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APTER 2
Chapter 2
X-ray Crystallography
2.1 Single crystal X-ray diffraction
2.1.1 Historical background and modern crystallography
Many scientists throughout history have pondered the mysteries of snow crystals what
they are, where they come from and why they are shaped the way they are. In 1611
Johannes Kepler published a short treatise on the Six-Cornered snowflake, which was
the first scientific reference to snow crystals. Kepler pondered the question of why
snow crystals always exhibit a six-fold symmetry [1]. Although he doesn't refer to the
atomistic view point, Kepler does speculate that the hexagonal close-packing of
spheres may have something to do with the morphology of snow crystals. He noted
that the closest packing arrangement of equal-sized balls in two dimensions is
hexagonal. He felt this model must be related in some way to the shape of the
snowflake, but was not able to account for the dendritic (multi branched) appearance
of most snowflakes. In 1665 Robert Hooke [2] published a large volume entitled
Micrographia, containing sketches of practically everything Hooke could view with
the latest invention of the day, the microscope. Included in this volume are many
snow crystal drawings, which for the first time revealed the complexity and intricate
symmetry of snow crystal structure. Philosopher and mathematician René Descartes
was the first to pen a reasonably accurate description of snow crystal morphologies,
about as well as can be done with the naked eye. These careful notes included obser-
vations of capped columns and 12-sided snowflakes, both rather rare forms [3].
Already in 1669 Niels Stensen proved the constancy of interplanar angles in quartz
crystals. Still it took more than a century before it was recognized that this property
holds for all crystal species and not just for quartz crystals. It was Jean Baptiste Louis
de Romé de l’Isle (1736-1790) who generalized this fundamental law of
crystallography that is presently known as "Steno's law" [4]. Actually this property
was incidentally discovered by de l'Isle's assistant, Arnould Carrangeot, in the course
17 2.1 X-ray Crystallography
of making terra cotta models of the crystals in de l'Isle's collection. For this purpose
in 1780 he developed a simple instrument to measure the angles between crystal
faces. The instrument that became known under the names of "Application
Goniometer" or "Contact Goniometer" was nothing more than two limbs connected
by a joint. The limbs could be applied to two adjacent crystal faces and eventually the
angle between the limbs could be measured. The accuracy of the contact Goniometer
was about 15 at best [5].
This chapter will describe the basic theory of X-ray diffraction by crystals, the
instrument used, data reduction along with the various corrections to be applied. It
also gives information used to determine the phases of the structure factors. In
addition it also gives information regarding the procedures and software used for the
analysis of diffraction data and structure determination.
2.1.2 The development of X-ray
X-radiation is also called Röntgen radiation, which is a form of electromagnetic
radiation. It has wavelengths that range from 0.1 to 10Å which is shorter than UV
radiation, but longer than γ-rays. The major use of X-rays is for diagnostic
radiography and crystallography. X-rays were first discovered in Crookes tubes.
Cathodes rays were created from electrons through the ionization of residual air in the
tube by a high DC voltage. This voltage accelerated the electrons coming from the
cathode to a sufficient velocity that created x-rays when the electrons struck the anode
or tube wall. Many early scientists did not realize the radiation from Crookes tubes
until Wilhelm Röntgen gave the first systematical investigation in 1895 [6].
Diffraction is the phenomenon of bending light passing an obstacle through a small
slit. The diffracted waves can interfere with each other giving bright and dark fringes,
depending on the phase differences of the wave. To explain the behavior of radiation,
a Dutch physicist Christian Huygens wrote a treatise on the theory of light wave
called Huygen’s principle. Max Von Laue was the first to use a crystal to diffract
X-rays in 1912 [7]. Since the crystal with the arrangement consists of parallel rows of
atoms equivalent to the parallel lines of the diffraction grating, the d-spacing could be
successfully determined from the separations of bright fringes of the diffraction
pattern. The classical Bragg law of diffraction relates the possibility of constructive
interference to the interplanar separations.
18 2.1 X-ray Crystallography
English physicists, Sir W.H. Bragg and his son Sir W.L. Bragg in 1913, derived
Bragg’s Law [8]. Some X-rays reflect off the first plane, but the rest subsequently are
reflected by succeeding planes (Figure 2.1.1) [9].
Figure 2.1.1: Diffraction of X-rays by a crystal
In first order reflection, scattered X-rays will have the difference in a whole number
wavelength. The secondary X-rays, scattered by atoms in all planes, are completely in
phase and reinforce each other. This is described as Bragg's Law:
where
λ = wavelength of x-rays
θ = glancing angle
d = inter planar separations
n = order of diffraction
The above equation can be conveniently written as:
where n is contained in dhkl and (hkl) refers to the Miller indices of the reflecting
plane.
2.1.3 X-ray crystallography
X-ray Crystallography is the study of determining the arrangement of atoms within a
crystal. The way this is accomplished is by examining the manner in which the beams
from an X-ray source scatter from the electrons within a crystal. This method can
ultimately produce a three dimensional picture of the density of the electrons within
the crystal. This can allow for determination of mean atomic positions. Diffraction of
19 2.1 X-ray Crystallography
X-ray’s in crystalline materials is a key step. Crystals are highly ordered solids in
which a particular arrangement of atoms (unit cell) repeats indefinitely along all three
axes known as basis vectors [10]. Atoms scatter X-rays primarily through their
electrons. An X-ray striking an electron produces a secondary spherical wave
emanating from the electron. This is known as scattering. A regular array of scatters
produces a regular array of spherical waves. Most of these cancel out in most
directions through destructive interference. However, some add constructively and
their direction follows Bragg’s law.
2.1.4 X-ray sources
In the X-ray source, electrons produced at a cathode are accelerated in a potential
field and bombard the metal target (Cu, for instance). Some electrons in the orbital
near the metal nucleus are removed by the bombardment. Then the electrons in the
outer shell transit into the vacated orbital and emit a characteristic x-radiation. K
series radiation is formed by electron transition from outer shell to K shell. MoKα
radiation with wavelength of 0.71073Å was used to determine the structure of the
crystals that had been reported in this thesis.
2.1.5 Diffraction of X-ray by crystals
The diffraction of X-ray by crystals was discovered by Max van Lau in 1912 [11].
