Lecture 3

MOLECULAR SYMMETRY

http://ocw.nctu.edu.tw/upload/classbfs120912043213088.pdf
Dr. S. M. Condren, Christian Brothers University
http://web-docs.gsi.de/~wolle/TELEKOLLEG/KERN/PPT/NH3-symmetry1.ppt

http://www.slideshare.net/ZuhriyatusSholichah/the-determination-of-point-groups

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 Lecture 3 Reading
• Molecular symmetry
[2]: chapter 4, focus on 4.1, 4.2, further reading 4.3, 4.4
[1]: 6.1-6.5

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 Molecular symmetry
Contents and practice skills
• Symmetry operations • Determine symmetry
and elements operations and elements
• Point groups • Assign point group
• Applications of
symmetry (self-reading)
– Polar molecules
– Chiral molecules
– Molecular vibrations
 Molecular Symmetry
sym·me·try
noun
1. the quality of being made up of exactly similar parts facing each other or around an
axis.
"this series has a line of symmetry through its center"
2. correct or pleasing proportion of the parts of a thing.
"an overall symmetry making the poem pleasant to the ear"
3. similarity or exact correspondence between different things.
plural noun: symmetries
"history sometimes exhibits weird symmetries between events"

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Molecular Symmetry –Point Group
– Symmetry elements: A point, line or plane about
which the symmetry operation is performed
– Symmetry operations: actions that leave the
molecule apparently unchanged

around the
center

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 Some common
symmetry elements and operations

1 None
2 Axis (Proper) Rotation
3
4 Center of inversion Inversion
5 Axis + mirror plane Improper Rotation

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 Identity operation (E)
• Cause no change in the molecule
• Apply for every molecule
• SiHClBrF: has only this symmetry
F

Si
Br Cl
H

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 Rotation operation (Cn)
• Proper axis of rotation → Cn
Where: rotation degree = 360/n
▪ n = 2, 180o rotation
▪ n = 3, 120o rotation
▪ n = 4, 90o rotation
▪ n = 6, 60o rotation
• Principal axis of rotation, Cn

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9
10
Rotations for a Trigonal Planar Molecule

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12
 Reflection Operations

Mirror planes
σh → mirror plane perpendicular to a principal axis of rotation
σv → mirror plane containing principal axis of rotation
σd → mirror plane bisects dihedral angle made by the principal axis
of rotation and two adjacent C2 axes perpendicular to principal
rotation axis
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Rotations and Mirrors in a Bent Molecule

σ+σ=E
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 Inversion Operation
Symmetry Element:
Center of inversion i
i×i=E

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Compare Inversion and C2

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 Improper Rotation (Sn)
• Sn: Rotation by 360o/n
• followed by reflection perpendicular to rotation axis

• S4: Rotation by 90o

• followed by reflection perpendicular to rotation axis

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Table of Symmetry Elements and Operations

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Table of Symmetry Elements and Operations

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 Point group
C2 ϭv ϭv

• Point group: A set of symmetry operations that

describes the molecule’s overall symmetry
• Classification:
– Groups of Low symmetry
– Groups of High symmetry
– Other groups
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 Groups of Low Symmetry
• Have few or no symmetry operations

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 The C1 point group
• No symmetry elements
• Rotate through 360º: remain unchanged.
• Axis: 360º/360º = 1-fold
→ C1 axis/group

I
I N
Cl
C H
Br
Cl
F

Bromo-chloro-fluoro-iodo- chloro-iodo-amine
methane
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 Cs and Ci groups
I σ • Only 1 σ

C → Cs
Cl
F
F
chloro-difluoro-iodo-
methane

• Only 1 (i)

→ Ci
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 Most land animals have bilateral symmetry, and
belong to the Cs point group:

Cs
Mirror planes (σ)
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 Naming point groups
• Letter: rotational group
• Subscript number: order of the principal rotational axis
(e.g. 3-fold or 4 fold etc.)
A ‘D’ indicates an n-fold
principal rotation axis
A “C ” indicates plus n 2-fold axes at
only one rotational right angles to it
axis

C3 C3v D4d D4h

3-fold rotational has σv but 4-fold d = no ‘h’ indicates
axis no σh mirror principal σh mirror a σh mirror
planes in a C group axis plane plane

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 Naming point groups
A subscript ‘h’ means that there is C3 principal axis
a σh mirror plane at right angles to only one
the n-fold principal axis: of the three
σv planes
C4 principal axis is shown
σv

D3d
σh A subscript ‘d’ (or v for C groups)
D4h means there is no σh mirror plane,
but only n σv mirror planes
containing the principal Cn axis.
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C2 , C 3 T = tetrahedral
O = octahedral
I = icosahedral
C2 , C 3 , C 4

C2 , C 3 , C5

Groups of High Symmetry

Many symmetry operations 27
C∞v group
• has NO center of inversion
• C∞ principal rotation axis
C∞ •
∞ ϭv (reflection containing C∞)

→ C∞v

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D∞h group
i • has a center of inversion (i)
• Linear: C∞ principal rotation
C∞ axis.
• ∞ ϭv (reflection containing C∞)
• → D∞h

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Td group
• 4 C3 principal rotation axis (more
than 1 principle axis Cn where n >2)
• No inversion center i
• 3 C2
• 6 ϭd

→ Td

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Oh and Ih groups

• Has an inversion center i

• 3 C4
• (48 symmetry operations total)
→ Oh

• 6 C5 principal rotation axis

• (120 symmetry operations total)
→ Ih

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 C and D groups
Symmetry n nv nh
operations
C Cn Cnv Cnh
D Dn Dnv Dnh
If there are n C2 axes at right angles (90o) to the
principal axis, we have a Dn point group, If not, it is a Cn
point group.

