Rhombohedral unit cells

The a-rhombohedral form of boron has the simplest crystal stmcture with slightly deformed cubic close packing. At 1200°C a-rhombohedral boron degrades, and at 1500°C converts to P-rhombohedral boron, which is the most thermodynamically stable form. The unit cell has 104 boron atoms, a central B 2 icosahedron, and 12 pentagonal pyramids of boron atom directed outward. Twenty additional boron atoms complete a complex coordination (2). 

The thermodynamically most stable polymorph of boron is the /3-rhombohedral modification which has a much more complex structure with 105 B atoms in the unit cell (no 1014.5 pm, a 65.28°). The basic unit can be thought of as a central Bn icosahedron surrounded by an icosahedron of icosahedra this can be visualized as 12 of the B7 units in Fig. 6.1b arranged so that the apex atoms form the central Bn surrounded by 12 radially disposed pentagonal dishes to give the Bg4 unit shown in Fig. 6.3a. The 12 half-icosahedra are then completed by means of 2 complicated Bjo subunits per unit cell,... 

The structures of boron-rich borides (e.g. MB4, MBfi, MBio, MB12, MBe6) are even more effectively dominated by inter-B bonding, and the structures comprise three-dimensional networks of B atoms and clusters in which the metal atoms occupy specific voids or otherwise vacant sites. The structures are often exceedingly complicated (for the reasons given in Section 6.2.2) for example, the cubic unit cell of YB e has ao 2344 pm and contains 1584 B and 24 Y atoms the basic structural unit is the 13-icosahedron unit of 156 B atoms found in -rhombohedral B (p. 142) there are 8 such units (1248 B) in the unit cell and the remaining 336 B atoms are statistically distributed in channels formed by the packing of the 13-icosahedron units. 

The materials for solid solutions of transition elements in j3-rh boron are prepared by arc melting the component elements or by solid-state diffusion of the metal into /3-rhombohedral (/3-rh) boron. Compositions as determined by erystal structure and electron microprobe analyses together with the unit cell dimensions are given in Table 1. The volume of the unit cell (V ) increases when the solid solution is formed. As illustrated in Fig. 1, V increases nearly linearly with metal content for the solid solution of Cu in /3-rh boron. In addition to the elements listed in Table 1, the expansion of the unit cell exceeds 7.0 X 10 pm for saturated solid solutions " of Ti, V, (2o, Ni, As, Se and Hf in /3-rh boron, whereas the increase is smaller for the remaining elements. The solubility of these elements does not exceed a few tenths at %. The microhardness of the solid solution increases with V . Boron is a brittle material, indicating the accommodation of transition-element atoms in the -rh boron structure is associated with an increase in the cohesion energy of the solid. 

Two modifications are known for polonium. At room temperature a-polonium is stable it has a cubic-primitive structure, every atom having an exact octahedral coordination (Fig. 2.4, p. 7). This is a rather unusual structure, but it also occurs for phosphorus and antimony at high pressures. At 54 °C a-Po is converted to /3-Po. The phase transition involves a compression in the direction of one of the body diagonals of the cubic-primitive unit cell, and the result is a rhombohedral lattice. The bond angles are 98.2°. 

Boron is as unusual in its structures as it is in its chemical behavior. Sixteen boron modifications have been described, but most of them have not been well characterized. Many samples assumed to have consisted only of boron were possibly boron-rich borides (many of which are known, e.g. YB66). An established structure is that of rhombohedral a-B12 (the subscript number designates the number of atoms per unit cell). The crystal structures of three further forms are known, tetragonal -B50, rhombohedral J3-B105 and rhombohedral j3-B 320, but probably boron-rich borides were studied. a-B50 should be formulated B48X2. It consists of B12 icosahedra that are linked by tetrahedrally coordinated X atoms. These atoms are presumably C or N atoms (B, C and N can hardly be distinguished by X-ray diffraction). 