Although X-rays had been discovered in 1895 by Röntgen, their nature was not
known. During the years following their discovery, a number of determined efforts
were made to prove them particles or waves. It was not, in fact, until diffraction by
crystals was observed that their wave character was proved. Diffraction effects are
observed when electromagnetic radiation impinges on periodic structures with
geometrical variations on the length scale of the wavelength of the radiation. The
inter-atomic distances in crystals and molecules amount to 0.15–0.4 nm which
correspond in the electromagnetic spectrum with the wavelength of X-rays having
photon energies between 3 and 8 Kev. Accordingly, phenomena like constructive and
destructive interference should become observable when crystalline and molecular
structures are exposed to X-rays. If X-rays are to be diffracted by a set planes the
incident ray should fall on the set of planes at a glancing angle θ is given by:
20 2.1 X-ray Crystallography
where n is an integer expressing the order of reflection from this set of planes having
interplanar spacing d and λ is the wavelength of the incident X-rays.
The above equation can be conveniently written as equation 2-2. Consider a unit cell
with translation a, b and c along its edges. It can be shown that the phase of the
wavelet scattered by an atom P. If there are N atoms in the unit cell, the resulting
amplitude of the diffracted beam is given by:
where fj is the atomic scattering factor of the jth atom. The quantity Fhkl is called the
structure factor. It’s modulus is called the structure amplitude and is defined as the
ratio of the amplitude of the radiation scattered in the order (hkl) by the contents of
the unit cell to that scattered by single classical electron kept at the origin under the
same conditions.
2.1.6 Processing the X-ray diffraction data
After a series of diffraction patterns has been recorded, the two-dimensional image
obtained must be converted to a three-dimensional model of the density of electrons
throughout the crystal. This is accomplished by a mathematical technique known as
Fourier transforms. Each spot corresponds to a different type of variation in the
electron density. The crystallographer determines which variation corresponds to
which spot (indexing), the relative strengths of each spot (merging and scaling), and
how the variations should be combined to yield the total electron density (phasing)
[11]. In order to process the data, the crystallographer must first index the reflections
within the multiple images recorded. A byproduct of indexing is determining the
symmetry of the crystal (space group). Once symmetry is assigned, the data is then
integrated. This converts hundreds of images, containing thousands of reflections, into
one file. A full data set can contain hundreds of separate images of the crystal taken at
different orientations. The images must be merged and scaled. This lets the
crystallographer know which peaks appear in two or more images and to scale the
relative images so they have a consistent intensity scale. Data collected from
21 2.1 X-ray Crystallography
diffraction experiments is a reciprocal space representation of the crystal lattice. The
position of each spot is controlled by size and shape of the unit cell and the symmetry
within the crystal. The intensity of each spot is recorded and is proportional to square
of the structure factor amplitude. Structure factor is a complex number containing
information relating to phase and amplitude of a wave.
In order to obtain an electron density map, both amplitude and phase must be known
[8]. Once an initial phase is known, an initial model can be constructed. The initial
model is used to refine the phases. Newer models are constructed and used to refine
again. This process is repeated until the best refinement is obtained. If there are few
flaws in the crystal, this ultimately leads to a structure that is reasonable [11].
2.1.7 General scattering expression for X-rays
X-ray scattering is a phenomena caused due to the interaction between the electron
and X-ray radiation. Coherent scattering happens with no X-ray energy loss and is
also called elastic scattering. Another X-ray scattering is called inelastic scattering or
Compton scattering. This inelastic scattering was proposed by Arthur Holly Compton
in 1923 [12].
The change in momentum of the X-ray radiation is due to the change in its direction
of the scattering electron. The energy of the scattered electron is thus less than the
energy of the incident X-rays. The scattering of X-rays from the electron of atoms is
possible in all the directions.
The intensity of radiation scattered by an electron is discussed by the classical
Thomson equation and called scattering power of an electron (fe). The amplitude of
wave scattered by an atom is proportional to its atomic number (Z) [13].
Also, atom scattering power, usually expressed as the ratio of scattering of an atom
factor to the scattering by a single electron under the same conditions [14-17]. Thus,
the scattering factors is expressed .The mean position of atoms in
the unit cell is vibrating at any temperature [18].
The scattering factor of an atom decreases with their amplitude of atomic vibration.
Also, the scattering factor decreases with the increase of the diffraction angle due to
the atomic size, showing the mutual destructive interference of the X-ray scattered
from the atoms. The scattering factor of an atom is given as [19]:
22 2.1 X-ray Crystallography
where f0 : scattering factor of an atom when it is rest and at 0°.
λ : wavelength of x-ray.
θ : angle of diffraction.
B : a constant (called isotropic temperature factor, which is related to the amplitude of
atomic vibration is given as where mean of square displacement of
the atom from the mean position). The exponential term is called Debye-Waller
factor).
A crystal lattice consists of atoms which form three-dimensional arrays. The structure
factor for a particular plane hkl and F(hkl) consistent angul part gj,θ and scattering
factor from the plan (hkl) and F(hkl). The structure factor of a plane hkl is expressed
as:
where
F(hkl) : Amplitude of scattered radiation from the plane hkl.
g (j, θ): Scattering factor of the atom j at the diffraction angle θ.
In an X-ray diffraction experiment, the intensity is promotional to the square of the
amplitude of the wave.
where
Io(hkl): experimental observed intensity
I(hkl): a function of the experimental conditions, Lorentz-polarization factor,
polarization, and absorption correction
N: a scale factor associated with the amplitude of scattered radiation.
23 2.1 X-ray Crystallography
2.1.8 Reciprocal lattice and Ewald sphere
The usefulness of the concept of the reciprocal lattice is to understand the diffraction
of X-rays from a crystal. A reciprocal lattice can be associated with every real
crystalline lattice. For every plane in the direct lattice, draw a normal from the origin
of the unit cell whose length is restricted to the reciprocal of the interplanar spacing.
A point is placed at the end of each limited normal and the collection of such points
constitutes a new lattice called the reciprocal lattice.
One can write the scattering vector S as:
S=hxa*+Kyb
*+Lzc*
where S is a vector in reciprocal space with the metric a*, b*, and c* (reciprocal lattice
vector). The relationship to the direct space with metric a, b, and c is still unknown.
