2.

Principles of X-ray crystallo

graphy

1
 The Seven Crystal Systems (1)
• Define unit cell shapes.
• Must fill 3D space – this imposes
constraints on allowed unit cell symmetry:

For example: it is not possible

to fill 2D space with
pentagons, so it is not
possible to have five-fold
crystallographic symmetry.

2
 Importance of Symmetry
• Model a crystal structure with atomic
positions.
• Making maximum use of symmetry
minimizes the number of parameters to be
determined.
• Crystal system defines the maximum
amount of symmetry that can expressed b
y a crystal structure.
3
The Concept in Molecules

This molecule has D4h symmetry.

Therefore the coordinates of
all F-atoms can be derived from
those of just one.

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5
 Ammonium oxalate hydrate
• Cell contains 38 atoms, each with 3
coordinates (114 positional parameters to
determine)
• If symmetry is taken into account this
reduces to 28.

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The Seven Crystal Systems (2)

only seven possible s

hapes of three dimen
sional unit cells; cryst
al systems

7
 Lattice centering
• Primitive; P
• Face-centered; F, A, B, C
• Body centered; I

8
Primitive vs. centered

9
 Centered Lattices

• In order to make maximum use of symmet

ry it is sometimes necessary to double the
area of a 2D unit cell (or 2x, 3x, 4x for a 3
D unit cell).
10
Not all centered lattices are unique.
Consider a centered square lattice:

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Not all centered lattices are unique.
Consider a centered square lattice:

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14 Bravais Lattices

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Crystal Planes and Miller Indexes

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The right-handed rule
• Thumb is x, forefinger is y and
middle finger is z.
• Right handed screw motions
are: +x into +y makes a
positive motion into +z. It
follows that +y into +z is a +x
screw and +z into +x is a +z
screw.
• Whenever in doubt, pull your
hand out of your pocket to set
up coordinate systems. Left
handed coordinate systems
lead to negative cell volumes!

15
Crystal Planes and Miller Indexes:
Planes and directions

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Crystal Planes and Miller Indexes:
Equivalent planes and directions

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 Animations
• Miller Indexes

• Equivalent planes

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 X-ray powder diffraction

• Identification of compounds
• Crystallinity
• Phases
• Wide uses in chemistry, minerals, material sciences 19
 Reciprocal lattice (1)
• P. P. Ewald in 1913

• The points of a reciprocal lattice represent the pl

anes of the direct (i.e. real) lattice that it is forme
d from.

• The direct lattice determines (through defined rel

ationships) the reciprocal lattice vectors, the latti
ce point spacing and the associated reciprocal di
rections.
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 Reciprocal lattice (2)

The reciprocal lattice has

Consider the two dimensio reciprocal vectors a* and b*,
nal direct lattice shown belo separated by the angle *. a* will
w. It is defined by the real v be perpendicular to the (100)
ectors a and b, and the ang planes, and equal in magnitude
le . The spacings of the (1 to the inverse of d100. Similarly,
00) and (010) planes (i.e. d b* will be perpendicular to the
(010) planes and equal in
100 and d010) are shown.
magnitude to the inverse of d010.
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Hence  and * will sum to 180º.
 Reciprocal lattice (3)
• Due to the linear relationship between planes (fo
r example, d200 = (1/2)d100), a periodic lattice is g
enerated. In general, the periodicity in the recipr
ocal lattice is given by

• In vector form, the general reciprocal lattice vect

or for the (hkl) plane is given by

• where nhkl is the unit vector normal to the (hkl) p

lanes.
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Array of points making up the
reciprocal lattice

23
For non-primitive lattices, such The reciprocal lattice is now construc
as a C-centred lattice, systemat ted using the different lattice vectors
ic absences can occur in the re and interplanar spacings. When it is l
ciprocal lattice and in the diffrac abelled with respect to the new recipr
tion patterns. This is due to the ocal lattice vectors, the dashed spots
construction of the lattices. are "absent".
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 Systematic Absence
• These absences help distinguish different
crystal lattice types from the diffraction
patterns, since each type has a
characteristic pattern of absences. In this
example, points with ( h + k ) as an odd
integer are absent, due to the definition of
the unit cell.

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 The Ewald Sphere
• Consider a circle of radius r, with points X and Y lying
on the circumference.

