Abstract: | Crystals of the novel title arsenic(III) phthalocyanine complex, [As(C32H16N8)]2[As4I14] or [(AsPc)+]2·[As4I14]2−, where Pc is phthalocyaninate(2−), have been obtained by the reaction of pure powdered As with phthalonitrile under a stream of iodine vapour at 493 K. The crystals are built up of separate but interacting [AsPc]+ cations and [As4I12]2− anions. The As atom of the [AsPc]+ unit is bonded to the four isoindole N atoms of the Pc macrocycle and lies 0.743 (2) Å out of the plane defined by these four N atoms. The anionic part of the complex consists of AsI3 and [AsI4]− units joined together into an [As4I14]2− anion. The arrangement of the oppositely charged moieties, [AsPc]+ and [As4I14]2−, in the crystal is determined mainly by ionic attraction and by donor–acceptor interactions between the [AsPc]+ and [As4I14]2− ions. |