[IF6O]- : C5v [IF7]: D5h

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 The C point groups
• Only a single rotational axis (high fold)
• Include Cn, Cnv, and Cnh
Cn : NO other symmetry elements
C2 C2v ϭv (next slide)
ϭv
Cnv : have also n mirror planes
containing the Cn rotational axis

Cnh : also have a σh mirror plane

C3h perpendicular to the principal
rotational axis.

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 The Cn point groups
These have a Cn axis as their only symmetry element. They generally
resemble propellers which have the front and back different. Important
examples are (hydrogens omitted for clarity):

triphenyl C3 Cobalt(III)
phosphine tris-glycinate
viewed down viewed down
C3 axis C3 C3 axis

C3 C3
C3 C3
triphenyl Cobalt(III)
phosphine tris-glycinate
viewed from viewed from
the side the side
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 Practice
• H2S, NH3, VOF4-, PF4I, SF4, COCl2

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 The D groups
• n C2 axes perpendicular to the principal axis
C2 principal
• Include Dn, Dnd, and Dnh C2 D2

C3 (3) σv contain C3
C2 [Cu(en)2]2+ (en =
ethylene diamine)
Staggered form
of ethane

D3d

Dn : NO other symmetry elements

D4h Dnd : have also vertical mirror

C2 planes containing the Cn axis
C2
C2 C2
σh Dnh : also have a σh mirror plane
bisecting the principal axis
C4 4 C2 C4 axis σh C4 axis 36
 σv and σd
• σv : Vertical reflection plane – contains the principle axis
• σd : Diagonal reflection plane – contains the principle axis, and
also bisecting the angle between a pair of C2.
→ σd is a special case of σv
 Dnh Examples
C2 C3 C3
C3

D2h D3h D3h D3h

C4
C5
C4 C5

D4h D4h D5h D5h

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Benzene, an example of the D6h point group
C6 C2
principal axis C2

C2
C6 σh C2
σv σv

D6h

C6
C6
principal axis
principal axis
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 Practice
• PtCl2(NH3)2
• C2H4
• PF5
• BH3
• SO3
• [PtCl4]2-

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 D2 point group
C2 principal
C2 D2

C2

[Cu(en)2]2+ (en = ethylene diamine)

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 D3 point group
C2 [Co(en)3]3+
C3 principal axis
C2

C2
axis
C2

C3 D3
principal axis

view down the C3 axis view down one of the

of [Co(en)3]3+ showing three C2 axes of [Co(en)3]3+
the three C2 axes. at right angles to C3
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 Dnd point groups
These have mirror planes containing/parallel to the principal
axis
C5 axis
C3 axis σv planes
contain the
principal
axis

D3d D5d
Staggered form
of ethane Staggered form of ferrocene
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 Determining point group

• Determine shape using Lewis Structure and VSEPR Theory

• Determine symmetry elements and operations

• Use the flow chart to determine the point group

– See if the molecule belong to special cases (High or Low symmetry)
– (If not the HL symmetry) Find the rotation axis with the highest n
(Cn – principle axis)
– Any C2 that perpendicular to Cn? (Yes: D group; No: C or S)
– Any σh? (Yes: Dnh, Cnh group; No: Dnd, Cnv)
– Any σv? (Yes: Dnd, Cnv , Sn group; No: Dn, Cn, S2n)

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 Decision Tree
Start here

OCS, PH3, N2F2, H2C=C=CH2 45

Flow chart for determining point groups
 HW2
• [2] page 111: 4.1-4.4, 4.5 (except g, i, j)

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 More examples after slide 39

Other examples of the D3 point group

C3 C2
C2 C2 principal axis

C2
C2

C2

D3 D3
[Co(oxalate)3]3- [Co(bipyridyl)3]3+
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 More examples after slide 39
Some cobalt(III) complexes belonging to the D3
point group:
C2
C2 C2 CH3
3+ 3+
NH2 H H3C O CH3
N
2
H2N N O O
N N
Co Co Co
O O
H2N N N N
H2 H3C O CH3
NH2 N

CH3

tris(ethylenediamine) tris(2,2’-bipyridyl) tris(acetylacetonato)

cobalt(III) cation cobalt(III) cation cobalt(III)

D3
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 More examples after slide 39

Comparison of C3 and D3 tris(chelates)

no C2 axis at
this point

C2
D3 O C3
3+
O H2
NH 2 H
2 H2N N
H2N N
Co Co
O O
H2N N O
H2 NH 2
NH 2 O

tris(ethylenediamine)cobalt(III) tris(glycinato)cobalt(III)
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 The D4d point group
C4 principal axis σv
C2 C2 σv σv
C2 C2
C2 σv

C4 C4
[ZrF8 ]4- principal axis
principal axis
Square antiprism D4d
As predicted by VSEPR, the [ZrF8]4- anion has a square anti-prismatic structure.
At left is seen the C4 principal axis. It has four C2 axes at right angles to it, so it
has D4 symmetry. One C2 axis is shown side-on (center). There are four σv mirror
planes (right), but no mirror plane at right angles to C4, so the point group does
not rate an h, and is D4d. 51
 [K(18-crown-6)]+, an example of a D3d point
group
C3
principal axis C3 principal axis σv
C2 C2
K+
σv
C2
C2 C2
C2 σv
D3d
The complex cation [K(18-crown-6)]+ above is an important structure that
has D3d symmetry. It has a C3 principal axis with 3 C2 axes at right
angles to it, as well as three σv mirror planes that contain the C3 axis,
but no σh mirror plane (because it’s not flat, as seen at center), so is D3d.
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