Face octahedra

One atom above the face of an octahedron, which is distorted chiefly by separating the atoms at the corners of this face. 0.592... 

Complex carbides are very numerous. Many newer compounds of this class have been discovered and their stmctures elucidated (20). The octahedron M C is typical where the metals arrange around a central carbon atom. The octahedra may be coimected via corners, edges, or faces. Trigonal prismatic polyhedra also occur. Defining T as transition metal and M as metal or main group nonmetal, the complex carbides can be classified as (/)... 

A similar type of isomerism occurs for [Ma3b3] octahedral complexes since each trio of donor atoms can occupy either adjacent positions at the comers of an octahedral face (/hcial) or positions around the meridian of the octahedron (meridional). (Fig. 19.12.) Geometrical isomers differ in a variety of physical properties, amongst which dipole moment and visible/ultraviolet spectra are often diagnostically important. 

The lowest coordination number of tantalum or niobium permitted by crystal chemistry formalism is 6, which corresponds to an octahedral configuration. X Me ratios that equal 3, 2 or 1 can, therefore, be obtained by corresponding substitutions in the cationic sub-lattice. A condition for such substitution is no doubt steric similarity between the second cation and the tantalum or niobium ion so as to enable its replacement in the octahedral polyhedron. In such cases, the structure of the compound consists of oxyfluoride octahedrons that are linked by their vertexes, sides or faces, according to the compound type, MeX3, MeX2 or MeX respectively. Table 37 lists compounds that have a coordination-type structure [259-261]. 

In order to construct an MeX-type compound (X Me = 1) using only octahedral elements, the octahedrons must be linked via their faces i.e. by sharing of three angles. This arrangement of the octahedral polyhedrons yields a rock-salt type structure (NaCl type structure). 

Thallium phthalocyanine (PcT12) can be obtained by heating phthalonitrile with an inter-metallic alloy of indium and thallium in an evacuated glass ampule.145 The structure of this compound is unique among metal phthalocyanines as the two thallium cations occupy two opposite corners of an octahedron, which is formed by the thallium cations and the four iso-indolinc nitrogen atoms facing the center of the macrocycle.147 Another unusual type of phthalocyanine can be prepared by heating phthalonitrile with thallium metal.148 It was identified as a bicyclic thallium(III) phthalocyanine (Pc3/2T1).14S... 

The Niccolite Structure. The substances which crystallize with the niccolite structure (B8) are compounds of transition elements with S, Se, Te, As, Sb, Bi, or Sn. The physical properties of the substances indicate that the crystals are not ionic, and this is substantiated by the lack of agreement with the structural rules for ionic crystals. Thus each metal atom is surrounded by an octahedron of non-metal atoms but these octahedra share faces, and the edges of the shared faces are longer than other edges (rather than shorter, as in ionic crystals). Hence we conclude that the bonds are covalent, with probably some metallic character also. 

AuSn has the nickel arsenide structure, B8, with abnormally small axial ratio (c/a = 1.278, instead of the normal value 1.633). Each tin atom is surrounded by six gold atoms, at the corners of a trigonal prism, with Au-Sn = 2.847 A. and each gold atom is surrounded by six tin atoms, at the corners of a flattened octahedron, and two gold atoms, at 2.756 A., in the opposed directions through the centers of the two large faces of the octahedron. 

The coordination theory, which has been applied successfully2 to brook-ite, the orthorhombic form of titanium dioxide, is based on the assumption that the anions in a crystal are constrained to assume positions about the cations such that they indicate the corners of polyhedra of which the cations mark the centers. These polyhedra are the fundamentally important constituents of the crystal retaining their form essentially, they are combined by sharing corners, edges, and faces in such a way as to build up a crystal with the correct stoichiometrical composition. Thus in rutile, anatase, and brookite there occur octahedra of oxygen ions about titanium ions in rutile each octahedron shares two edges with adjoining octahedra, in anatase four, and in brookite three. 

Particles of face centered cubic (FCC) crystal would be exclusively terminated by (100) surfaces, whereas cubo-octahedron-type particles may have a dominance of the more stable (111) surfaces. 

Solid-state cluster chemistry is dominated by octahedral (M 5L8)L6 and (MsLi2)L units which are the focus of this paper. These two cluster types are different in the way the metal octahedral core is surrounded by the ligands. In (MsLg)L6-type clusters (Fig. 6.1a), typical for molybdenum and rhenium halides, chalcogenides, and chalcohalides, eight innei hgands (L ) cap the octahedron faces and six outer ligands (L ) are located in the apical positions [9]. For metals with a smaller number of valence electrons, the (M6L i2)L -type clusters... 

The Lewis stmeture of SFg, shown in Figure 9-24a. indicates that sulfur has six S—F bonds and no lone pairs. The molecular geometry that keeps the six fluorine atoms as far apart as possible is octahedral in shape, as Figure 9-24Z) shows. Figure 9-24c shows that an octahedron has eight triangular faces. 

Views of sulfur hexafluoride (a) Lewis stmeture (b) ball-and-stick model (c) ball-and-stick model showing the triangular faces of the octahedron. 

The three like ligands lie in a plane that forms one face of the octahedron, shown in outline in the drawing. This is... 

Fig. 6.1 The fundamental structural unit found in the Chevrel phases (cluster MoeXg full circles Mo atoms) displayed in three ways to emphasize different views of the connectivity. In (a) an octahedron of molybdenums (Mo-Mo = 2.7 A) is encased in a cube of chalcogens (Mo-S 2.45 or Mo-Se 2.6 A). Scheme (b) exhibits the same cluster as consisting of an octahedron with its triangular faces capped by chalcogenides. In (c), the cluster has been reoriented so that a threefold axis is vertical. (Reproduced from [10])...

---