The vector S must obey the Laue equations:
This is fulfilled only when aa* =1, hx = h and ab* and ac* =0. Similar equations can
be derived for the other two Laue conditions. Thus, vector S is a vector of a lattice in
reciprocal space. The relationship between the direct and reciprocal lattices is given
by the following:
It follows from these that a*┴ b; c; b* ┴ a; c; c*┴ a; b; and vice versa. The metric
relationships can also be derived from these relationships. They adopt the following
form for the general case of the triclinic crystal system:
24 2.1 X-ray Crystallography
This means that the inverse lattice vectors are perpendicular to the plane, which is
spanned by the two other non-inverse lattice vectors. Bragg’s law can now be derived
by inspection of figure 2.1.2.
Figure 2.1.2: Geometric representation of diffraction geometry; 2θ glance angle; θ Bragg angle.
The wave vectors for the incident wave S0 and the scattered wave s have the same
absolute value of 1/λ. Vector S must be a vector of the reciprocal lattice, and its
absolute value is equal to d*. From figure 2.1.2 the following equations 2 -13 to 2-16
can be obtaining.
The general equation for Bragg’s law is:
where n is the order of reflection and d the interplanar distance in the direct lattice.
'The Ewald sphere is a geometrical combination of the Bragg's law and the reciprocal
lattice. The Ewald construction is contained in Figure 2.1.3. A sphere of radius 1/λ is
drawn, and the origin of the reciprocal lattice is located where the wave vector s0 ends
on the Ewald sphere. The incident x-ray beam is along its diameter. The origin of the
reciprocal lattice is positioned at the point where the incident beam emerges from the
sphere.
25 2.1 X-ray Crystallography
Figure 2.1.3: Diffraction geometry in the rotation method usually applied in macromolecular X-ray diffraction systems.
A diffracted beam is generated if a reciprocal lattice vector d*hkl with an absolute
value of 1/dhkl cuts the Ewald sphere. The beam is diffracted in the direction of the
connection of the origin of the Ewald sphere and the intersection point of the
reciprocal lattice point on the Ewald sphere. The diffraction pattern of a lattice is itself
a lattice with reciprocal lattice dimensions [20].
2.1.9 Selection of single crystal
The first step in a crystal structure analysis is concerned with the selection and
mounting of a suitable specimen. Ideally, a crystal whose structure is to be determined
must be a single crystal of 0.1 mm to 0.5 mm size, not cracked and not twinned by
examining it under a polarizing microscope. Preliminary photographic examination of
the crystal provides information regarding the crystal system, unite cell dimension
space group etc.
26 2.2 Diffraction amplitude
2.2 Diffraction amplitude
2.2.1 The structure factor
The structure factor is the central concept in structure analysis by diffraction methods.
Its modulus is called the structure amplitude. The structure amplitude is a function of
the indices of the set of scattering planes h, k and l, and is defined as the amplitude of
scattering by the contents of the crystallographic unit cell, expressed in units of
scattering. The complex form of the structure factor means that the phase of the
scattered wave is not simply related to that of the incident wave. However, the
observable, which is the scattered intensity, must be real. It is proportional to the
square of the scattering amplitude [21]. The structure factor is directly related to the
distribution of scattering matter in the unit cell which, in the X-ray case, is the
electron distribution, time-averaged over the vibrational modes of the solid. The
structure factor may be represented as a complex vector [22]:
where A(hkl) and B(hkl) are the real and imaginary components of F(hkl) (Figure 2.1.
4).
The magnitude or length of the vector |F(hkl)| may then be represented as:
Alternatively, F(hkl) may be expressed as an exponential quantity:
where |F(hkl)| is the amplitude of the scattered wave and α(hkl) is its phase angle.
From Figure 2.1.4 it may be seen that:
27 2.2 Diffraction amplitude
Figure 2.1.4: Structure factor F(hkl) plotted on a diagram. α (hkl) is the phase angle and the amplitude is represented by OF.
|F(hkl)| may be calculated directly from the measured intensity I(hkl) for a reflection,
since
where K is a constant. However, the phase angle α(hkl) cannot be measured
experimentally and must therefore be obtained indirectly through a variety of
numerical techniques. The central problem in the solution of a crystal structure is the
assignment of phase angles to each reflection in the data set. The solution of the phase
problem is considerably simplified for crystals that possess crystallographic centers of
symmetry, since, to a first approximation, the imaginary components B(hkl) are zero
for centrosymmetric space groups and the phase angles are therefore restricted to
values of 0° or 180°. A structure is considered solved when a set of phase angles has
been found that allows the atoms to be located and the experimental diffraction
pattern to be matched to the calculated diffraction pattern. Since the electron density
in a crystal varies continuously and periodically in three-dimensional space, the
electron density ρ(xyz) at a point with fractional coordinates x, y, z in a unit cell of
volume V may be expressed as a three dimensional Fourier series:
If both the amplitude |F(hkl)| and the phase α(hkl) of each reflection are known, the
electron density within the unit cell of the crystal can be calculated directly. On the
other hand, if the positions of the atoms in the unit cell are known, both the structure
28 2.2 Diffraction amplitude
factor and the phase for each reflection may be calculated from the structure factor
equation:
where fj is the atomic scattering factor for the atom j and xj, yj, zj are its fractional
coordinates. In an actual structure determination both forms of the Fourier transform
equations are utilized to arrive at a model structure from which the observed
diffraction pattern can be reproduced [23].
2.2.2 Collection of intensity data
In an actual X-ray diffraction experiment, one measures the intensities Ihkl rather than
the amplitude of the reflected beam. The measure of the total number of photons
which are diffracted in the proper direction by reciprocal lattice point is known as
intensities. It is from these intensities the electron density distribution and the
positions of the atoms in the unit cell are deduced. Two general methods, ω or ω-2θ
scan are available for measuring the intensity of a diffracted beam. Either the beam
may be detected by some sort of quantum counting device, which measures the
number of photons directly or by measuring the blackening is proportion to the beam
intensity. Intensity data for crystals reported in this thesis were collected by Bruker
SMART CCD diffractometer [24] and Oxford Diffraction Xcalibur [25] diffract-
ometer.
