Ionic compounds crystal structure

The melting and boiling points of the aluminium halides, in contrast to the boron compounds, are irregular. It might reasonably be expected that aluminium, being a more metallic element than boron, would form an ionic fluoride and indeed the fact that it remains solid until 1564 K. when it sublimes, would tend to confirm this, although it should not be concluded that the fluoride is, therefore, wholly ionic. The crystal structure is such that each aluminium has a coordination number of six, being surrounded by six fluoride ions. 

Crystal Structure and Ionic Radii. Crystal structure data have provided the basis for the ionic radii (coordination number — C-N — 6). For both M3+ and M4 10ns there is an actinide contraction, analogous to the lanthanide contraction, with increasing positive charge on the nucleus. As a consequence of the ionic character of most actinide compounds and of the similarity of the ionic radii for a given oxidation state, analogous compounds are generally isostmctural. 

Usually an ionic compound crystallizes into a structure that permits optimum packing of the ions. With close packing, the distance between negative and positive ions is as short as possible, and this... 

For example, many ionic compounds crystallize from a water solution with water molecules incorporated into their crystal structure, forming a hydrate. Hydrates have a specific number of water molecules chemically bonded to each formula unit. A chemist may know the formula of the ionic part of the hydrate but not how many water molecules are present for each formula unit. 

J. J. W. Eshuis, Y. Y. Tan, A. Meetsma, and J. H. Teuben, Organometallics, 11, 362 (1992). Kinetic and Mechanistic Aspects of Propene Oligomerization with Ionic Organozirconium and -Hafnium Compounds Crystal Structures of [CpJMMe(THT)]"[BPh4] (M = Zr, Hf). 

X-ray structural studies have played a major role in transforming chemistry from a descriptive science at the beginning of the twentieth century to one in which the properties of novel compounds can be predicted on theoretical grounds. When W.L. Bragg solved the very first crystal structure, that of rock salt, NaCl, the results completely changed prevalent concepts of bonding forces in ionic compounds. 

Crystal structure, crystal defects and chemical reactions. Most chemical reactions of interest to materials scientists involve at least one reactant in the solid state examples inelude surfaee oxidation, internal oxidation, the photographie process, electrochemieal reaetions in the solid state. All of these are critieally dependent on crystal defects, point defects in particular, and the thermodynamics of these point defeets, especially in ionic compounds, are far more complex than they are in single-component metals. I have spaee only for a superficial overview. 

Oxygen and fluorine ions have very similar ionic radii. This steric similarity ensures relatively easy substitution of the oxygen in the compounds, by fluorine ions. Such substitution opens up huge possibilities for the synthesis of oxyfluoride compounds with desired crystal structure and properties. 

Since hydrofluoride synthesis is based on thermal treatment at relatively high temperatures, the possibility of obtaining certain fluorotantalates can be predicted according to thermal stability of the compounds. In the case of compounds whose crystal structure is made up of an octahedral complex of ions, the most important parameter is the anion-cation ratio. Therefore, it is very important to take in to account the ionic radius of the second cation in relation to the ionic radius of tantalum. Large cations, are not included in the... 

The radius of the second cation in known MuNbOFs, MU2Nb03F3 and Mul2Nb05F compounds containing bi- and trivalent metals, is usually similar to that of niobium s ionic radius. Such compounds cannot be considered as having an island-type structure and will be discussed later on. Only bismuth-containing compounds (Bi3+) display the presence of different cationic sublattices in their crystal structure. 

Other examples of compounds that are considered MeX3-type compounds are lithium hexafluorotantalate (-niobate), LiTaF6 and LiTaF6, which have crystal structures similar to A1F3. Both lithium and tantalum (niobium) cations have similar ionic radii and are located in the centers of octahedrons that are composed of fluorine anions. 

The formulated principals correlating crystal structure features with the X Nb(Ta) ratio do not take into account the impact of the second cation. Nevertheless, substitution of a second cation in compounds of similar types can change the character of the bonds within complex ions. Specifically, the decrease in the ionic radius of the second (outer-sphere) cation leads not only to a decrease in its coordination number but also to a decrease in the ionic bond component of the complex [277]. 

The crystal structures of Hf 2 (OH) 2 (S0O 3 (H2O) i, (14) and Ce2(0H)2(S0i,)3 (H20)it (14) also have been determined and found to be isomorphous to the zirconium compound. The cell constants for this series of four isomorphous compounds reflect the effect of the ionic radii on the dimensions of the unit cell. The values for these cell constants are in Table II. Thus, the cell constants for the zirconium and hafnium compounds are nearly identical and smaller than the cell constants for the cerium and plutonium compounds which are also nearly identical. This trend is exactly that followed by the ionic radii of these elements. 

The theoretical result is derived that ionic compounds MXS will crystallize with the fluorite structure if the radius ratio Rm/Rx is greater than 0.65, and with the rutile (or anatase) structure if it is less. This result is experimentally substantiated. 

Reactions of UCI4 with [Li RC(NCy)2 (THF)]2 (R = Me, Bu ) in THF gave the tris(amidinate) compounds [RC(NCy)2]3UCl that could be reduced with lithium powder in THF to the dark-green homoleptic uranium(lll) complexes [RC(NCy)2]3U. Comparison of the crystal structure of [MeC(NCy)2]3U with those of the lanthanide analog showed that the average U-N distance is shorter than expected from a purely ionic bonding model. ... 

The packing in ionic crystals requires that ions of opposite charges alternate with one another to maximize attractions among ions. A second important feature of ionic crystals is that the cations and anions usually are of different sizes. Usually the cations are smaller than the anions. Consequently, ionic compounds adopt a variety of structures that depend on the charges and sizes of the ions. One way to discuss ionic structures is to identify a crystal lattice for one set of ions, and then describe how the other ions pack within the lattice of the first set. 

Recognizing Cause and Effect In a crystal lattice structure, the electrons are held tightly by the ions, which are rigidly held in place by electrostatic attraction. Discuss how this characteristic explains why ionic compounds generally (a) have high melting points and (b) do not conduct electricity in the solid state. 

If two ionic compounds have the same structure type, but in such a way that the cationic positions of one compound are taken by the anions of the other and vice versa ( exchange of cations and anions ), then they sometimes are called antitypes . For example in Li20 the Li+ ions occupy the same positions as the F ions in CaF2, while the O2- ions take the same positions as the Ca2+ ions Li2Q crystallizes in the anti-CaF2 type . 

On the other hand, the crystal structures of ionic compounds with small molecular ions depend mainly on how space can be filled most efficiently by the ions, following the principle of cations around anions and anions around cations. Geometric factors such as the relative size of the ions and the shape of molecular ions are of prime importance. More details are given in Chapter 7. 

The structures of ionic compounds comprising complex ions can in many cases be derived from the structures of simple ionic compounds. A spherical ion is substituted by the complex ion and the crystal lattice is distorted in a manner adequate to account for the shape of this ion. 

---