BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

After studying this lecture you should be able to:-

1. draw Miller index of some crystal planes and directions of cubic as
well as hexagonal crystal types.
2. describe the principles of XRD and its applications
3. identify some kinds of crystal defects

3.1 Introduction

The crystallographic directions are fictitious lines

linking nodes (atoms, ions or molecules) of a crystal.
The crystallographic planes are fictitious planes
linking nodes.
Some directions and planes have a higher
density of nodes;

These dense planes have an influence on the behaviour of the crystal:

 Optical properties: in condensed matter, the light "jumps" from one atom to the
other with the Rayleigh scattering; the velocity of light thus varies according to
the directions, whether the atoms are close or far; this gives the birefringence.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

 adsorption and reactivity: the adsorption and the chemical reactions occur on
atoms or molecules, these phenomena are thus sensitive to the density of
nodes;
 surface tension: the condensation of a material means that the atoms, ions or
molecules are more stable if they are surrounded by other similar species; the
surface tension of an interface thus varies according to the density on the
surface.
- the pores and crystallites tend to have straight grain boundaries following
dense planes.
- cleavage
 dislocations (plastic deformation).
- The dislocation core tends to spread on dense planes (the elastic perturbation
is "diluted"); this reduces the friction (Peierls-Nabarro force), the sliding
occurs
more frequently on dense planes;
- The perturbation carried by the dislocation (Burgers vector) is along a dense
direction: the shift of one node in a dense direction is a lesser distortion;
- The dislocation line tends to follow a dense direction, the dislocation line is
often a straight line, a dislocation loop is often a polygon.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.2 Miller Indices

There are two equivalent ways to define the meaning of the Miller indices (Ashcroft
& Mermin, 1976): via a point in the reciprocal lattice, or as the inverse intercepts
along the lattice vectors. Both definitions are given below. In either case, one needs
to choose the three lattice vectors a1, a2, and a3 as described above. Given these,
the three primitive reciprocal lattice vectors are also determined, denoted b1, b2, and
b3.

Then, given the three Miller indices h, k, l, (hkl) denotes planes orthogonal to:
hb1 + kb2 + lb3
That is, (hkl) simply indicates a normal to the planes in the basis of the primitive
reciprocal lattice vectors. Because the coordinates are integers, this normal is itself
always a reciprocal lattice vector. The requirement of lowest terms means that it is
the shortest reciprocal lattice vector in the given direction.

Equivalently, (hkl) denotes a plane that intercepts the three points a1/h, a2/k, and a3/l
or some multiple thereof. That is, the Miller indices are proportional to the inverses
of the intercepts of the plane, in the basis of the lattice vectors. If one of the indices
is zero, it means that the planes do not intersect that axis (the intercept is "at
infinity").

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

The related notation [hkl] denotes the direction:

ha1 + ka2 + la3

That is, it uses the direct lattice basis instead of the reciprocal lattice. Note that [hkl]
is not generally normal to the (hkl) planes, except in a cubic lattice as described
below.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

Miller Conventions -- a guide for when to use { } vs ( ) and [ ] vs < >

1. As a crystal is periodic, there exist families of equivalent directions and planes.
2. Use the [ ] notation to identify a specific direction, i.e. [1,0,-1]
3. Use the < > notation to identify a family of equivalent directions, i.e. <110>
4. Use the ( ) notation to identify a specific plane, i.e. (113)
5. Use the { } notation to identify a family of equivalent planes, i.e. {311}

type: <100>
Equivalent directions:
[100],[010],[001]
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type: <110>
Equivalent directions:
[110], [011], [101],[-1-10], [0-1-1],
[-10-1], [-110], [0-11], [-101],
[1-10], [01-1], [10-1]
type: <111>
Equivalent directions:
[111], [-111], [1-11], [11-1]
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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

Case of the cubic structures

For the special case of cubic crystals, the lattice vectors are orthogonal and of
equal length; similarly for the reciprocal lattice. So, in this common case, the Miller
indices (hkl) and [hkl] both simply denote normals/directions in Cartesian
coordinates.

Diamond Unit Cell {100} planes {110} planes {111} planes

Exercises:
Draw the unit cell of NaCl and CsCl types of crystals and then draw:
1. {100} planes, {110} planes, {111} planes of both crystals.
2. The plane of (200), (121), (020) and (102) of both crystals.
3. The directions of [111] and [222] of both crystals.
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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

Case of the hexagonal and rhombohedral structures

With hexagonal and rhombohedral crystal systems, it is possible to use the
Bravais-Miller index which has 4 numbers (h k i l)
i = -h-k
where h, k and l are identical to the Miller index.
The (100) plane has a 3-fold symmetry, it remains unchanged by a rotation of
1/3 (2π/3 rad, 120°). The [100], [010] and the directions are really similar.
If S is the intercept of the plane with the axis, then
i = 1/S
i is redundant and not necessary.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3 X-Ray Diffraction

