Experimental Determination of Crystal Structures(Ch

3 of CMP)
Basics of Scattering
X‐Ray Diffraction: formulation of Bragg and Laue
Reciprocal Lattice
Laue Condition and Ewald’s Construction
X‐Ray, Neutron, and Electron
Why should we be interested?
Important terms for crystals
 CRYSTAL PLANES AND MILLER INDICES

The use of crystal planes to describe the

structure of crystals goes back to the
start of crystallography and crystal
planes were used by Bragg to explain
diffraction as will be seen later.
Crystal planes are defined by the
intercepts they make on the
crystal axes of the unit cell.
The inverse of these fractions are
the Miller Indices of the planes.

In (a) the intercepts are ½, ½, 1 and

the Miller Indices are (2 2 1).
In (c) the intercepts on b and c are at
infinity the inverse of which is 0 and
the plane is the (2 0 0).
In (d) the plane cuts the negative c
axis at -1 and thus is (1 1 -1). In
crystallography -1 is often written ī
and pronounced “Bar 1”.
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Characteristics of cubic lattices

Simple Body-centered Face-centered

Lattice
1 2 4
points/cell
Number of
nearest 6 8 12
neighbours
nearest
neighbour
a 3/2 a a/2
distance

Packing 2/6  = 0.740

/6 = 0.524 3/8  = 0.680
fraction
Hexagonal; Miller-Bravais indices
Production and Properties of X-Rays

• X-rays were discovered

in 1895 by Röntgen
• Invisible in nature
• Penetrate much more
than visible light
X-ray interaction with matter
Fundamentals of Diffraction
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 Diffraction

Diffracted
wave


a a a
3.0  1.5 
6.0 

Screen

• If a wave encounters a barrier that has an opening of dimension

similar to the wavelength, the passing wave will flare (spread) –
will diffract – in the region behind the barrier.
• Diffraction limits geometircal optics – will cause the light to spread
Origin of X-rays
 Diffraction and Bragg‘s law

• Structural information can be obtained by

using X-rays, electrons or neutrons
• The incident radiation must have a
wavelength between 0.1 and 1 .
• The interference of x-rays when scattered
from the atoms within a crystal lattice.
 DIFFRACTION AND THE BRAGG EQUATION

Max von Laue was the first to incident

beam
reflected
beam
o o
suggest that crystals might A x B
oo
diffract X-rays and he also (1,0,0) d a
UNIT
CELL
provided the first explanation m
o o
n

for the diffraction observed. C y D

However, it is the explanation

(a)
provided by Bragg that is simpler
and more popular.
incident reflected
In the Bragg view crystal beam o o beam
planes act a mirrors. A
oo
x B

Constructive interference d

is observed when the path m

o o
n
a
UNIT
(2,0,0) y CELL
difference between the two E F

reflected beams in (a) = nl. O P d

The path difference in (a) is C D

Z
2my. Since my/d = sin
2my = 2dsin = nl
where d is the interplanar spacing. (b)
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Fig. 11
 Bragg’s Law animated

In (a) above it is clear that the planes are the (1,0,0) set of planes.
If the path difference is simply one wavelength the Bragg condition
can be stated as

2d (1,0,0 ) sin  
This is a first order reflection. If the path difference is
two wave lengths the Bragg condition becomes
2d (1,0,0 ) sin  2
and the reflection is a second order reflection.

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• A monochromatic beam of X-rays with coherent
radiations incident on a crystal
• The atoms are arranged as sets of parallel planes
and these atoms act as a reflection mirror for X-rays
 Relation between plane spacing and
lattice constant
• For a cubic crystal,

Where (h k l) are called miller indices

• For constructive interference, the beams scattered on different
planes need to be in phase i.e.
(figure 1)

The above relation is called Bragg‘s law.

