Abstract: | Isomorphous triclinic forms of dichlorophthalocyaninato(2?)]tin(IV), Sn(C32H16N8)Cl2], and dichlorophthalocyaninato(2?)]germanium(IV), Sn(C32H16N8)Cl2], and a monoclinic form of the latter have been obtained from the reaction of pure tin and germanium powder, respectively, with phthalonitrile under a stream of ICl vapour. All three crystal structures consist of centrosymmetric SnPcCl2] and GePcCl2] Pc is phthalocyaninate(2?)] molecules, which are separated but interacting. In the triclinic forms (Sn and Ge), the Pc macrocycles are not staggered but slipped, and in the monoclinic form (Ge), the molecules are additionally inclined. In both cases, the central Sn or Ge atom is six‐coordinated by the four isoindole N atoms of the Pc macrocyclic ligand and by two Cl atoms (located trans) into a tetragonal–bipyramidal structure. The arrangement of SnPcCl2] and GePcCl2] molecules in the crystal structure is determined mainly by intermolecular C—H?Cl, π–π and van der Waals interactions. |