, in the crystal structure is determined mainly by their ionic attractions and by pi-pi interactions between the aromatic phthalocyaninate(2-) macrocycles.
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