For the first order diffraction i.e. n =1
 = 2d(hkl)sin
 SELECT A SUITABLE
SOLVING A CRYSTAL STRUCTURE BY CRYSTAL
SINGLE CRYSTAL DIFFRACTION TECHNIQUES A
N.B. The crystal must be a single crystal.
CRYSTAL SYSTEM
and
UNIT CELL DIMENSIONS
Bragg's equation specifies that, if a crystal is rotated
B
within a monochromatic X-ray beam, such that every
conceivable orientation of the crystal relative to the beam FULL DATA SET
COLLECTION
is achieved, each set of planes will have had the C
opportunity to satisfy the Bragg equation and will have
BRAVAIS LATTICE
given rise to reflection.
In order to solve a crystal structure it is necessary D

to record a large number of reflections. SPACE GROUP

This implies accurately measuring their intensities and E

recording their directions with respect to crystal orientation CONSTRUCT AN

and initial X-ray beam direction. ELECTRON DENSITY
MAP
Many experimental techniques have been devised F
to achieve this. The steps involved in a crystal structure
LOCATE ATOM
determination are summarised in the flow chart. POSITIONS
G

STRUCTURE
REFINEMENT

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 Diagram Of An Area Detector X-Ray Data Collection System.
Image Plate / CCD
The first crystallographic
data collection systems used Diffracted Beam & Spot

photographic methods. These

were replaced by automated
diffractometers which measured
reflections one at a time. A typical Crystal
Beam Stop


data collection took several days.
modern systems use area detectors
which measure 100s at a time.X-ray Beam

The crystal is oscillated over < 2°

while an image is collected then
rotated by the same amount
and oscillated again. The process is
repeated over a total range of about 180°.
Each image is exposed for < 100s.
Thus if readout time is ignored total
data collection time is often < 3 hr.
A typical image shown to the left.
A computer program is used to predict
the unit cell from several images.
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 Determination of the Lattice type and Space Group

High symmetry can lead to reflections being systematically absent from the
data set. Absent reflections have no measurable intensity. There are two types
of absences, General Absences and Special Absences.
The general absences determine the lattice type;
Primitive (P) has no general absences and no restrictions on h, k or l.
End Cantered (C) h+k=2n+1 are all absent.
Face Cantered (F) only h, k, l, all even or all odd are observed.
Body Cantered (I) h+k+l=2n+1 are all absent.

The special absences refer to specific sets of reflections and are used to
detect the presence of glide planes and screw axes. Some Space Groups
are uniquely determined by special absences but in many cases several
Space Groups will have to be considered.

Computer programs are able to lay out the data in tables with absences
indicated and possible Space Groups can be suggested however the choice of
Space Group will often need much thought.
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 Problems with X-ray Crystallography

Locating Hydrogen atoms - Hydrogen atoms make extremely small contributions

and for this reason X-ray crystallography is not a good technique for accurately
locating hydrogen atom positions. If the location of hydrogen atoms is of specific
interest (e.g. in the study of hydride structures and hydrogen bonding interactions)
use has got to be made of the much more expensive and less available
technique of neutron diffraction. The theory of neutron diffraction is very similar
to that for X-ray diffraction but an essential difference is that hydrogen atoms
scatter neutrons as effectively as many other atoms and for this reason they
can be located with good accuracy in the structure determination.

The Need for Single Crystals - In order to carry out a detailed X-ray structure
determination, it is essential to have a crystal of the material in question.
Many compounds cannot be crystallised and thus are not amenable to
diffraction studies. There are also commercially important materials such
as glasses and many ceramics which owe their unique properties to their
amorphous nature. Being amorphous (no long range order), the structures
of these materials cannot be investigated in detail by diffraction techniques.
Low Temperature Structure Determination – When X-ray data are collected at
low temperature (<-150 ºC) thermal ellipsoids are smaller and better defined.
N.B. bond lengths show very little variation with temperature.
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 POWDER X-RAY DIFFRACTOMETRY

A crystalline powder sample will

diffract X-rays but since the
orientations of the individual
crystals are random the data set
produced is a plot of intensity v.s.
diffraction angle or Bragg angle .

Here the sample is sitting on a

flat plate and the plate is turned
about the centre of the
diffractometer at half the rate
through which the counter
moves. This is the /2 or Bragg
scan method.
Notice the plot contains 2 on
the X-axis and X-ray intensity
on the y-axis.

