Symmetry and crystal lattices

4. Consider the crystal structure of calcium fluoride

4.1 Calculate the number of calcium and fluoride ions in the unit cell using the following symmetry
operators.

Ca: (0,0,0) + FCC translations

F: (¼,¼,¼) + FCC translation
F: (¾,¾,¾) + FCC translation
FCC = (1/2 0 1/2; 1/2 1/2 0; 0 1/2 1/2)
4.2. Check if the molecular formula (CaF2) is consistent with the unit cell content.

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Symmetry and crystal lattices (cont)

This Figure is not necessary to solve the problem.

Unit cell

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Symmetry and crystal lattices (cont)
Faces
Ca: (0,0,0) + FCC translations
FCC = (1/2 0 1/2; 1/2 1/2 0; 0 1/2 1/2)

(0,0,0) + (1/2 0 1/2) = (1/2 0 1/2)

(0,0,0) + (1/2 1/2 0) = (1/2 1/2 0)

(0,0,0) + (0 1/2 1/2) = (0 1/2 1/2)

The atomic positions of the calcium cation on 3 faces of the unit cell (cube)

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Symmetry and crystal lattices (cont)

How are the other Ca atomic positions on remaining faces generated?

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Symmetry and crystal lattices (cont)

Crystals have translational symmetry

(0 0 1) (1 0 0) (0 0 1)

Remaining three faces

(0,0,0) + (1/2 0 1/2) = (1/2 0 1/2) (0 1 0) + (1/2 0 1/2) = (1/2 1 1/2)

(0,0,0) + (1/2 1/2 0) = (1/2 1/2 0) (0 0 1) + (1/2 1/2 0) = (1/2 1/2 1)

(0,0,0) + (0 1/2 1/2) = (0 1/2 1/2) (1 0 0) + (0 1/2 1/2) = (1 1/2 1/2)

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Symmetry and crystal lattices (cont)
Corners
(0,0,0) + (0 0 1) = (0 0 1)
Ca: (0,0,0) + FCC translations

Crystals have translational symmetry (0,0,0) + (1 0 0) = (1 0 0)

(0 0 1) (1 0 0) (0 0 1) (0,0,0) + (0 0 1) = (0 0 1)

000
000

<
<

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Symmetry and crystal lattices (cont)

Translational symmetry Remaining four

(0,0,0) + (0 0 1) = (0 0 1)
(0 0 1) + (1 0 0) = (1 0 1)

(0,0,0) + (1 0 0) = (1 0 0) (1 0 0) + (0 1 0) = (1 1 0)
(0,0,0) + (0 0 1) = (0 0 1)
(0 1 0) + (0 0 1) = (0 1 1)

(0 1 0) + (1 0 1) = (1 1 1)

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Symmetry and crystal lattices (cont)
F-

F: (¼,¼,¼) + FCC translation The two F- anions are not related by any
F: (¾,¾,¾) + FCC translation symmetry operation

FCC = (1/2 0 1/2; 1/2 1/2 0; 0 1/2 1/2)

Remaining three
(¼,¼,¼) + (1/2 0 1/2) = (3/4 1/4 3/4)

(¼,¼,¼) + (1/2 1/2 0) = (3/4 3/4 1/4)

(¼,¼,¼) + (0 1/2 1/2) = (1/4 3/4 3/4)

Four positions in the unit cell related by symmetry

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Symmetry and crystal lattices (cont)
F-

F: (¼,¼,¼) + FCC translation The two F- anions are not related by any
F: (¾,¾,¾) + FCC translation symmetry operation

FCC = (1/2 0 1/2; 1/2 1/2 0; 0 1/2 1/2)

Remaining three
(¾,¾,¾)+ (1/2 0 1/2) = (5/4 3/4 5/4) Out of unit cell (5/4 3/4 5/4)+ (-1 0 -1) = (1/4 3/4 1/4)

(¾,¾,¾) + (1/2 1/2 0) = (5/4 5/4 3/4) (5/4 5/4 3/4) + (-1 -1 0) = (1/4 1/4 3/4)

(¾,¾,¾) + (0 1/2 1/2) = (3/4 5/4 5/4) (3/4 5/4 5/4) ) + (0 -1 -1) = (3/4 1/4 1/4)

Four positions in the unit cell related by symmetry

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 Symmetry and crystal lattices (cont)