If the angle XAY is defined as , then the angle XOY will be

2by geometry. Also,
sin  = XY/2r

If this geometry is constructed in reciprocal space, then it has26

some important implications.
• The radius can be set to 1/, where  is the wavelength
of the X-ray beam.

• If Y is the 000 reciprocal lattice point, and X is a general

point hkl, then the distance XY is 1/dhkl

• Hence

• i.e.
 = 2 dhkl sin 

• This is Bragg's Law. Effectively, the application of this cir

cle to the reciprocal lattice defines the points which satisf
y Braggs’ Law (X on the diagram). Therefore the (hkl) pla
nes corresponding to these reciprocal points will diffract
X-rays of wavelength  at the angle .

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• Crystal lattices are three-dimensional, a
nd hence so are their reciprocal lattices.
The necessary circle is now a sphere. T
his is known as the Ewald sphere. 28
The Ewald sphere construction shares the p
roperties of Bragg's law.

29
• Diffraction occurs when a reciprocal lattice point intersect
s the Ewald sphere.

30
• The "limiting sphere“ sphere represents the limit of resolution of yo
ur crystal. So for a crystal diffracting to 2 Å this sphere would have
a radius of 1/2. All reciprocal lattice points within this sphere can in
principle be made to diffract by letting them intersect the Ewald sph
ere.

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Resolution and disorder

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View a step by step construction of
the Ewald sphere.

• http://www.msm.cam.ac.uk/doitpoms/tlplib/
DD2/ewald.php

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 Ewald’s sphere construction in 3D
• http://www.matter.org.uk/diffraction/geome
try/ewald_sphere_construction_3D.htm

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Limiting sphere – the complete data
set

If one rotates the Ewald sphere co

mpletely about the (000) reciproca
l lattice point in all three dimension
s, the larger sphere (of radius 2/λ)
contains all of the reflections that i
t is possible to collect using that w
avelength of X-rays. This construc
tion is known as the “Limiting sphe
re” and it defines the complete dat
a set. Any reciprocal lattice points
outside of this sphere can not be o
bserved.

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• Note that the shorter the wavelength of the X-radiation, t
he larger the Ewald sphere and the more reflections may
be seen (in theory).

• The limiting sphere will hold roughly (4/3πr3/ V*) lattice p

oints. Since r = 2/λ, this equates to around (33.5/ V*λ3) or
(33.5 V/λ3) reflections.

• For an orthorhombic cell with a volume of 1600Å3, this m

eans CuKαcan give around 14,700 reflections while MoKα
would give 152,000.

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 The Sphere of Reflection and Bra
gg’s Law

Copper radiation used for

macromolecular structure
s of large unit cell and org
anic molecules. Diffracted
beams are more separate
d on a detector if a longer
wavelength is used.

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A reciprocal lattice plot

38
 h

Different sets of planes

in the crystal give rise to Circles of constant
different diffraction spots. k theta (resolution)
39
 x
O

y
40
 x
O
(100) planes

y
41
 h

k 42
 x
O
(200) planes

y
43
 x
O

y
44
 x
O

X-axis cut
At +1
Y-axis cut
at 1/2

Z-axis not cut at all y

= Cut at . 45
 x
O

(1,2,0) planes
y
46
 h

k 47
 h

k 48
Direct Lattice vs. Reciprocal Latti
ce
• Recall that X-rays reflect from electrons.
• The direct lattice representation shown earlier is filled wit
h atoms and molecules which diffract X-rays.
• The reciprocal lattice adopts an inverse motif where the
axes are measured in Å-1. The volume between the recip
rocal lattice vertices is void. The relative intensity is mark
ed at integer indices, e.g., (123).
• Bragg’s Law, 2dsinθ =nλ, can be rearranged to test for th
e appearance of reflections. The general form for Bragg’
s Law in reciprocal space is sinθ =nλ/ 2d. This means th
at diffracted beam is redirected by a known value for a c
ertain d-spacing and X-ray wavelength.

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Orthorhombic Direct and Recipro
cal Cell Relationships

50
Monoclinic Direct and Reciprocal
Cell Relationships

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Triclinic Direct and Reciprocal C
ell Relationships

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 Questions
• http://www.msm.cam.ac.uk/doitpoms/tlplib/
DD2/questions.php

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