2.2.2.1 Bruker SMART CCD diffractometer
The Bruker SMART CCD detector system is used to collect single crystal or powder
diffraction data. The Single crystal diffractometer is a 3-axis goniometer module with
SMART APEX detector, radiation safety enclosure with interlocks and warning
lights. In addition the facility also has an Oxford Cryo-systems nitrogen stream setup,
which allows data acquisition at lower temperatures (90K) see Table 2.1.1. The
external view of diffractometer and sealed X-ray tube with goniometer are shown in
figures 2.1.5 and 2.1.6 respectively [24].
29 2.2 Diffraction amplitude
Table 2.1.1: BRUKER SMART configuration.
SMART APEX Configuration
Data collection details Combination of omega and phi scans
Data Reduction Integration with the SADABS; Sheldrick 2004 and
SADABS Bruker 2001.
X-ray Source Mo Kα
Wavelength 0.71073 Å
X-ray Generator 50kV, 40mA Max.
20kV, 5mA Min.
Monochromator Graphite crystal
Collimator 0.3mm, 0.5mm
SMART can control up to 4 diffractometer axes. These are 2-theta (2θ), omega (ω),
phi (ф) and kappa (or chi (χ)). This EPICS software will also work with diffracto-
meters with fewer axes, and we have successfully used it to collect data with a simple
system with a single rotation stage, which could be called phi or omega. The diagram
of the circles is shown in figure 2.1.7.
The four circle geometry employed in the diffractometer, is used
1. for manual sample mounting on the diffractometer.
2. to keep the crystal within the beam.
3. to keep the crystal in any orientation.
4. for bring desired reflecting plane to the correct glancing angle with the
incident beam.
5. for rotating the detector arm and positioning it at an angle equal to twice the
glancing angle with respect to incident beam.
30 2.2 Diffraction amplitude
Figure 2.1.5: Overall view of Bruker Smart Apex with CCD
Figure 2.1.6: Sealed-off X-ray tube shield and goniometer of Bruker Smart Apex diffractometer.
31 2.2 Diffraction amplitude
Figure 2.1.7: Schematic diagram of a four circle diffractometer.
2.2.2.2 Oxford Diffraction Xcalibur diffractometer
The Oxford Xcalibur is a 4-circle kappa diffractometer equipped with both point and
CCD detector. The high resolution achieved and the accuracy of the data is
fundamental for electron density studies and situations where small, weak samples are
being studied. This four circle CCD (sapphire detector) diffractometer is equipped
with two low temperature devices, namely, a nitrogen cooler, CRYOJET, allowing a
routine working temperature of 90K, and a helium cooler, HELIJET , allowing to
reach a temperature as low as 15K (see Table 2.1.2). The external view of
diffractometer and sealed X-ray tube with goniometer are shown in figures 2.1.8 and
2.1.9 respectively [25].
Table 2.1.2 Oxford diffractometer configuration.
Oxford Diffractometer Configuration
Data collection details Combination of omega and phi scans to maximize reciprocal space coverage to at Least 80° 2θ.
Data Reduction Integration with the CrysAlis PRO RED software provided by Oxford Diffraction
X-ray Source MoKα, graphite
Wavelength 0.71073 Å Scan speed 0.05deg/sec, frame width 1 degree, total frames 1328. Monochromator Graphite crystal Collimator 0.3mm, 0.5mm
32 2.2 Diffraction amplitude
Figure 2.1.8: Overall view of Oxford Diffraction Xcalibur Diffractometer
Figure 2.1.9: Sealed-off X-ray tube shield and goniometer of Oxford Diffraction Xcalibur Diffractometer
33 2.3 Data reduction
2.3 Data reduction
The measured intensity, I(hkl), of diffracted X-ray beam can by calculated using the
formula of Galton Darwin for a crystal rotating with a uniform angular velocity, ω,
through a reflecting position [26]:
This equation shows that the structure factor amplitude, |F(hkl)|, is a function of the
intensity, I(hkl), of a diffracted beam. This conversion of I(hkl) to |F(hkl)| involves
the application of corrections for X-ray background intensity (I), polarization (P),
Lorentz (L), Absorption (A), Extinction and thermal motion. This process is known
as data reduction [27].
2.3.1 The polarization factor
The radiation from normal X-ray tube is unpolarized. When a totally unpolarized
beam is diffracted by a crystal, the beam will be partially polarized and the diffracted
intensity is affected by a factor called polarization factor. So the correction for
polarization turns out to be [28]:
where 1 + cos22θ denotes the polarization factor, sin 2θ describes the change in
irradiated volume of a crystal as a function of 2θ (the single crystal Lorentz factor).
The correction to be applied to the measured intensity is 1/p. Since we use graphite
crystal monochromator in a diffractometer the incident beam on the crystal itself will
be partially polarized. Hence polarization factor is:
where θm is the Bragg angle for monochromatizing crystal and pf is the perfection
factor for monochromatizing crystal.
34 2.3 Data reduction
2.3.2 The lorentz factor
The Lorentz factor takes into account the fact that for a constant angular velocity of
rotation of the crystal, different reciprocal lattice points pass through the sphere of
reflection at different rates. When the crystal rotates, the three-dimensional reciprocal
lattice also rotates. The reciprocal lattice point near rotation axis will cut across the
Ewald sphere more slowly than one away from the rotation axis. So they have
different times of reflection. For a 4-circle diffractometer measurement, Lorentz
correction is
2.3.3 Absorption
When X-rays of intensity Io pass through a material their intensities are attenuated.
The trans-mission of the x-ray beam through the crystal is given by [29]:
where ti and td are the incident and diffracted beam path lengths and μ is the linear
absorption coefficient. If the shape of the crystal is exactly known, then it is possible
to correct for absorption by calculating
where dV is an infinitesimal volume of the crystal [30].
However if' the crystal faces are not well defined it is necessary to resort to empirical
methods which attempt to measure T experimentally [31]. For intensities measured
with the Oxford Diffraction Xcalibur and BRUKER SMART diffractometers, multi-
scan [32] and Ψ-scan correction method [33] respectively are found to be successful.
In the present work multi-scan and Ψ-scan were used.
