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Master of Science (Chemistry)

Semester-I
Core Course-III (Organic Chemistry)

Unit 2
Stereochemistry- Elements of Symmetry

Sonu Ram Shankar

Assistant Professor
University Department of Chemistry
Lalit Narayan Mithila University, Darbhanga

1
Symmetry Around
Symmetry in Nature
 Symmetry Perception

What do you see?

A bright white triangle on top of another triangle."

or

Just empty space surrounded by three Pac-Man look-alikes and some floating V’s.

The brain creates whiter-than-white triangle

 Symmetry in Nature

Visual perception: Quickly and accurately organizing visual information.

Symmetry helps us distinguish figures from their backgrounds.

Aesthetic experience: Associated with beauty, and is considered a key aspect of classical art.

People tend to prefer symmetrical abstract patterns.

Neural mechanisms: Abstracting long-range spatial dependencies between image regions.

 Elements of Symmetry

Symmetry Operations

A symmetry operation is a transformation applied to a molecule that results in an orientation indistinguishable

from its original position. These operations are fundamental in the study of molecular symmetry and include

various types, such as:

Identity (E): Leaves the molecule unchanged.

Inversion (i): Moves each point of the molecule through a central point (center of symmetry) to an opposite

position.

Rotation (Cn): Rotates the molecule around an axis by a specific angle. Where n is the number of rotation to

achieve the identity.

Reflection (σ): Reflects the molecule across a mirror plane.

Symmetry Elements Elements of Symmetry
Symmetry elements are specific features within a molecule that enable certain symmetry operations, allowing the

molecule to maintain its indistinguishable orientation. Based on their combinations, symmetry elements can be classified

as follows:

Basic Elements:

Identity (E): The element associated with no change.

Point: A central point in the molecule, such as the center of symmetry.

Line (Axis): An axis around which rotational symmetry operations are performed.

Plane (Mirror Plane): A plane across which reflection symmetry operations are performed.

Combined Elements:

Improper Rotation (Sn): A combination of rotation and inversion, where a rotation is followed by an inversion

through the center of the molecule.

 Elements of Symmetry
Point or center of symmetry:

A point (or center) of symmetry is a feature of a molecule where each point within the structure can be mapped to an

equivalent point diametrically opposite and equidistant from a central point within the molecule. When a molecule

possesses a center of symmetry, every component point has a corresponding counterpart on the opposite side of this

central point. This operation is formally known as inversion and is represented by the symbol i.

Example: symmetrically substituted aceteylene, 2, 3-dimethylbutene, benzene

 Elements of Symmetry
Axis of symmetry: An imaginary line through a molecule around which the structure can be rotated by a specific angle, resulting

in an orientation indistinguishable from the original.

The symmetry operation associated with an axis of symmetry is called rotation

Denoted by Cₙ, where n represents the number of times the molecule can be rotated to match its original position within a full

360° turn. Thus, n = 360° / angle of rotation.

A molecule may possess multiple axes of symmetry,

The axis with the highest value of n is designated as the principal axis

Example H2O; C2 NH3; C3 Benzene; C6

Axis of symmetry Elements of Symmetry
An axis of symmetry Cn has specific subcategories depending on the order of rotation applied around the axis.

These subcategories are represented as 𝑐 , 𝑐 , … , 𝑐 ,

where the superscript indicates the number of rotations by the basic angle

Nested Axes: An axis of symmetry may include lower-order axes, which occur when 𝑐 =𝑐

For example 𝑐 = 𝑐 ; 𝑐 = 𝑐

Reverse Rotation: A negative integer in the superscript indicates rotation in the opposite direction. 𝑐 = 𝑐

Example: 𝑐 = 𝑐 =𝑐

×
a rotation (or two-thirds of a full rotation) on c6, is equivalent to a single rotation in the opposite direction on c3

Identity Element: The rotation 𝑐 represents a complete 360° rotation, which brings the molecule back to its original orientation
and is equivalent to the identity element E.