The spinel blocks in (3-alumina are related by mirror planes that mn through the conduction planes that is, the orientation of one block relative to another is derived by a rotation of 180°. A second form of this compound, called (3"-alumina, has similar spinel blocks. However, these are related to each other by a rotation of 120°, so that three spinel block layers are found in the unit cell, not two. The ideal composition of this phase is identical to that of (3-alumina, but the unit cell is now rhombohedral. Referred to a hexagonal unit cell, the lattice parameters are a = 0.614 nm, c = 3.385 nm. The thickness of the spinel blocks and the conduction planes is similar in both structures.3... 

The unique axis in the monoclinic unit cell is mosdy taken as the b axis. Rhombohedral unit cells are often specified in terms of a bigger hexagonal unit cell. 

The unit cell of corundum is rhombohedral, but the structure is usually described with respect to hexagonal axes. Each of the cations is surrounded by six oxygen ions in a slightly distorted octahedral coordination. The anions are close to a hexagonal close-packed array and the cations occupy two-thirds of the available octahedral positions in this array in an ordered fashion. The structure is also adopted by a-Fe203 and Q2O3. 

Cl 6c +(u,u,u +m, + m, + m + w, + w, +m) w= This structure has a rhombohedral symmetry but is usually described in terms of a triple-volume hexagonal cell, which makes comparison with the idealized Cdl2 structure simpler. The idealized unit cell is adequate for the purposes of this book. In this representation the anion layers are in cubic closest packing. .. ABC ABC ABC... The metal and nonmetal stacking sequence is... 

A crystal structure analysis proved SeF4-NbF5 to have the same unit-cell dimensions as SeF4-TaFs. The atomic arrangement in the rhombohedral crystals is shown in Fig. 2 and is consistent with the ionic formulation (SeF3)+(NbF6) , with, however, substantial fluorine... 

Figure 3.4. The crystal systems and the Bravais lattices illustrated by a unit cell of each. All the points which, within a unit cell, are equivalent to each other and to the cell origin are shown. Notice that, in the primitive lattices the unit cell edges are coincident with the smallest equivalence distances. For the rhombohedral lattice, described in terms of hexagonal axis, the symbol hR is used instead of a symbol such as rP. In the construction of the so-called Pearson symbol ( 3.6.3), oS and mS will be used instead of oC and mC.

Description of a rhombohedral unit cell in terms of the equivalent, triple-primitive, hexagonal cell (see Fig. 3.9). 

A detailed example of the alternative descriptions of a given compound, both in terms of its hexagonal unit cell and of the corresponding rhombohedral primitive cell is presented in Chapter 4 the rhombohedral compound Mo6PbSx (the prototype of the family of the so-called Chevrel phases) is described and unit cell constants and atomic positions are listed for its conventional hexagonal cell and for the rhombohedral primitive cell. 

Description of a cubic (primitive, body centred or face centred) unit cell (ac) in terms of the equivalent, primitive rhombohedral, (a,-, a) and triple-primitive hexagonal, cells (ah, ch). See Fig. 3.11. 

In this book, the Pearson symbol will be used throughout and the convention has been adopted indicating in every case the number (ideal or effective) of atoms contained in the chosen unit cell. In the case, therefore, of rhombohedral substances for which the data of the (triple primitive) hexagonal cell are generally reported, the number of atoms is given which is in the hexagonal cell and not the number of atoms in the equivalent rhombohedral cell (Ferro and Girgis 1990). So, for instance,... 

The nearly cubic, rhombohedral unit cell of Mo6PbS8 is shown in Fig. 4.30. The bonding between different clusters in the crystal structure of the Chevrel phase Mo6PbS8 is indicated in Fig. 4.31. 

Figure 4.31. Crystal structure of the Chevrel phase Mo6PbS8. Portions of four rhombohedral unit cells with one common Pb atom (black) are shown. The bonding between different clusters is suggested by the Mo—S inter-cluster links.

The identity of the polytype present in a given LDH sample may, in principle at least, be determined from the powder XRD pattern, although as we shall see for many LDHs this is not possible, as the amoimt of useful information therein is limited. By convention, the indexing of powder patterns for rhombohedral polytypes is based on a triple hexagonal unit cell (see Fig. 3). 

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