The crystal is assumed to be totally bathed by the incident X-ray beam. Consider a
point P (Figure 2.1.10) in the diffractometer plane and on the Ewald sphere. If the
crystal is rotated about the vector r* the point P will still remain on the diffracting
35 2.3 Data reduction
position and the variation in observed intensity may be attributed to absorption
effects.
Figure 2.1.10: The bisecting geometry arrangement
In practice, the φ rotation axis is brought to a direction coincident with that of the
vector r* which require the choice of a reflection with a x value of 90o. Then the
azimuthal angle Ψ is equivalent to the diffractometer angle φ.
The relative transmission factor for a given value of is given by:
where the Imax(ф) (cp) is the maximum intensity observed as φ is varied over the
360° range.
2.3.4 Extinction
Attenuation of diffracted beams may also occur due to extinction effects: primary and
secondary [34].
v Primary extinction causes weakening of intensity by multiple reflections
suffered by the incident wave for different lattice planes. Each scattering
causes a phase lag of π/2. Thus when the unscattererd radiation is joined
by the double) scattered radiation with a phase lag of π, destructive
interference results. Primary extinction is often negligible in single crystals
whereas secondary extinction is predominant in sufficiently perfect
crystals. Correction for the secondary extinction is generally considered at
the end of the refinement and can be given by approximate equation:
36 2.3 Data reduction
where k is the scale constant and g is secondary extinction coefficient and
is characteristic of the crystal for a given radiation.
v Secondary extinction accounts for the fact that lattice planes first
encountered by the primary beam will reflect a significant fraction of the
primary intensity so that the deeper planes receive less primary radiation.
This causes a weakening of the diffracted intensity, mainly observable for
high intensity reflections at low sin θ/λ values [35].
In the crystal structure refinement package SHEIXL-97 [36], an extinction parameter
x is refined by least squares,
where K is the overall scale factor.
2.3.5 Temperature factor
The size of the electron density cloud around an atomic nucleus is independent of the
temperature, at least under normal conditions. This would suggest that X-ray
scattering by a crystal would also be independent of the temperature. However, this is
not true because the atoms vibrate around an equilibrium position. The X-rays do not
meet identical atoms on exactly the same position in successive unit cells. This is
similar to an X-ray beam meeting a smeared atom on a fixed position, the size of the
atom being larger if the thermal vibration is stronger. This diminishes the scattered X-
ray intensity, especially at high scattering angles. Therefore, the atomic scattering
factor of the atoms must be multiplied by a temperature-dependent factor (Figure
2.1.11).
Figure 2.1.11: The atomic scattering factor of a carbon atom multiplied by the
appropriate.
37 2.3 Data reduction
The vibration of an atom in a reflecting plane h k l has no effect on the intensity of the
reflection (h k l). Atoms in a plane diffract in phase and, therefore, a displacement in
that plane has no effect on the scattered intensity. The component of the vibration
perpendicular to the reflecting plane does have an effect. In the simple case in which
the components of vibration are the same in all directions, the vibration is called
isotropic. Then the component perpendicular to the reflecting plane and thus along S
is equal for each (h k l), and the correction factor for the atomic scattering factor is:
Assuming isotropic and harmonic vibration, it can be shown that the thermal
parameter B is related to the mean square displacement of the atomic vibration:
If the atomic vibration is split into three perpendicular components—one
perpendicular to the reflecting plane [vibr( )] and two in the plane, vibr(||1) and
vibr(||2)—then vibr( ) is the only one giving rise to the temperature factor with
parameter [37].
For anisotropic vibration, the temperature factor is much more complicated. In this
case , depends on the direction of S. It can be shown that the temperature factor is
given by:
with U11 the value along a , U22 along b*, and U33 along c*. In general,
along a unit vector e is given by:
38 2.4 Scaling
with e1, e2, and e3 the components of e along unit axes a*, b*, and c*. The points for
which is constant form an ellipsoid: the ellipsoid of vibration. For display
purposes, the constant can be chosen such that the vibrating atom has a chance (e.g.,
50%) of being within the ellipsoid (Figure 2.1.12).
Figure 2.1.12: The plot of an organic molecule with 50% probability of thermal ellipsoids. Waleed Fadl Ali Al-eryani et al. (2010). Acta Cryst. E66, o1742.
In summary, an appropriate treatment is to describe the thermal ellipsoid by a tensor
U having six independent components in the general case. So we have the correction
due to thermal motion by using equation 2-33.
2.4 Scaling
The incident X-ray beam intensity fluctuations and possible radiation damage to the
crystal may be monitored by measuring four standard reflections of moderate
intensities at regular intervals. The average of these intensities relative to the average
of their starting values is smoothed and used to re-scale the raw intensity data. If S is
the scale factor, then the total correction applied is
where Ir is the corrected relative intensity.
39 2.5 Structure determination
2.5 Structure determination
2.5.1 The phase problem
To be able to solve the three dimensional structure of a molecule the position of each
atom in the unit cell has to be determined. The image of the scattering matter in the
point x, y, z can be represented by a Fourier summation:
where V is the volume of the unit cell, F(hkl) is the structure factor for the particular
set of h,k,1. (h, k.1 are the Miller indices with which the crystal plane or face make
intercepts a/h. b/k, c/i with the edge of the unit cell of lengths a. b, and c), x,y,z are the
fractional coordinates which are the atomic coordinates expressed as the fractions of
the unit cell length
and
Where, |F(hkl)| is the amplitude of the structure factor, |F(hkl)|2 is proportional to the
intensity of the reflections. α is the phase of the scattered beam. We can measure the
amplitude which is proportional to the square root of the intensity of the
reflections, but the direct measurement of the relative phase is not possible. So the
trick of crystallography lies in the finding of the phase.
2.5.2 Methods of structure solution
Since the electron density in a crystal varies continuously and periodically in three-
dimensional space, the electron density ρ(xyz) at a point with fractional coordinates x,
y, z in a unit cell of volume V may be expressed as a three-dimensional Fourier series:
where the summation is from -∞ to +∞ over all the hkl values and V is the unit cell
volume.
40 2.5 Structure determination
The magnitude of structure factors can be determined from the measured intensities of
the reflections, but it is not normally practicable to measure their relative phases.