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Uses of X-ray Powder Diffraction

In general, powder diffraction data are unsuitable for solving crystal structures.
Some advances have recently been made using the Rietveld method. However
this is far from trivial and it works best in relatively simple cases. It is very difficult
to be sure that the unit cell is correct as the reflections overlap and are difficult to
resolve from one another.
Important advantages and uses of powder diffraction:
1. The need to grow crystals is eliminated.
2. A powder diffraction pattern can be recorded very rapidly and the technique
is non-destructive.
3. With special equipment very small samples may be used (1-2mg.)
4. A powder diffraction pattern may be used as a fingerprint. It is often superior to
an infrared spectrum in this respect.
5. It can be used for the qualitative, and often the quantitative, determination of
the crystalline components of a powder mixture.
6. Powder diffractometry provides an easy and fast method for the detection of
crystal polymorphs. Powder patterns are provided when a drug is being
registered with the FDA. (Polymorphs are different crystal forms of the same
substance.)

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Calculations using X-ray powder diffraction patterns.
For an orthogonal system (a = b =  = 90°) the relationship
between
interplanar spacing (d) and the unit cell parameters is given by the
expression:
1 h2 k 2 l 2
2
 2  2  2
d ( h, k , l ) a b c

This is the expression for an orthorhombic crystal.

For the tetragonal system it reduces to
1 (h 2  k 2 ) l2
2
 2

d ( h,k ,l ) a c2

and, for the cubic system, it further reduces to

1 (h 2  k 2  l 2 )
2

d ( h,k ,l ) a2

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 Important Cubic Lattice Types
Two of the most important cubic lattice types are the NaCl type and the
CsCl type.

NaCl crystallizes in the Space Group Fm-3m

Stoichiometry (formula) from the Unit Cell

Site Na+ Cl-
Central 0 1
Face 6/2 0
Edge 0 12/4
Corner 8/8 0
Total 4 4

In the CsCl structure both ions have coordination numbers of 8 and the structure
is a simple primitive one with no centring.

Formula Cs at centre = 1
8 x 1/8Cl = 1 = CsCl

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Cubic close packed spheres

The unit cell of a cubic close packed

Metal has a face cantered or F type lattice
The formula of the unit cell is:
6 x ½ + 8 x 1/8 = 4

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The Bragg equation may be rearranged (if n=1)
2
from n  2d sin  to 2
 sin 2

4d

If the value of 1/(dh,k,l)2 in the cubic system equation above is inserted into
this form of the Bragg equation you have

2 2
sin   2 (h  k 2  l 2 )
2
4a

Since in any specific case a and l are constant and if l2/4a2 = A

sin 2   A(h 2  k 2  l 2 )

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 ANALYSIS OF X-RAY POWDER DIFFRACTION DATA

Diffraction data have been collected on a powder diffractometer for a series of

compounds that crystallise in the cubic system.
In the practical course each person will calculate the unit cell parameter and
density from an X-ray powder diffraction pattern.

Question 1
Aluminium powder gives a diffraction pattern that yields the following eight
largest d-spacings: 2.338, 2.024, 1.431, 1.221, 1.169, 1.0124, 0.9289
and 0.9055 Å. Aluminium has a cubic close packed structure and its
atomic weight is 26.98 and l = 1.5405 A .
Index the diffraction data and calculate the density of aluminium.

The Bragg equation,   2d sin  can be used to obtain sin, sin  
2d
The ccp lattice is an F type lattice and the only reflections observed are those
with all even or all odd indices.
Thus the only values of sin2 in sin 2   A( h 2  k 2  l 2 ) that are allowed

are 3A, 4A , 8A, 11A, 12A,16A and 19A for the first eight reflections.
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 Insert the values into a table and compute sin and sin2.
Since the lowest value of sin2 is 3A and the next is 4A the first
Entry in the Calc. sin2 column is (0.10854/3)*4 etc.

d/Å Sin Sin2 Calc. Sin2 (h, k, I)

2.338 0.32945 0.10854 (1,1,1)
2.024 0.38056 0.14482 0.14472 (2,0,0)
1.431 0.53826 0.28972 0.28944 (2,2,0)
1.221 0.63084 0.39795 0.39798 (3,1,1)
1.169 0.65890 0.43414 0.43416 (2,2,2)
1.0124 0.76082 0.57884 0.57888 (4,0,0)
0.9289 0.82921 0.68758 0.68742 (3,3,1)
0.9055 0.85063 0.72358 0.72360 (4,2,0)

The reflections have now been indexed.

