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6 Molecular Symmetry

BS Chemistry (Pamantasan ng Lungsod ng Maynila)

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Molecular Symmetry ● Symmetry is the basis if a particular vibration

CHM 4112 will appear in the IR spectrum (IR-active
vibrational mode)
Recording : Molecular Symmetry ○ Di lahat ng vibrations will appear as IR
Fayree - 0:00:00 to 0:27:19 peaks in the spectrum
Bea - 0:27:20 to 0:54:04 ● The NMR spectrum shows different kinds of
Amie - 0.54:05 to end nuclei (e.g. 1H, 13C)
● Chemically equivalent nuclei appear as a
single peak.
Recall:
● Chemically equivalent nuclei are
● Lewis structures
interconvertible by a symmetry operation
○ No. of valence e- = group no.
○ E.g. the carbons in benzene, which is
○ Formal charge - used to assess the
a planar hexagonal molecule, will be
stability of resonance structure interconvertible with each other hence
○ FC = grp no. - no of bonds - no. of the single peak (same case with the
lone pairs (nonbonding e) protons)
○ Negative FC must be at
electronegative atom
○ Smaller FC = more stable
● VSPER Theory
○ Steric number = no. of sigma bonds
+ lone pairs on central atom
helps us determine
the hybridization of
an atom
● Molecular Geometry
IV. SYMMETRY AND POLARITY
I. SYMMETRY AND NATURE ● Molecules with polar bonds are not all polar.
● Bilatereral symmetry - divisible into ○ Requirement for polarity is ofc
symmetrical halves on either side of a unique merong polar bonds.
plane. ● The symmetry of a molecule is always
● Radial symmetry - symmetry in which the considered in predicting polarity.
sides exhibit correspondence or regularity of
parts around a central axis (e.g. fivefold
symmetry of starfish)

II. SYMMETRY AND STRUCTURE

● Symmetry of a molecule reveals information
about its properties (structure, spectra,
- For example is CO2, the CO bonds here are
polarity, and chirality)
● Symmetry is considered in constructing and
polar but for the molecule symmetry CO2 is
labeling molecular orbitals. non polar.
- For the water molecule, we have polar
III. SYMMETRY AND SPECTRA bonds and a net dipole so this is a polar
● Symmetry is used to explain molecular molecule.
spectra e.g. infrared (IR) and nuclear
magnetic resonance (NMR) V. SYMMETRY AND CHIRALITY (HANDEDNESS)
● The IR spectrum shows molecular vibrations ● A chiral object has a non-superimposable
at different frequencies. mirror image.
● Symmetry is used to label vibrational modes. ● Symmetry gives the criteria for chirality.

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SYMMETRY OPERATIONS N-FOLD ROTATION,

CN (N=INTEGER)
● Rotation by 360°/n about a particular axis
defined as the n-fold rotation axis.
● C2 = 180° rotation
● C3 = 120° rotation
SYMMETRY AND REACTIVITY
● C4 = 90° rotation
● The stereochemistry of pericyclic reactions
● C5 = 72° rotation
is governed by orbital symmetry
● C6 = 60° rotation
(Woodward-Hofmann rules).
Example:

- These pericyclic reactions are one-step

reactions and they will involve molecular
orbitals. - Water molecule
- Para mag react siya dapat ‘yung symmetry - C2 rotation axis
of molecular orbitals ay tama. - Once ma perform ‘yung symmetry
operation parang walang nangyari
SYMMETRY OPERATIONS/ELEMENTS sa molecule kasi bumalik ‘yung mga
● A molecule or object is said to possess a atoms.
particular symmetry operation if that - Ammonia
operation when applied leaves the molecule - Trigonal pyramidal structure
unchanged. - C3 rotation axis (nakaturo sa atin)
○ Kapag ginawa itong symmetry - 120°
operations sa isang molecule, para
lang walang nangyari. Identify the rotation axes in the ff. molecules.
● Each person is performed relative to a point, ● Trigonal planar BF3 molecule
line, or plane - called a symmetry element.

SYMMETRY OPERATIONS
1. Identity
2. n-Fold Rotations
3. Reflection
4. Inversion
5. Improper n-Fold Rotation - three C2 axis, collinear with the BF bonds
- C3 axis, perpendicular with the molecular
SYMMETRY OPERATIONS IDENTITY, E plane
● Does nothing, has no effect Principal rotation axis - pinaka malaking value ng
● All molecules/objects possess the identity n. Always aligned with the z-axis
element, E.
● E has the same importance as the number ● Square planar molecule XeF4
1 does in multiplication (E is needed in
order to define inverses).

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- Rotation axes that are collinear with the XeF - For water molecule, there are two types
bonds. mirror planes
- One C2 axis na nasa gitna ng dalawang C2 - σv - hinati niya ‘yung molecule into
rotation axes na collinear with the XeF two
bonds - σ’v - when this is performed, hindi
- C4 axis na perpendicular to the molecular gagalaw ‘yung atoms
plane (rotation by 90°) ● Vertical plane (σv): plane contains the
- C2 axis that is collinear with the C4 principal rotation axis (i.e., parallel)
● Horizontal plane (σh): plane is
● NH3 molecule perpendicular to the principal rotation axis.
● Diagonal/dihedral plane (σd): plane is
parallel to the principal rotation axis, but
bisects angle between two C2 axes.