4.2. Check if the molecular formula (CaF2) is consistent with the unit cell
content.

F-
8 F- inner

Ca2+
Occupation factor
6 on Faces and 8 at corners

Number of Ca2+ in the unit cell 6x1/2+8x1/8 = 4 Ca2+:F- = 4:8 = 1:2 CaF2

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Structure factors calculations

1. The unit cell of a two-dimensional crystal structure contains four atoms, two of type P, and
two of type Q, with the following fractional coordinates

1.1 Calculate the F(hkl) for the reflections 5,0; 0,5; 5,5 and 5,10 as function of fP
and fQ.

1.2 Assuming fP = 2fq, calculate the phase of each reflection.

x y
P1 0.1 0.2
P2 0.9 0.8
Q1 0.2 0.7
Q2 0.8 0.3

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 !"#$%&'#()%**,- +,,,

F (hkl ) = F (hkl ) eij ( hkl )

F (hkl ) = A(hkl )2 + B(hkl )2

tan f (hkl ) = B(hkl ) / A(hkl )

n n
2 π i (hx +ky j +l z j ) iφ j
Fhkl = ∑ f j e = ∑ f je
!"#$%"&'#$()$#&*"$+#)#*,-(.$"/0
j=1 j=1

!"#$%&'( )*&"%&+
e± if = cos j ± isenj
$

𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#
$

𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

2023 !"# X-ray Crystallography
𝐹 ℎ𝑘𝑙 = 𝐴 ℎ𝑘𝑙 + 𝑖𝐵 ℎ𝑘𝑙

$
P1 N=4

𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#

$ P1 = blue solid circles

𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!
!"# P2 = red open circles

𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#

𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#
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 For all five reflections
The crystal has only two dimensions
%
x y
𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦!
P1 0.1 0.2
!"#
P2 0.9 0.8
$ Q1 0.2 0.7
𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! Q2 0.8 0.3
!"#

Refection (5,0)

$ $

𝐴 5,0 = & 𝑓% cos 2𝜋 5𝑥! + 0𝑦! + & 𝑓& cos 2𝜋 5𝑥! + 0𝑦!
!"# !"#

𝐴 5,0 = 𝑓% cos 2𝜋 5𝑥0.1 + 𝑓% cos 2𝜋 5𝑥0.9 + 𝑓& cos 2𝜋 5𝑥0.2 +𝑓& cos 2𝜋 5𝑥0.8

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 𝐴 5,0 = 𝑓% cos 2𝜋 5𝑥0.1 + 𝑓% cos 2𝜋 5𝑥0.9 + 𝑓& cos 2𝜋 5𝑥0.2 +𝑓& cos 2𝜋 5𝑥0.8

𝐴 5,0 = 𝑓% cos 𝜋+ 𝑓% cos 9𝜋+ 𝑓& cos 2𝜋+𝑓& cos 8𝜋

𝐴 5,0 = −𝑓% -𝑓% + 𝑓& +𝑓&

𝐴 5,0 = −2𝑓% +2𝑓&

B 5,0 = 𝑓% sen 2𝜋 5𝑥0.1 + 𝑓% sen 2𝜋 5𝑥0.9 + 𝑓& sen 2𝜋 5𝑥0.2 +𝑓& sen 2𝜋 5𝑥0.8

𝐵 5,0 = 𝑓% sen 𝜋+ 𝑓% sen 9𝜋+ 𝑓& sen 2𝜋+𝑓& sen 8𝜋 =0

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 Reflection A(h,k) B(h,k)
(5,0) −2𝑓6 +2𝑓7 0
(0,5) 2𝑓6 −2𝑓7 0
(5,5) −2𝑓6 − 2𝑓7 0
(5,10) −2𝑓6 + 2𝑓7 0

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 x y
'
P1 0.1 0.2
𝐴 0,5 = & 𝑓! cos 2𝜋 0𝑥! + 5𝑦!
P2 0.9 0.8
!"#
Q1 0.2 0.7
Q2 0.8 0.3

𝐴 0,5 = 𝑓& cos 2𝜋 5𝑥0.2 + 𝑓& cos 2𝜋 5𝑥0.8 + 𝑓' cos 2𝜋 5𝑥0.7 + 𝑓' cos 2𝜋 5𝑥0.3

A 0,5 = 𝑓& cos 2𝜋 + 𝑓& cos 8𝜋 + 𝑓' cos 7𝜋 + 𝑓' cos 3𝜋

A 0,5 = 2𝑓& −2𝑓'

