8- 2, space group

In all of these stmctures the atomic positions are fixed by the space group syimnetry and it is only necessary to detennine which of a small set of choices of positions best fits the data. According to the theory of space groups, all stmctures composed of identical unit cells repeated hi three dimensions must confomi to one of 230 groups tliat are fomied by coinbinmg one of 14 distinct Bmvais lattices with other syimnetry operations. 

These include rotation axes of orders two, tliree, four and six and mirror planes. They also include screM/ axes, in which a rotation operation is combined witii a translation parallel to the rotation axis in such a way that repeated application becomes a translation of the lattice, and glide planes, where a mirror reflection is combined with a translation parallel to the plane of half of a lattice translation. Each space group has a general position in which the tln-ee position coordinates, x, y and z, are independent, and most also have special positions, in which one or more coordinates are either fixed or constrained to be linear fimctions of other coordinates. The properties of the space groups are tabulated in the International Tables for Crystallography vol A [21]. 

If the space group contains screw axes or glide planes, the Patterson fiinction can be particularly revealing. Suppose, for example, that parallel to the c axis of the crystal there is a 2 screw axis, one that combines a 180° rotation with... 

All tenus in the sum vanish if / is odd, so (00/) reflections will be observed only if / is even. Similar restrictions apply to classes of reflections with two indices equal to zero for other types of screw axis and to classes with one index equal to zero for glide planes. These systematic absences, which are tabulated m the International Tables for Crystallography vol A, may be used to identify the space group, or at least limit die... 

The two exponential tenns are complex conjugates of one another, so that all structure amplitudes must be real and their phases can therefore be only zero or n. (Nearly 40% of all known structures belong to monoclinic space group Pl c. The systematic absences of (OlcO) reflections when A is odd and of (liOl) reflections when / is odd identify this space group and show tiiat it is centrosyimnetric.) Even in the absence of a definitive set of systematic absences it is still possible to infer the (probable) presence of a centre of synnnetry. A J C Wilson [21] first observed that the probability distribution of the magnitudes of the structure amplitudes would be different if the amplitudes were constrained to be real from that if they could be complex. Wilson and co-workers established a procedure by which the frequencies of suitably scaled values of F could be compared with the tlieoretical distributions for centrosymmetric and noncentrosymmetric structures. (Note that Wilson named the statistical distributions centric and acentric. These were not intended to be synonyms for centrosyimnetric and noncentrosynnnetric, but they have come to be used that way.)... 

It is often difficult to represent inorganic compounds with the usual structure models because these structures are based on complex crystals space groups), aggregates, or metal lattices. Therefore, these compounds are represented by individual polyhedral coordination of the ligands such as the octahedron or tetrahedron Figure 2-124d). 

Periodic boundary conditions can also be used to simulate solid state con dition s although TlyperChem has few specific tools to assist in setting up specific crystal symmetry space groups. The group operation s In vert, Reflect, and Rotate can, however, be used to set up a unit cell manually, provided it is rectangular. 

Energy minimisation and normal mode analysis have an important role to play in the study of the solid state. Algorithms similar to those discussed above are employed but an extra feature of such systems, at least when they form a perfect lattice, is that it is can be possible to exploit the space group symmetry of the lattice to speed up the calculations. It is also important to properly take the interactions with atoms in neighbouring cells into account. 

Compoun d Color Melting point, °C Symmetry Space group or stmcture type nm Q, i Q, nm Angle, deg nm Density. g/mL... 

CAS Registry Number mol wt crystal system space group lattice constants, nm... 

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