- C3 rotation axis
- If your hydrogen atoms are labeled 1,2,3
perform a clockwise rotation (this is a
symmetry operation)
- For benzene molecules we have many
types of rotation axes.
SYMMETRY OPERATIONS REFLECTION, σ
- Principal rotation axis is C6 (pinakamalaking
● Symmetry element: mirror plane or plane of
value ng n)
symmetry
- σh: molecular plane of the benzene
● If reflection about a mirror plane gives the
molecule
same molecule/object back, then there is a
- σv: perpendicular with σh (ito ‘yung
plane of symmetry (σ).
tumatama sa mga atoms, ‘yung carbon
hydrogen atoms)
- σd: between σv (nasa gitna ng dalawang C2
axis)

SYMMETRY OPERATIONS INVERSION, I

● Symmetry element: center of inversion.
● Objects/molecules containing an inversion
center are called centro symmetric.

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● This inversion is like a reflection but with

respect to a point.
● The operation is to move every atom in the
molecule in a straight line through the
inversion center to the opposite side of the
molecule.
Example: Sulfur hexafluoride - A molecule that contains an s for rotation
axis is the methane molecule which is a
tetrahedral molecule.
- Performing C4 rotation and reflection with
respect to C4
- For methane molecule, you have an S4
improper rotation axis

Important Reactions
- An octahedral molecule
- The molecule contains a center of
conversion which is at the sulfur atom
- Performing inversion to this molecule, all
outer atoms will change position (1 will
change with 6, 2 with 4, and 5 with 3)
- This is still a symmetry operation
*another example
GROUP THEORY
● Involves cataloging of the symmetry of
molecules.
● A branch of advanced mathematics.
● A mathematical method by which aspects of
a molecule’s symmetry can be determined.
To be a group several conditions must be met:
1. Any result of two or more operations must
produce the same result as application of
one operation within the group, i.e., the
group multiplication table must be closed.
- Atom A will interchange with D, and B with
a. A mathematical group is you have a
C
set of elements and a binary
operation.
SYMMETRY OPERATIONS IMPROPER
b. Binary operations will lead two
ROTATION, SN
elements of the group.
● n-fold rotation followed by reflection through
c. Performing binary operations in two
the mirror plane perpendicular to the
elements, its result must be also an
rotation axis.
element of the group.
● Note: n is always 3 or larger because S1=σ
2. Must have an identity E.
and S2=inversion (i).
3. All elements must have an inverse i.e., for a
given operation A there must exist an
operation B such that AB = E .
a. B is an inverse of A
4. The associative property must hold A (BC)
= (AB) C.

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The number of elements in a group is called its - We are given the human projection
order (h). for a molecule.
- We have an inversion center. If we
SYMMETRY CLASSIFICATION perform inversion to the molecule,
● Certain symmetry operations can be Br, Cl, and H nagpalit.
present simultaneously, while others cannot.
● There are certain combinations of symmetry 2. Rotation Groups
operations which can occur together. a. Cn: E and Cn only (rotational symmetry)
● Symmetry groups combine symmetry E.g.
operations that can occur together. C2: H2O2 (skew)
● Symmetry groups contain elements and
their mathematical operations.

POINT GROUPS
● For the individual molecule, we have the
point groups. They are called point groups
because all the symmetry elements
intersect at a point.
- Assume molecule is rigid, nasa gitna
E: identity element
si C2.
σ: mirror plane
C3: PPh3 (Triphenylphosphine)
I: inversion
C2: rotation by 180 degrees
Cn: rotational symmetry

1. Low Symmetry Groups

a. C1: only E (trivial group)

- Like a propeller
- Medyo nakapyramid structure
- No rotation, & no mirror plane
- No mirror plane but my C3 rotation
- Only has identity
axis na nakaturo sa atin.
- All of them are chiral
- The one lone pair is nasa likod ni
b. Cs: E and σ only (reflection symmetry)
Phosphorous.

- 2 hydrogen separates the molecule

into two (mirror plane)
b. Cnv: E and Cn and n σv's (pyramidal
c. Ci: E and i only (inversion symmetry)
symmetry)

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❖ Borric acid

- C3 nakaturo sa atin
- We have molecular plane, if the
shape is planar then we have σh

Cnv vs. C2h Point Groups

• C2v: E, C2, 2 σv H2O (water molecule)

1 σv :Molecular plane
2 σv :Separates the molecule into two
• C3v: E, C3, 3 σv NH3 (ammonia molecule)
N & H lies on σv

3. Dihedral Groups
a. Dn: E, Cn, n C2
axes perpendicular to Cn (dihedral
symmetry)
- No mirror planes
- No molecular planes/symmetry
planes
c. Cnh: E and Cn and σh (and others as
❖ E.g. Oxalato-cobalt(III) complex
well)
- We have σh which is perpendicular
to Cn (principal rotation axis)
C2h: E, C2, σh, i