𝐵 0,5 = 𝑓& sen 2𝜋 5𝑥0.2 + 𝑓& sen 2𝜋 5𝑥0.8 + 𝑓' sen 2𝜋 5𝑥0.7 + 𝑓' sen 2𝜋 5𝑥0.3

B 0,5 = 𝑓& sen 2𝜋 + 𝑓& sen 8𝜋 + 𝑓' csen 7𝜋 + 𝑓' sen 3𝜋 = 0

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 The crystal has only two dimensions
Refection (5,5) x y
P1 0.1 0.2
%
P2 0.9 0.8
𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦!
Q1 0.2 0.7
!"#
Q2 0.8 0.3

𝐴 5,5 = & 𝑓! cos 2𝜋 5𝑥! + 5𝑦!

!"#

𝐴 5,5 = 𝑓& cos 2𝜋 5𝑥0.1 + 5𝑥0.2 + 𝑓& cos 2𝜋 5𝑥0.9 + 5𝑥0.8 + 𝑓' cos 2𝜋 5𝑥0.2 + 5𝑥0.7 + 𝑓' cos 2𝜋 5𝑥0.8 + 5𝑥0.3

𝐴 5,5 = 𝑓& cos 10𝜋 0.3 + 𝑓& cos 10𝜋 1.7 + 𝑓' cos 10𝜋(0.9) + 𝑓' cos 10𝜋 1.1

𝐴 5,5 = 𝑓& cos 3𝜋 + 𝑓& cos 17𝜋 + 𝑓' cos 9𝜋 + 𝑓& cos 11𝜋 = −2𝑓& − 2𝑓'
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 𝐵 5,5 = 𝑓& sen 3𝜋 + 𝑓& sen 17𝜋 + 𝑓' sen 9𝜋 + 𝑓& sen 11𝜋 = 0 The crystal has only two dimensions

x y
P1 0.1 0.2
Refection (5,10)
P2 0.9 0.8
% Q1 0.2 0.7
𝐴 5,10 = & 𝑓! cos 2𝜋 5𝑥! + 10𝑦! Q2 0.8 0.3
!"#

𝐴 5,10 = 𝑓& cos 2𝜋 5𝑥0.1 + 10𝑥0.2 + 𝑓& cos 2𝜋 5𝑥0.9 + 10𝑥0.8 + 𝑓' cos 2𝜋 5𝑥0.2 + 10𝑥0.7 +
𝑓' cos 2𝜋 5𝑥0.8 + 10𝑥0.3

𝐴 5,10 = 𝑓& cos 2𝜋 2.5 + 𝑓& cos 2𝜋 12.5 + 𝑓' cos 2𝜋 8 + 𝑓' cos 2𝜋 7

𝐴 5,10 = 𝑓& cos 5𝜋 + 𝑓& cos 25𝜋 + 𝑓' cos 16𝜋 + 𝑓' cos 14𝜋 = −2𝑓& + 2𝑓'

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 The crystal has only two dimensions
Refection (5,5) x y
P1 0.1 0.2
%
P2 0.9 0.8
𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦!
Q1 0.2 0.7
!"#
Q2 0.8 0.3

𝐴 5,5 = & 𝑓! cos 2𝜋 5𝑥! + 5𝑦!

!"#

𝐴 5,5 = 𝑓& cos 2𝜋 5𝑥0.1 + 5𝑥0.2 + 𝑓& cos 2𝜋 5𝑥0.9 + 5𝑥0.8 + 𝑓' cos 2𝜋 5𝑥0.2 + 5𝑥0.7 + 𝑓& cos 2𝜋 5𝑥0.8 + 5𝑥0.3

𝐴 5,5 = 𝑓& cos 10𝜋 0.3 + 𝑓& cos 10𝜋 1.7 + 𝑓' cos 10𝜋(0.9) + 𝑓& cos 10𝜋 1.1

𝐴 5,5 = 𝑓& cos 3𝜋 + 𝑓& cos 17𝜋 + 𝑓' cos 9𝜋 + 𝑓& cos 11𝜋 = −2𝑓& − 2𝑓'
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𝐵 5,5 = 𝑓& sen 3𝜋 + 𝑓& sen 17𝜋 + 𝑓' sen 9𝜋 + 𝑓& sen 11𝜋 = 0