3.3.1 Basic Principles of X-Ray Diffraction

Laue equation
a sin  = n
The first
discovery of
X-ray

Bragg Law

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

X-Ray PRODUCTION

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

SINGLE CRYSTAL vs POLYCRYSTALLINE XRD

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.2 A Comparison of Some Diffraction Techniques

Neutron A nuclear reactor
Kinds and
sources of Electron A synchrotron
incident beams
X-ray A generator
Cu, Mo, Cr, Fe, Ag

Because neutron is scattered by atomic nuclei, neutron diffraction is useful for locating hydrogen
atoms (which have a much larger relative effect on neutron than X-ray scattering). Neutron diffraction
is also able to distinguish the heavy elements that are neighbor each other in the periodic system.
Since it does not have any charge but magnetic moment, the neutron diffraction can be applied to
investigate magnetic structure. Disadvantages are that, this method required larger crystal and
longer measuring time.

Electron diffraction can be used for structural investigation of small molecules even with only a few
atoms because the interaction of electron radiation with material not only with nuclei but also
electron mantel. But it is thermally sensitive and only two dimensional structural information can be
obtained.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.3 Single Crystal XRD

Measurements:
• on a Nonius (CAD4) Mac 3 diffractometer
• at low temperature (-70 °C)
• employing vaporized liquid nitrogen

Monocromator:
• graphite - monochromated Mo-K1 radiation
( = 0.71069 Å)

Solving a crystal structure:

• direct methods SHELXS 86
• full-matrix least squares refinement SHELXL 97

Viewing a crystal structure:

• ORTEP.
Enraf-Nonius CAD4 XRD

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

The steps involved in a crystal structure determination

Time taken Operation Information obtained

? 1. Select a suitable crystal

and mount it.

minutes/hours 2. Obtain unit cell geometry and a, b, c and , , 

preliminary symmetry crystal system, space
information group

hours/days 3. Measure intensity data list of hkl I(I)

minutes 4. Data reduction (various list of : hkl F(F) or

corrections applied to data) hkl F2(F2)

from minutes 5. Solve the structure: some or all non-H

upwards a. Patterson methods atom positions
b. Direct methods
c. Other methods

minutes/hours 6. Complete the structure to all atom positions

find all atoms: Fourier and
difference Fourier synthesis

minutes - days 7. Refine the structure atom positions and

displacement parameter

? 8. Interpret the results molecular geometry,

packing arrangement, etc.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

Single Crystal XRD studies on donor power of

R3PSeX2 (R = C6H11, (CH3)2N; X2 = I2, IBr)

Comparison of d(I-I) in Å
I2 2.67
(C6H11)3PSeI2 2.9477(7)
((CH3)2N)3PSeI2 2.9678(6)

Donor power
((CH3)2N)3PSe > (C6H11)3PSe
ORTEP views of (C6H11)3PSe I2

Bond lengths [Å] (C6H11)3PSeI2 (C6H11)3PSeIBr ((CH3)2N)3PSeI2

R and X2 affect
I - Se 2.7261(9) 2.6843(11) 2.7035(14)
the donor power
Se - P 2.1831(18) 2.192(3) 2.190(8)

Karyasa, I W., 2002, Proceedings of International 7th ISSM 2002, Berlin, 415-421.
Karyasa, I W., 2002, Proceedings of International SKET 2002 IASI, Hamburg, 106-109.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.4 Powder X-Ray Diffraction

The scheme of a X-ray diffractometer

RT-Diffraktometer HT-Diffraktometer
Siemens D5000 (Cu K1,  = 154.18 pm) STOE Stadi P (Mo Ka1,  = 70.9 pm)

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.5 The Uses of Powder XRD

 to identify phases
 to analyze phase quantity
 to determine unit cell parameters
 to determine crystal structure
 to measure particle size
 to study crystal defects and disorder

A Comparison between single crystal (left) and powder XRD (right) (Nader and Proffen, 1996)

Diff. peak in perfect single crystal is without peak Diff. peaks in powder polycrystalline are overlapping
overlapping and broadening and broadening, so their profile is bad.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.6 Phase Identification

Powder XRD Patterns a “fingerprint“ Powder Diffraction File (PDF)

A Solid State Reaction of Synthesized -SiC with Vanadium

Figure 2. X-ray diagram of a sample in the V-Si-C

Figure 1. X-ray diagram of synthesized -SiC at 1500°C
system. Solid -SiC reacts with the transition metal
(8h; vacuum). Instead of main phase -SiC (PDF no. 29-
vanadium at temperature of 1200°C under vacuum
1129, there are carbon and an unknown reflection (?)
which corresponds to disorder or defects in -SiC phase. resulting silicide, V5Si3 (PDF no. 8-0379) and carbide,
V8C7 (PDF no. 35-0786) phases instead of -SiC.