Except for the phase, all quantities on the right hand side of equation (2-38) are
known. This loss of phase information constitutes the 'phase problem' in X-ray
crystallography.
An attempt to find solutions to the phase problem started around 1934 [38]. Two
substantially different approaches are used in crystallography to solve the phase
problem. While one tries to determine the phases of the reflections directly (direct
methods) by using statistical methods, the other makes use of the so-called Patterson
function which can be calculated from the experimental intensities [39].
2.5.2.1 Patterson method
In 1934, Patterson, A. L. introduced and discussed the physical significance of Fourier
series which can be directly calculate from experimental intensity data [40]. This
method can be applied to structures in which one or a few atoms are markedly heavier
than the rest. It is possible to find the locations of the heavy atoms by use of the
Patterson function which does not require a prior knowledge of the phases. The
Patterson map, commonly designated ρ(uvw), is a Fourier synthesis that uses the
indices, h,k,l, and the square of the structure factor amplitude, , of each
diffracted beam. It is usual describe the Patterson map in vector space defined by u,v,
and w, rather than x,y,z as used in electron-density maps. The Patterson method
consists of evaluating Patterson function which can be represented with the following
equation:
If the electron density is known, the Patterson function at any point u,v,w may be
calculated by multiplying the electron density at a point x, y, z with that at x+u, y+v,
z+w, doing this for all values of x, y and z and summing the products [41]:
41 2.5 Structure determination
In other words, the Patterson function is the convolution of the electron density at all
points x, y, z in the unit cell with the electron density at points . A
peak at in the Patterson map represents a vector from the origin of the
Patterson function to the point u,v,w. This means that if any two atoms in the unit cell
are separated by a vector then there will be a peak in the Patterson map at
u,v,w. The peaks in a Patterson map are inherently broader than those in a Fourier
map for finite size of atoms. Instead of N peaks in a unit cell of a Fourier map, there is
a crowding of N(N-1) peaks in the same volume of the Patterson map enhancing the
probability of superposition. However, when the structure contains one or more heavy
atoms, the peaks due to interactions of the heavy atom stand out among other peaks of
lower magnitude making interpretation comparatively easy. The Patterson technique
is therefore best applicable to heavy atom structures. The difficulty with the Patterson
method is that a unit cell with N independent atoms will have N2 inter-atomic vectors
(peaks in the Patterson map). When N is large as for a macromolecule, the peak
overlaps make it difficult to solve the structure directly using this method [42].
2.5.2.2 Direct methods
The term 'direct methods' is applied to that class of methods which seek directly to
solve the phase problem by the use of phase relationships based on the observed
intensities [43]. Direct methods, implemented in widely used highly automated
computer programs such as SHELXS [36] provide computationally efficient solutions
for structures with fewer than about 100 independent non-H atoms. Until the last
decade most of the advances in the field of direct methods concentrated on the
development of the methods [44] themselves, i.e., the intensity data used for these
developments corresponded to ideal single crystal diffraction experiments. More
recently, however, developments like the direct methods modulus sum function have
helped to extend the applicability of such methods to less favourable situations like
the crystallography of reconstructed surfaces.
In direct methods structure factor phases are derived directly from the observed
amplitudes through purely mathematical techniques; without assuming any kind of
molecular structure. When the number of structure amplitudes measured is more than
ten times the number of the parameters to be determined, direct methods, which
utilize the sign and phase relations, can be used to solve the structure. One such
42 2.5 Structure determination
relation applicable to centrosymmetric system, where phase can only be 0o or l80o, is
that the sign of F(hkl) is probably equal to the product of sign of F(h`k
`l`) and F(h-h,k-
k`,l-l
`). Possible phases can be derived from systematically searching for sets of
reflections (with high intensities) whose indices are related in this way. An electron
density map can then be calculated. Peaks are assigned for the atoms in the structure
to get the trial structure. From the trial structure the new phases are calculated. The
structure can be solved by repeating this cycle. This method is mainly used for small
molecules with up to roughly 50 non-hydrogen atoms.
The various steps involved in the direct methods are [45]:
Step I Conversion of observed structure factor |Fhkl| to normalized
structure factor |Ehkl| which are independent of θ.
Step II Setting up of phase relations using triple phase relation
(triplets) and four phase relations (quartets).
StepIII Selection of few reflections, the phase of which are assigned apriori.
Step IV Phase propagation and refinement using tangent formula.
Step V Calculation of best phase sets and expressing the reliability
of the phases in term of Combined Figure of Merit (CFOM).
Step VI Calculation of electron density map (E-map) with |Ehkl| as
the Fourier coefficient.
The electron density at a point with position vector r can be expressed as
and the quantity F( k) is given by:
where the integration is carried over the unit cell volume. For a unit cell having n
discrete atoms this becomes,
The Phase of this quantity is given by:
43 2.5 Structure determination
This is an indirect method of estimating the values of ( k)’s.
2.5.2.3 Unitary structure factor
While searching for relations between the phases and the magnitudes of |F|, we must
remember that apart from their dependence on the position of the atoms [46], |F| s are
also affected by the finite size of the atoms and thermal vibration contributes due to
these factors are evident for our purpose and the magnitudes of |F| may
advantageously stripped off of these two effects by suitable modification, so that the
modified values correspond to the idealized situation of a structure built up by
stationary point atoms. One way of doing this is to express Fh as a fraction of its
maximum value, which is
Thus we get the unitary structure factor the values of which
evidently lie between –1 and +1.
2.5.2.4 Normalized structure factor
In direct methods, the measured structure factors are modified so that the maximum
information on atomic position can be extracted from them. Other effects, such as the
falloff of intensity at high scattering angles due to atomic size and atomic vibrations
are eliminated, to be considered when the structure has been determined. The
structure-factor data are therefore converted to those expected for a structure
composed of point atoms at rest (not vibrating). The scattering factor expression for
real atoms involves the scattering of an atom with a finite size (represented by ),
and an exponential factor representing atomic vibrations and disorder. The expression
is:
44 2.5 Structure determination
In direct methods it is usual to replace this expression by one for that of point atoms,
so that X-ray scattering is now essentially independent of sinθ/λ. This is done by
dividing F(hkl) by a function of that eliminates any fall-off of intensity as a function
of sinθ/λ (Figure 2.1.13).