1.1 Calculate the F(hkl) for the reflections 5,0; 0,5; 5,5 and 5,10 as function of fP and fQ

Reflection A(h,k) B(h,k)

(5,0) −2𝑓% +2𝑓& 0

F(h,k)
(0,5) 2𝑓% −2𝑓& 0
(5,5) −2𝑓% − 2𝑓& 0
(5,10) −2𝑓% + 2𝑓& 0

Depending on the magnitude of fp and fq scattering

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factors
1.2 Assuming fP = 2fq, calculate the phase of each reflection

Reflection A(h,k) A(h,k) Phase ∅ 𝑓𝑞 > 0

final
(5,0) −2𝑓6 +2𝑓7 −4𝑓7 +2𝑓7 −2𝑓7 𝜋 tan f (hkl ) = B(hkl ) / A(hkl )

(0,5) 2𝑓6 −2𝑓7 4𝑓7 −2𝑓7 2𝑓7 0 ((*+,) /

tan 𝜙 = =
(.(*+,)) .(*+,)
(5,5) −2𝑓6 − 2𝑓7 −4𝑓7 -2𝑓7 −6𝑓7 𝜋
(5,10) −2𝑓6 + 2𝑓7 −4𝑓7 +2𝑓7 −2𝑓7 𝜋
tan 𝜙 = 0 𝑡ℎ𝑒 𝑎𝑛𝑔𝑙𝑒 𝑖𝑠 0

tan 𝜙 = 0 𝑡ℎ𝑒 𝑎𝑛𝑔𝑙𝑒 𝑖𝑠 𝜋

Depending on the signal of A component

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 2. The a-Uranium crystallizes in the orthorhombic unit cell with uranium occupying four special
positions given by

±{0,y, ¼; ½, ½+y,1/4}

and the real and imaginary components of the structure factor are given as
$
A(hk0) = 4cos2p[ky+(h+k)/4]cos2p(h+k)/4
𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!
!"#
B(hk0) = 0 $

𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#
2.1 the crystal is centrosymmetric. Comment this statement.

0,y, ¼; ½, ½+y,1/4

0,-y, -¼ -½, -½- y,-1/4

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 2. Among 0.15 and 0.10 indicate the most probable value for the y coordinate using the intensity data
of 020 and 110 (see below)

hkl |Fo(hkl)| fU

020 88.5 70.0

110 268.9 80.0

Strategy: we have to calculate the |Fc(hkl)| followed by the comparison between |Fc(hkl)| and |Fo(hkl)|

2023 X-ray Crystallography

 A(hk0) = 4cos2p[ky+(h+k)/4]cos2p(h+k)/4

A(020) = fU4cos2p[2y+(0+2)/4]cos2p(0+2)/4

A(020) = fU4cos2p[2y+1/2]cos2p(1)/2

-1
A(020) = -4fUcos2p(2y+1/2)

y=0.1 y=0.15

A(020) = -4fUcos2p(2x0.1+1/2) A(020) = -4fUcos2p(2x0.15+1/2)

A(020) = -4fUcos2p(0.7) A(020) = -4fUcos2p(0.8)

A(020) = -4fUcos1.4p A(020) = -4fUcos1.6p

-0.309 0.309
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 A(020) = -4fUcos1.4p A(020) = -4fUcos1.6p
-0.309 0.309

A(020) = -4x70.0xcos1.4p =86.15 A(020) = -4x70x0.309 =-86.15

𝐹(ℎ𝑘𝑙) = 𝐴(ℎ𝑘𝑙)0 + 𝐵(ℎ𝑘𝑙)0

𝐹(020) = 𝐴(020)0 + 0

A(110) = -4x80.0x(-0.809)
= (−86.15)0 +0 = 86.15

It is necessary to use another reflection

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 110

A(hk0) = 4fUcos2p[ky+(h+k)/4]cos2p(h+k)/4

A(110) = 4fUcos2p[1y+(1+1)/4]cos2p(1+1)/4

A(110) = 4fUcos2p(y+1/2)cos2p(1/2)
-1 A(110) = -4fUcos2p(0.1+1/2)
A(110) = -4fUcos2p(y+1/2)

y=0.15
y=0.1

A(110) = -4fUcos2p(0.1+1/2) A(110) = -4fUcos2p(0.15+1/2)

A(110) = -4fUcos2p(0.6) A(110) = -4fUcos2p(0.65)

A(110) = -4fUcos1.2p A(110) = -4fUcos1.3p

2023 X-ray Crystallography
 A(110) = -4fUcos1.2p A(110) = -4fUcos1.3p

-0.809 -0.588

A(110) = -4x80.0x(-0.809) A(110) = -4x80.0x(-0.588)

188.6
258.8

𝐹(110) = 𝐴(110)0 = 258.8 𝐹(110) = 𝐴(110)0 = 188.6

Conclusion. The correct coordinate is y=0.10

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3. Determine the structure factor and the phases for a centrosymmetric crystal.

𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧! xyz

!"#
P1
-x,-y,-z
$

𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#

𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#

$/0 $

𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧! + & 𝑓! cos 2𝜋 ℎ(−𝑥! ) + 𝑘(−𝑦! ) + 𝑙(−𝑧! )
!"# $
2#
0

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 $/0 $

𝐴 ℎ𝑘𝑙 = & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧! + & 𝑓! cos 2𝜋 ℎ(−𝑥! ) + 𝑘(−𝑦! ) + 𝑙(−𝑧! )
!"# $
2#
0

cos −𝛼 = cos 𝛼

$/0

𝐴 ℎ𝑘𝑙 = 2 & 𝑓! cos 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧!

!"#

$/0 $

𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧! + & 𝑓! sen 2𝜋 ℎ(−𝑥! ) + 𝑘(−𝑦! ) + 𝑙(−𝑧! )
!"# $
2#
0

sen −𝛼 = −se𝑛 𝛼
$/0 $/0

𝐵 ℎ𝑘𝑙 = & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧! − & 𝑓! sen 2𝜋 ℎ𝑥! + 𝑘𝑦! + 𝑙𝑧! = 0
!"# !"#
2023 X-ray Crystallography
 ((*+,) /
tan 𝜙 = = =0
(.(*+,)) .(*+,)

Depending on the signal of A(hkl) the reflections phases will be zero or 𝜋

2023 X-ray Crystallography

Around the Bragg’s Law

1. Among the following features, please indicate which ones determine the positions of
the spots in a photo obtained with a X-ray scan.

A. Wavelength
B. Crystal size
C. Unit cell dimensions
D. Atomic number

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 2. Among the following features, please indicate which ones are involved in
the single-crystal X-ray diffraction.

A. Electron scattering
B. Crystallographic planes
C. Nuclear interactions
D. Constructive interference.

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 3. What is the maximum distance between planes in the
single crystal X-ray diffraction?

A. 0.5λ
B. 2λ
C. λ
D. No limit.

λ = 2dsen𝜃 sen𝜃 = 1

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5. A cubic material crystallises in a unit cell with an edge length of 4.2 Å. The
data were measured with molybdenum radiation (λ = 0.7173 Å).

A. Calculate the q angle for the reflection 111.

B. Calculate the distance between the planes 111.

(!
𝑠𝑒𝑛$ 𝜃 = ℎ$ + 𝑘 $ + 𝑙 $
') !

λ = 2dsen𝜃

2023 X-ray Crystallography

A. 0 /.4#/4!
𝑠𝑒𝑛 𝜃 = 10 + 10 + 10
%(%.0)!

𝑠𝑒𝑛 0 𝜃 = 0.021

𝑠𝑒𝑛 𝜃 = 0.1465

𝜃 = 8.43

B.

𝜆 = 2𝑑𝑠𝑒𝑛𝜃

5 /.4#/4
𝑑= = = 2.42 Å
06789 0:/.#%;<

2023 X-ray Crystallography

6. A cubic material exhibits two reflections 111 and 220 with interplanar distances of 4.15 and
2.55 Å, respectively. The data were recorded with copper radiation (l= 0.1537 nm). Calculate
the length of the unit cell edges.

𝜆 = 2𝑑𝑠𝑒𝑛𝜃
( #.,'#
𝑠𝑒𝑛𝜃 = = 𝜃 = 15.7
$* $-'.#,

( #.,'#
𝑠𝑒𝑛𝜃 = = 𝜃 = 17.59
$* $-$.,,

/.4#/4! 𝑎 = 7.19 Å
𝑠𝑒𝑛 0 (17.59) = 20 + 20 + 00
%(=)!

2023 X-ray Crystallography

 END
Now, I’m really happy!.....

I wish you good luck for the exam

2023 X-ray Crystallography