Diffraction data, X-ray

Simply stated, the goal of data collection is to determine the indices and record the intensities of as many reflections as possible, as rapidly and efficiently as possible. One cause for urgency is that crystals, especially those of macromolecules, deteriorate in the beam because X rays generate heat and reactive free radicals in the crystal. Thus the crystallographer would like to capture as many reflections as possible during every moment of irradiation. Often the diffracting power of the crystal limits the number of available reflections. Protein crystals that produce measurable reflections from interplanar spacings down 

In the following sections, I will discuss briefly a few of the major instruments employed in data collection. These include the X-ray sources, which produce an intense, narrow beam of radiation detectors, which allow quantitative measurement of reflection intensities and cameras or diffractometers, which control the orientation of the crystal in the X-ray beam and thus direct reflections having known indices to detectors. 

A monochromatic (single-wavelength) source of X rays is desirable for crystallography because the diameter of the sphere of reflection is 1/X, and a source producing two distinct wavelengths of radiation gives two spheres of 

Whatever the source of X rays, the beam is directed through a collimator, a narrow metal tube that selects and reflects the X rays into parallel paths, producing a narrow beam. After collimation, beam diameter can be further 

X-ray sources pose some dangers that the crystallographer must consider in daily work. X-ray tubes require high-voltage power supplies containing large 

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Spackman M A 1992 Molecular electric moments from X-ray diffraction data Chem. Rev. 92 1769... 

Gavezzotti A and G Filippini 1996. Computer Prediction of Organic Crystal Structures Using Partial X-ray Diffraction Data, journal of the American Chemical Society 118 7153-7157. 

The monolayer resulting when amphiphilic molecules are introduced to the water—air interface was traditionally called a two-dimensional gas owing to what were the expected large distances between the molecules. However, it has become quite clear that amphiphiles self-organize at the air—water interface even at relatively low surface pressures (7—10). For example, x-ray diffraction data from a monolayer of heneicosanoic acid spread on a 0.5-mM CaCl2 solution at zero pressure (11) showed that once the barrier starts moving and compresses the molecules, the surface pressure, 7T, increases and the area per molecule, M, decreases. The surface pressure, ie, the force per unit length of the barrier (in N/m) is the difference between CJq, the surface tension of pure water, and O, that of the water covered with a monolayer. Where the total number of molecules and the total area that the monolayer occupies is known, the area per molecules can be calculated and a 7T-M isotherm constmcted. This isotherm (Fig. 2), which describes surface pressure as a function of the area per molecule (3,4), is rich in information on stabiUty of the monolayer at the water—air interface, the reorientation of molecules in the two-dimensional system, phase transitions, and conformational transformations. 

A = 100 pm 1 D = 3.336x 10 C m. X-Ray diffraction data are enclosed in parentheses. Data taken from <74PMH(6i53>, which see for references to the original literature. 

The normal mode refinement method is based on the idea of the normal mode important subspace. That is, there exists a subspace of considerably lower dimension than 3N, within which most of the fluctuation of the molecule undergoing the experiment occurs, and a number of the low frequency normal mode eigenvectors span this same subspace. In its application to X-ray diffraction data, it was developed by Kidera et al. [33] and Kidera and Go [47,48] and independently by Diamond [49]. Brueschweiler and Case [50] applied it to NMR data. 

The molecular orbital description of the bonding in NO is similar to that in N2 or CO (p. 927) but with an extra electron in one of the tt antibonding orbitals. This effectively reduces the bond order from 3 to 2.5 and accounts for the fact that the interatomic N 0 distance (115 pm) is intermediate between that in the triple-bonded NO+ (106 pm) and values typical of double-bonded NO species ( 120 pm). It also interprets the very low ionization energy of the molecule (9.25 eV, compared with 15.6 eV for N2, 14.0 eV for CO, and 12.1 eV for O2). Similarly, the notable reluctance of NO to dimerize can be related both to the geometrical distribution of the unpaired electron over the entire molecule and to the fact that dimerization to 0=N—N=0 leaves the total bond order unchanged (2 x 2.5 = 5). When NO condenses to a liquid, partial dimerization occurs, the cis-form being more stable than the trans-. The pure liquid is colourless, not blue as sometimes stated blue samples owe their colour to traces of the intensely coloured N2O3.6O ) Crystalline nitric oxide is also colourless (not blue) when pure, ° and X-ray diffraction data are best interpreted in terms of weak association into... 

X-ray diffraction data relating to the ditholium salt shown in (b) for M = 12. A and B correspond to the rectangular lattice vectors shown in D and a and b correspond to the N,-q to Dh and to D, phase transitions. Reproduced from reference 30 with permission. 

Table 16-3. Single-crystal X-ray diffraction data for OPVs. 

It is appropriate to emphasize again that mechanisms formulated on the basis of kinetic observations should, whenever possible, be supported by independent evidence, including, for example, (where appropriate) X-ray diffraction data (to recognize phases present and any topotactic relationships [1257]), reactivity studies of any possible (or postulated) intermediates, conductivity measurements (to determine the nature and mobilities of surface species and defects which may participate in reaction), influence on reaction rate of gaseous additives including products which may be adsorbed on active surfaces, microscopic examination (directions of interface advance, particle cracking, etc.), surface area determinations and any other relevant measurements. 

There has been considerable interest in the structure and properties of poly(tetra-methylene terephthalate) 4GT, stemming from the observation that when the oriented polymer is stretched, the crystalline regions are transformed from one structure to a new one30,3l). It appears from the X-ray diffraction data that in the structure... 

We have developed a new method of interpretation of the photographs which does not suffer from this disadvantage. This radial distribution method, which is closely related to the method of interpretation of x-ray diffraction data developed by Zemike and Prins3 for the study of the structure of liquids and applied by Warren and Gingrich4 to crystals, consists in the calculation (from... 

X-rays. This was followed by the mathematical solution of crystal structure from X-ray diffraction data in 1913 by Bragg. Since that, many applications of X-ray were foimd including structure determination of fine-grained materials, like soils and days, which had been previously thought to be amorphous. Since then, crystals structures of the day minerals were well studied (Ray and Okamoto, 2003). 

Otwinowski Z, Minor W. Processing of X-ray diffraction data collected in oscillation mode. Methods Enzymol 1997 276 307-26. 

Some virus particles have their protein subunits symmetrically packed in a helical array, forming hollow cylinders. The tobacco mosaic virus (TMV) is the classic example. X-ray diffraction data and electron micrographs have revealed that 16 subunits per turn of the helix project from a central axial hole that runs the length of the particle. The nucleic acid does not lie in this hole, but is embedded into ridges on the inside of each subunit and describes its own helix from one end of the particle to the other. 

Solvay subsequently published in vitro, in vivo, computational and X-ray diffraction data relating to this series of 3,4-diaryIpyrazolines [297]. In this... 

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