E.g.
❖ derivative of naphthalene

D3: E, C3, 3 C2 perpendicular to C3

(e.g. [Co(ox)3]3-, ox = oxalate)
- shape looks like a propeller
- C3 nakaturo sa atin
- C2 nasa blades ng propeller
- C2 nakaturo sa atin
- Mirror plane (σh) perpendicular with
the C2 which is the molecular plane b. Dnh: E, Cn, n C2 axes perp. to Cn, σh
(prismatic symmetry)

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- We have mirror plane (σh) - Walang σh but may σd

❖ E.g. Boron trifluoride & eclipsed ethane - Symmetry of antiprisms
(D3h: E, C3, 3 C2 perp. to C3, σh) - Yung eclipsed ethane point group ay D3h
pag staggered ang ethane wala ng mirror
plane na perpendicular sa C3, pero may
mga mirror planes na σd
❖ E.g. staggered ethane (D3d: E, C3, 3 C2
perp. to C3, 3 σd:)

- 3 C2 perp. to C3
- We have mirror plane
❖ Platinum complex (D4h: E, C4, 4 C2 Symmetry of antiprisms
perp. to C4, σh)

❖ Benzene (D6h: E, C6, 6 C2

perp. to C6, σh)

D groups - all of them has n C2 perpendicular to Cn

Symmetry of prisms (principal rotation axis)
Dn - no mirror plane
Dnh - with σh
Dnd - w/out σh but with σd

C vs D Point Groups

c. Dnd: E, Cn, n C2 axes perp. to Cn,

σd (antiprismatic symmetry)

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4. Sn Group For continuous group of cone & cylinder:

- quite rare
• S2n: E, Cn, S2n
(no mirror planes)
• S4, S6, S8, etc.
(Note: never S3, S5, etc.)
• S4: E, C2, S4
❖ E.g.

- We have S4 improper rotation axis; no

mirror planes.

5. Continuous Groups
- For linear molecules you can either
have: 6. The Platonic Solids
a. C∞v: E, C∞ , ∞σv - Highly symmetric objects
- No σh - Plato said that these solids have magical
❖ E.g. HF, HCN, HCl properties
a. Td: E, 8 C3, 3 C2, 6 S4, 6 σd (full tetrahedral
symmetry)
- Tetrahedral structures
- Total of 24 symmetry elements
- No need to identify all the symmetry
elements - simply recognize Td shape (a
molecule that has Td point group)
- Multiple C2 and C3 rotation axis
b. D∞h: E, C∞ , ∞ C2 perp. C∞, σh: ❖ E.g. methane, CH4
- With σh
- We have center of inversion/mirror
plane
❖ E.g. CO2 ; H2

b. Oh: E, 8 C3, 6 C2, 6 C4, 3 C2 (=C42), i,

6 S4, 8 S6, 3 σh, 6σd (full octahedral symmetry)
- Octahedral or cubic structures
- Multiple C4 axis
- No need to identify all the symmetry
elements - simply recognize Oh shape.

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❖ E.g.

Rare High Symmetry Groups

7. Th (pyritohedral symmetry)
- derived by adding a center of inversion to
the T point group
❖ E.g.
- Multiple C3 but has a center of inversion
Cubooctahedron - generate this from
octahedron by cutting the corners of
the octahedron

c. Ih: E, 12 C5, 20 C3, 15 C2, i, 12 S10,

20 S6, 15 σ (full icosahedral symmetry)
- About 120 symmetry elements
- Multiple C5 axis
❖ E.g. Pyritohedron - parang malaking crystal
Dodecahedron (12 phases for this pyrite
polyhedron), icosahedron (20
phases for this polyhedron; 8. Purely rotational subgroups
B12H122-) or truncated icosahedron - the only symmetry operations other than
(C60 fullerene). identity are proper axes of rotation
- Quite rare (chiral point groups)
- All of them does not have mirror plane but
have rotation axis
T (chiral tetrahedral symmetry)
- Td na walang mirror planes
O (chiral octahedral symmetry)
- Oh na walang mirror planes
C60 fullerene - looks like a soccer I (chiral icosahedral symmetry)
ball - No mirror planes also
❖ E.g.

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* Some are proteins.

9. Spherical Point Group

Kh
- The symmetry of perfect spheres
- Only atoms but no molecules belong
to this point group.
- No application sa chemistry because
wala namang molecule na spherical.

SUMMARY OF POINT GROUPS

Point Group Assignment Method

Worked examples

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- We have E, C2, σh (mirror plane perpendicular to

C2), and i/inversion (performing this magpapalit 2 F
& yung 2 N) . Thus, the point group is C2h.

- We have E, 3C2 (perpendicular with C3) , C3

(colinear with axial Phosphorus fluorine bonds), σh
(dito nakalagay 3 Fluorine). Since C2 is
perpendicular with C3 (highest rotation axis is C3),
our point group is D3h.

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