Figure 2.1.13: Scattering curves for regular atoms and stationary point atoms.
The resulting normalized structure factor, |E(hkl)| is:
where was defined in Equation (42-2) and the integer ε the epsilon factor is a factor
that is generally unity, but is needed to account that certain classes of Bragg
reflections, such as those with one zero index, that have, as a group, an average
intensity higher than that for the rest of the Bragg reflections [47]. Values for ε for
each type of Bragg reflection can be found in International Tables [48].
2.5.3 Structure invariant and semi-invariants
Although the values of individual phases are known to depend on the structure and the
choice of origin, certain linear combinations exist of the phases whose values are
determined by the structure alone and are independent of the choice of origin. The
linear combinations of the phases are called the structure invariants [49].
45 2.5 Structure determination
2.5.4 Refinement of structure
The atomic positions in the first solution are not the direct result of the diffraction
experiment but an interpretation of the electron density calculated from the measured
intensities and the ‘somehow-determined’ initial phase angles. New, usually more
accurate phase angles can be calculated from the atomic positions, which allow re-
determining the electron density function with a higher precision. From the updated
electron density map, more accurate atomic positions can be derived, which lead to
even better phase angles, and so forth. New atoms can be introduced into the model,
when the most recent electron density function shows a high value at a place in the
unit cell where the model does not contain an atom yet. Sometimes, atoms need to be
removed from the model when they occupy positions in the cell corresponding to a
low value in the electron density function. When the atomic model is complete, atoms
can be described as ellipsoids rather than spheres (anisotropic refinement) and
hydrogen atom positions can be determined or calculated. Every step in this process is
undertaken to improve the accuracy of the model, and the entire procedure from the
initial atomic positions to the complete, accurate and (if achievable) anisotropic model
with hydrogen positions is called the refinement. A critical point in this process is the
evaluation of the model, as the model should only be altered if a change improves its
quality. There are several mathematical approaches to define a function which is
assumed to possess a minimum for the best possible model: in the world of small
molecules (typically less than 200 independent atoms) the least-squares approach is
by far the most common method.
A few cycles of least-square refinement can lead to best adjusted parameters. The
refinement [Refinement is the process of adjusting the model to find a closer
agreement between the calculated and observed structure factors] is continued until
the shifts in the parameters are some small fraction of the estimated standard
deviation of corresponding parameters [50].
SHELXL [51] was used to refine the structures reported in this thesis. The refinement
of the structures against F2 in this program makes possible the refinement of all the
data except those known to suffer from systematic errors. At the end of the refinement
the program computes the weighted R-factor and the Goodness of fit, GOOF (also
called the standard deviation of an observation of unit weight).
46 2.5 Structure determination
2.5.4.1 Residual factors
The quality of the model can be judged with the help of various residual factors or ‘R-
factors’. These factors should converge to a minimum during the refinement and are
to be quoted when a structure is published. The three most commonly used residual
factors are [52]:
v The weighted R-factor based on F2: ωR (or ωR2 in SHELXL), which is
most closely related to the refinement against squared structure factors.
where being the standard deviation of Fo.
v Albeit based on F values and hence mostly of historical value, the most
popular one is the unweighted residual factor based on F: R (or R1 in
SHELXL), given by
Thus R measures the relative discrepancies between Fc and Fo, so that
the lower the value of R, the better is the agreement. In an ideal case R =
zero.
v Finally, there is the goodness of fit: GooF, GoF, or simply S, given by:
where NR is the number of independent reflections and NP the number of
refined parameters.
A goodness of fit S < 1 suggests the model is better than the data.
Obviously this is suspicious and usually a sign that there are some
problems with the data and/or the refinement. Frequently, failure to
47 2.5 Structure determination
perform a proper absorption correction leads to underestimated GooF
values, but refinement in the wrong space group can also have this
effect.
2.5.5 Difference Fourier synthesis
The structure factors have been calculated for a given electron density in the unit cell.
It is also possible to calculate the electron density in the unit cell by inverse operation
for a given set of structure factor, this inverse operation can be given by the three
dimensional Fourier series by [53]:
where
is electron density at (x,y,z) in the unit cell V: is the unit cell volume
(x, y, z): are the coordinates which represent crystallographic axes.
A difference synthesis can by performed by subtracting an electron density, calculated
using Fc from the usual one containing Fo.
This can be given by
where
Note that the same phases c are used both calculations.
or
where c is the phase of Fc
From the value of maximum and minimum the missing atoms or
misplaced atoms or the atom which has been considered as a different atom can be
48 2.5 Structure determination
identified. In general (xyz) for hydrogen atoms are not calculated and are fixed at
chemical acceptable positions.
2.5.6 Weighting scheme
The weighting scheme is defined as follows:
where σi is the standard deviation. The reciprocal of the variance is indeed a measure
of its reliability, and the function minimized is:
Where σ is the standard deviation and it can be shown that
where N is number of counts. In diffractometer while measuring the X-ray reflection,
left background and right background counts are considered and the standard
deviation turns out to be
where K is a scale constant, L is the Lorentz factor, P is the polarization factor and
2.5.7 Some results derived from the refined structure
The most important results that can be derived from the refined structure are the
distances between bonded atoms and the angles between pairs of bonds. It is also
necessary to find the equation of the mean plane passing through a group of atoms
supposed to lie on a plane, to check the deviation of the atoms in such a group from
the plane and perhaps also to calculate the distance of some other atoms from it.