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 Calculation of a
For the first reflection (for which h2 + k2 + l2 = 3)
sin2 = 3A = 3 ( l2 / 4a2 )
a2 = 3l2 / 4sin2
a = 4.04946 Å = 4.04946 x 10-8 cm.

Calculation of the density of aluminium

a3 = 66.40356 Å3 = 66.40356 x 10-24 cm3.
If the density of aluminium is r (g. cm.-3), the mass of the unit cell is
 x 66.40356 x 10-24 g.
The unit cell of aluminium contains 4 atoms.
The weight of one aluminium atom is 26.98/(6.022 x 1023) = 4.48024 x
10-23
and the weight of four atoms (the content of the unit cell) is 179.209 x
10-24.
r x 66.40356 x 10-24 = 179.209 x 10-24
p = 2.6988 g.cm-3.

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 The X-ray powder diffraction pattern of AgCl obtained using radiation of
wavelength 1.54Å is shown below. The peaks are labelled with 2θ values

Answer each of the following.

On the basis that the structure is cubic and of either the NaCl or CsCl type
1. Index the first six reflections. [15 marks], 2. Calculate the unit cell
parameter.[5 marks], 3. Calculate the density of AgCl. [5 marks]
(Assume the following atomic weights: Ag, 107.868; Cl, 35.453;
and Avogadro’s number is 6.022 x 1023)
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Since  values are available sin2 values can be calculated and inserted
in a table.

2  Sin2 Calc. Sin2

27.80 13.90 0.0577
32.20 16.10 0.0769 0.07693
46.20 23.10 0.1539 0.1539
54.80 27.40 0.2118 0.2116
57.45 28.73 0.2310 0.2308
67.45 33.73 0.3083 0.3077

From Sin2 = A(h2 + k2 + l2) the possible values are:

1. for a face centred lattice 3A, 4A , 8A, 11A, 12A and 16A
2. for a primitive lattice 1A, 2A, 3A, 4A, 5A and 6A
The second option is not possible as the first 2 are not in the ratio of 1:2.
To test the first option, divide the first by 3 and multiply the result by 4, 8 etc.

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Density of AgCl

Since sin2 = l2(h2 + k2 + l2)/4a2

a2 = (1.54)2.(16)/4(0.3083) using the largest (most accurate) 2
a2 = 30.7692
a = 5.547Ǻ (1Ǻ = 10-8 cm)
Formula wt. of unit cell = 4AgCl = 573.284g
This is the weight of 4 moles of AgCl.
The weight of 4 molecules is 573.284 / (6.02 x 1023)
Density = 573.284 / (6.02 x 1023)(5.547 x 10-8)3
A is in Ǻ thus the answer should be multiplied by 1 / 10-24

Density = 5.580 g/cm3

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Preferred Orientation Effects in X-ray Powder Diffraction Patterns
It is possible to calculate the theoretical diffraction pattern if the
crystal structure is known.

Nifedipine

Calculated pattern

Observed pattern

There are no preferred orientation effects here as all reflections have their
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 Benzoic acid

Calculated pattern

002
Observed pattern
004

There is clear preferred orientation here.

The 002 is the flat face exposed when the
needles lie down on a flat plate.
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Some points relating to preferred orientation effects.

• Preferred orientation effects are often observed for needles and plates.

• Preferred orientation effects can be reduced by sample rotation etc.

• However it is possible to obtain useful information when a stationary flat

sample holder is used without rotation and when preferred orientation
effects are at a maximum.

• If deviations from a theoretical pattern are measured they may be used

to monitor the morphology (shape) of crystals in a production batch.

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