Karyasa, I W., Walter, D., 2002, Proceedings of International 7th ISSM, Berlin: 449-453.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.7 Quantitative Analysis

A Quantitative Analysis on Phase Transformation

of Doped and Vacuum Sintered -SiC

Peak 1 Peak2 Calibration

 (101)  (102)
 (111) method

R = 0.98301

The -SiC (SiC-6H) phase

Peak area 1 of -SiC (101)
-SiC phase content =
Peak area 2 of -SiC(102) + -SiC(111)
X-ray diagram of calcium doped and vacuum
content (%) versus calcium
sintered -SiC (1950°C; 2hours) in
doping concentration (%
comparison with a diagram of starting
mol) of vacuum sintered -
material -SiC at room temperature and
SiC (1950°C; 2 hours).
vacuum sintered undoped -SiC (1950°C; 2
hours)

Karyasa, I W., Walter, D., 2003, Proceedings of International 8th ISSM 2003, Delft: 175-179.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.8 Rietveld Method and Solving Crystal Structure

of a Powder XRD Diagram
XRD peak F(2) principally consists of a background (B), an integral peak intensity
(I) and peak profile in which its spreading spectra of used radiation (W) splits (*)
into the instrumental influence (G) and corresponding its real structure of sample
(S) (Klug and Alexander, 1974).

The use of Rietveld method can help to reach a better profile fitting, so that the phase
problem can be solved, Furthermore it can used to refine the solved structure.

Profile fitting of a peak of XRD spectra of a Sodalith material after Rietveld refinement: without asymmetric correction (left);
with asymmetric correction (middle); and with asymmetric correction after axial divergence (right) (van Smaalen, et. al,
1997).
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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

Powder XRD of a new CoSi (CsCl type)

Powder XRD of a new ternary
stabilized by -SiC Matrix
compound in system Cr-Si-C

Rietveld refinement (GSAS) of powder XRD diagram (Cu K1) Rietveld refinement (Fullprof) of powder XRD diagram
of the vacuum sintered sample of Co + Si + C (1:1:1) at (Cu K1) of the vacuum sintered sample of Cr + Si + -SiC
1400°C (8 h). (5:2:1) at 1200°C (40 h).

Crystal system: hexagonal

Space group: Pm3 m (Nr. 221); Space group P 63/mcm (no. 193)
Cell parameter a = 698.454(22) pm
Cell parameter: b = 698.454(22)pm
a = 281,62(2) pm; c = 474.072(14) pm
Cell volume 200.28(8) x 106 pm3
V = 22,337(7) x 106 pm3 Calculated density 5.655 g/cm3
Atomic coordinates:
Atom Wyck. Occ. x y z
Cr1 6g 0.25 0.24 0 1/4
Karyasa, I W., Dissertation, TU Berlin, 2004 Cr2 12i 0.15 1/3 2/3 0
Si1 6g 0.25 0.60 0 1/4
Walter D., Karyasa, I W., Irran, E., Kurzreferate Band 8, GDCh- C1 2b 0.05 0 0 0
Jahrestagung Chemie, München, 2003, 157.
Karyasa, I W., Dissertation, TU Berlin, 2004

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.9 High Intensity XRD from Synchrotron Radiation

Synchrotron Cycle at Hasylab (DESY-Hamburg) XRD (Synchrotron) of the system Cr-Si-C

CoSi
(CsCl type) Rietveld refinement (Fullprof) of powder XRD
diagram (Synchrotron, = 70,9942 pm) of the
vacuum sintered sample of Cr + -SiC (5:3) at
1400°C (8 h). It shows multiphase sample that its
XRD diagram (Siemens D5000) could not be well
characterized.

Rietveld refinement (Fullprof) of powder XRD diagram (Synchrotron,

= 70,9942 pm) of the vacuum sintered sample of Co + Si + C (1:1:1)
at 1400°C (8 h). The refinement result is in a good agreement with
that of XRD Siemens D5000 (Cu K1) but better intensity.

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BASIC CRYSTALLOGRAPHY FOR CHEMISTRY Chapter 3

3.3.10 High Temperature XRD

• to study structural polymorphism and phase transition

Effect of SiC-Matrix on Stabilizing the

new CoSi (CsCl type)*
• CoSi (CsCl type) found im system Co-Si-
C (1400°C, vacuum) and stable until
1600°C in the fully covered by SiC matrix.
Without the presence of carbon atom or
SiC matrix (i.e. in system Co-Si) no such
compound observed under those
conditions.
• Effect of SiC-Matrix was investigated
through ball milling the powdered sample
until at least parts of CoSi (CsCl type) not
fully covered by SiC matrix, than followed
18000
by in situ XRD measurements up to 
 -SiC
16000
* -CoSi (FeSi-Typ)
1000°C. After in situ experiment the 14000 
Co2Si
Absolute Intensität (counts)

sample was cooled down to RT and 12000 

measured again. 10000

*
• It can be seen that CoSi(CsCl) without
8000

-SiC-Matrix-



fully covered by SiC matrix is stable up to

6000
* 

4000 

influence
750°C (upper diagrams left and right), *
  





* *
2000 
  *** * 
* 

higher temperature than that it was 0
CoSi -CoSi
transferred to CoSi (FeSi type) and Co2Si 10 20 30 40 50 (CsCl type) (FeSi type)
2  (deg)
(lower diagram)

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