In our computer programs for all such calculation, the fraction coordinates of any
atom X(= x,y,z) with respect to crystallographic axes are transformed into coordinates
in Å, with respect to the orthogonal coordinates whose x-axis is
49 2.5 Structure determination
coincident with the crystallographic a-axis, y-axis lies in ab-plane and z-axis along
c*-direction. These transformed coordinates are given by:
where U is transformation matrix, given by
2.5.8 Bond distances, angles and their standard deviations
Calculation of interatomic distances and angle using the orthogonal coordinate system
is too simple to be described here. If σx,σy, σz, are the estimated deviations of the
fractional coordinates x, y, z of an atom, then the matrix Po with respect to
crystallographic axes is
The variance matrix Ps with respect to orthogonal axes, as defined above, is given by
where denotes matrix transposition. For an atom with variance matrix Ps, the
variance in the direction with direction cosine L=(1,m,n) is
Now, for a distance between atoms A and B having respective variances and
in the direction of bond, the variance is given by
In case of distance of symmetry related atoms
For the angle between atoms A, B and A, C of respective lengths rAB, rAC, the
variance [30] is given by
50 2.5 Structure determination
where and are the variance of atoms B and C in the direction at right angle to
and respectively, and is the variance of A in the direction of the center of
the circle passing through B, A and C. when A and B are related by symmetry
In our calculation of standard deviation of bond angles it is assumed that the variances
of the atomic coordinates are spherically symmetric,
2.5.9 Mean planes
The equation of a plane in orthogonal coordinate system at a distance p from the
origin is:
where l, m, n are direction cosines of the normal to the plane. The distance of a point
(Xi, Yi, Zi) from the plane being
The equation of the mean plane through a group of N atoms is obtained by
minimizing the quantity
where
The condition,
gives,
51 2.5 Structure determination
or
where
showing that the mean plane passes through the centroid of group of N
atoms. Writing now,
The condition gives three liner homogeneous equation in l,m,n which
are solved by a procedure described be Blow [54], remembering that l2+m2+n2+1=0.
Thus equation for the mean plane referred to orthogonal axes as,
The deviation of the N atoms from the plane may be calculated and we
can also calculate
where
2.5.10 Hydrogen bonding
A hydrogen bond is a bond between a functional group X—H and an atom or group of
atom A in the same or a different molecule [55]. Hydrogen bonds are formed only
when X is oxygen, nitrogen, or fluorine and when A is oxygen, nitrogen or fluorine.
The oxygen may be singly or doubly bonded and the nitrogen singly, doubly, or triply
bonded. The bonds are usually, represented by dotted lines, as shown in the following
examples (Figure 2.1.14):
52 2.5 Structure determination
Figure 2.1.14: some examples in hydrogen bond.
Hydrogen bonds can exist in the solid and liquid phases in solution [56]. Hydrogen
boning has been detected in many ways, including measurements of dipole moments,
solubility behavior, freezing-point lowering, and heats of mixing, but the most
important way is by the effect of the hydrogen bond on IR [57] and other spectra.
The bond may be described in terms of the d, D, θ and r as shown in (Figure 2.1.15)
Figure 2.1.15: Definition of the geometers d, D, θ and ф for a hydrogen bond.
Hydrogen bonds are important because of the effects they have on the properties of
compounds, among them:
v Intermolecular hydrogen bonding raises boiling points and frequently
melting points.
v If hydrogen bonding is possible between solute and solvent, this greatly
increases solubility and often results in large or even infinite solubility
where none would otherwise be expected. It is interesting to speculate what
the effect on the human race would be if ethanol had the same solubility in
water as ethane or chloroethane.
v Hydrogen bonding causes lack of ideality in gas and solution and solution
laws.
v As previously mentioned hydrogen bonding changes spectral absorption
positions.
v Hydrogen bonding, specially the intermolecular variety, changes many
chemical properties.
53 2.5 Structure determination
v Table 2.1.3 lists properties of hydrogen bonds that we classify as very
strong, strong and weak. These properties are geometrical, energetic,
thermodynamic and functional in nature [58].
Table 2.1.3 Some Properties of very strong, strong and weak hydrogen bonds.
Very strong Strong Weak
Bond energy (-Kcal/mol) Examples
15-40 [F-H···F]-
[N-H···N]+
P-OH···O=P
4-15 O-H···O = C N-H···O = C O-H···O-H
<4 C-H···O O-H···π Os-H···O
Bond length H-A≈ X-H H···A > X-H H…A >> X-H Length of X-H(Å) 0.05-0.2 0.01–0.05 ≤ 0.01 D(X…A) range (Å) 1.2–1.5 1.5–2.2 2.0–3.0 Bonds shorter than vdw 100% Almost 100% 30–80% Θ(X-H···A) range (0) 175-180 130-180 90-180 KT (at room temperature) < 25 7-25 < 7
2.5.11 Torsion angles
Torsion angles (or angle of twist) of ring system or chain of atoms are the dihedral
angles between planes formed by consecutive bonds. For a sequence of atoms
A,B,C,D the torsion angle of bond B—C is the angle between the positive normals to
the planes (B—A, B —C) and (C— B, C—D), where the positive direction of a normal
is defined to be that which forms a right-handed set with the two vectors defining the
plane. The torsion angle between groups A and D is then considered to be positive if
the bond A–B is rotated in a clockwise direction through less than 180 in order that it
may eclipse the bond C–D; a negative torsion angle requires rotation in the opposite
sense.
Stereochemical arrangements corresponding to torsion angles between 0 and
90 are called syn (s), those corresponding to torsion angles between 90 and
180 anti (a). Similarly, arrangements corresponding to torsion angles between
30 and 150 or between –30 and 150 are called clinal (c) and those between 0 and
30 or 150 and 180 are called periplanar (p). The two types of terms can be
combined so as to define four ranges of torsion angle; 0 to 30 syn-periplanar (sp);
30 to 90 and –30 to –90 syn-clinalal sc); 90 to 150 , and –90 to –150 anti-clinal
(ac); 150 to 180 anti-periplanar (ap) [59] (Figure 2.1.16).
54 2.5 Structure determination
Figure 2.1.16: Torsion angles.
2.6 Computations
Data collection: SMART (Bruker, 2001) [24]; CrysAlis PRO RED; CCD (Oxford
Diffraction, 2010) [25]; cell refinement: CrysAlis RED (Oxford Diffraction, 2004)
[25]; SAINT–Plus [24]; data reduction: CrysAlis RED [25]; SAINT –Plus [25] ;
program(s) used to solve structure: SHELXS-97 [36]; program(s) used to refine
structure: SHELXL-97 [36]; molecular graphics: MERCURY [60]; ORTEP-3 [61] and
PLATON [62]; software used to prepare material for publication: WinGX [63];
SHELXL-97[36] and PLATON [62].
55 Reference
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