%0 Journal Article %A Dance, IG %T The Prototype centro-Cl-tetrahedro-Zn4-icosahedro-(µ-SPh)12-tetrahedro-(ZnSPh)4 Molecular Structure, and Topological Analysis of Surface Ligand Packing for an Ensemble of High Symmetry M8(µ-SR)12 Aggregates and Derivatives %J Australian Journal of Chemistry %D 1985/09/01 %V 38 %N 9 %P 1391-1411 %K %R https://doi.org/10.1071/CH9851391 %U https://www.publish.csiro.au/paper/CH9851391 %X The aggregate [ClZn8( SPh )16]- (1) has been characterized by diffraction analysis of crystals obtained as the minor product from a mixture of Zn(NO3)2, PhSH , Et3N and Me4NCl in methanol. The new and prototypical structure of (1) contains a bitetrahedron (tetracapped tetrahedron) of zinc atoms, centred by the monatomic ligand and bridged on the twelve edges by thiolate ligands , and with four terminal thiolate ligands. All metal atoms are tetrahedrally coordinated. In terms of expanding concentric regular polyhedra (1) is centro-Cl-tetrahedro-Zn4-icosahedro -(μ- SPh )12-tetrahedro-Zn4-tetrahedro-( SPh )4, introducing the structural principle of aggregation in which metal atoms are inside and outside a regular polyhedron of bridging ligands. The cage framework and the substituents of the bridging ligands virtually adhere to the symmetry of the rare point group T: the packing of obliquely inclined ligand substituents over the surface of the aggregate is responsible for this unusually high symmetry configuration. Alternative aggregate stereochemistries bitetrahedro-M8-cuboctahedro-(μ-SR)12, hexahedro-M8- icosahedro (μ-SR)12, and hexahedro-M8-cuboctahedro-(μ-SR)12, structurally plausible and accessible to (1) without bond breaking or angular strain, are analysed topologically. Again high symmetry is required in the array of substituents from bridging ligands . It is shown that in these aggregates based on a (μ-SR)12M8 framework, the polyhedron formed by the twelve a-carbon atoms of substituents and the S12 polyhedron manifest an icosahedron/cuboctahedron complementarity. Crystal data: orthorhombic P bcn, a 23.493(3), b 29.726(4), c 17.835(2), Z = 8×[Cl0.5Zn4(SC6H5)8- + uncertain cation], 2715 observed data, Cu Kα, R = 0.12. Identification of the central ion of (1) as Cl - rather than the possible alternative s2- is not definite.