Crystals of a novel antimony(III)-phthalocyanine complex, [Sb(C(32)H(16)N(8))](4)[Sb(6)I(22)] or [SbPc](4)[Sb(6)I(22)], where Pc is the phthalocyaninate(2-) macrocycle, have been obtained from the reaction of pure powdered antimony with phthalonitrile under oxidation conditions of iodine vapour at 533 K. The crystal structure is built up from separate but interacting [SbPc](+) cations and [Sb(6)I(22)](4-) anions. Each Sb atom of the two independent [SbPc](+) cations is bonded to the four isoindole N atoms of the Pc macrocycle and lies 0.986 (1) A out of the plane defined by these N atoms. The anion consists of six distorted SbI(6) octahedra linked via bridging I atoms into a centrosymmetric [Sb(6)I(22)](4-) anion. The arrangement of the oppositely charged species, viz. [SbPc](+) and [Sb(6)I(22)](4-), in the crystal structure is determined mainly by the ionic attractions between the ions, forming a centrosymmetric [(SbPc)(4)(Sb(6)I(22))] unit. Neighbouring [(SbPc)(4)(Sb(6)I(22))] units related by translation interact via pi-pi interactions between the aromatic macrocycles in a back-to-back fashion.