𝑐 =𝐸
 Elements of Symmetry
Plane of Symmetry or Mirror Plane

an imaginary plane that divides a molecule into two symmetrical halves.

When a molecule is reflected across this plane, it generates an identical copy of its original orientation, effectively creating a

mirror image.

This type of symmetry operation is represented by the symbol σ

σ .σ = σ2 = E

σn = E for n = even number

σn = σ for n = odd number

 Elements of Symmetry
Plane of symmetry:

Horizontal plane of symmetry: A mirror plane that is perpendicular to the principal axis of the molecule, σh

either in planar molecule or plane contains maximum atoms

Vertical plane of symmetry: A mirror plane that is aligned parallel to the principal axis of the molecule, σv

Dihedral plan of symmetry: A mirror plane that bisects the angle between two other symmetry elements,

often between two perpendicular rotational axes. two 2-fold rotation axes perpendicular to the principal axis σd

Vertical plane Horizontal plane Dihedral plan

 Elements of Symmetry

Improper rotation axis or a rotary-reflection axis,

Combines two sequential symmetry operations:

Rotation: The molecule is first rotated by an angle 360°/n about the axis

Reflection: The rotated structure is then reflected in a plane perpendicular to the axis.

This type of symmetry operation is represented by the symbol, Sn

Subcategories

The improper rotation axis has subcategories denoted as 𝑆 , 𝑆 … . 𝑆

where the superscript indicates the number of times the combined rotation and reflection operation is applied around the Sn.
 Elements of Symmetry

Subcategories of Sn

Each subcategory 𝑆 represents the improper rotation operation being applied k times.

This operation involves:

Rotating by × 𝑘, about Sn axis, denoted as 𝐶 .

Reflecting in a mirror plane perpendicular to the axis, denoted as 𝜎 .

Thus, 𝑺𝒌𝒏 = 𝒄𝒌𝒏 . 𝝈𝒌𝒉

 Elements of Symmetry
Improper Rotation Axis

Subcategories of Sn

𝑺𝒏 = 𝒄𝟏𝒏 . 𝝈𝟏𝒉 , 𝒄𝟐𝒏 . 𝝈𝟐𝒉 , … 𝒄𝒏𝒏 . 𝝈𝒏𝒉

Examples

𝑺𝟏𝟏 = 𝒄𝟏𝟏 . 𝝈𝟏𝒉 = 𝑬σ = σ

Since 𝑐 is simply the identity operation E,

𝑆 acts as a mirror plane σ.

𝑺𝟏𝟐 = 𝑺𝟏𝟐 (𝐜𝟐𝟏 . 𝛔𝟏𝐡 = 𝐜𝟐 σ = i),

S2 represents inversion symmetry when applied once

𝑺𝟐𝟐 = (𝒄𝟐𝟐 . 𝝈𝟐𝒉 = 𝑬𝑬 = E)

S2 represents the identity operation when applied twice.

 Elements of Symmetry
Improper Rotation Axis

Improper axes of odd order n, Example PF6

Carrying out the rotation-reflection n times

equivalent to a single reflection through the horizontal mirror plane σh

𝑆 = 𝑐 . 𝜎 = 𝐸𝜎

as the rotations effectively cancel each other out.

Rotation-reflection 2n times to reach the identity

Since 2n is always even (e)

𝑆 = 𝑐 . 𝜎 = 𝐸𝐸 = 𝐸
 Elements of Symmetry
Improper Rotation Axis

Example S6

𝑆 = 𝑐 .𝜎

𝑆 = 𝑐 .𝜎 = 𝑐 .𝐸 = 𝑐

𝑺𝟑𝟔 = 𝒄𝟑𝟔 . 𝝈𝟑𝒉 = 𝒄𝟐 . 𝝈 = 𝒊

𝑆 = 𝑐 .𝜎 = 𝑐 .𝐸 = 𝑐

𝑆 = 𝑐 .𝜎 = 𝑐 .𝜎 = 𝑐 .𝜎

𝑺𝟔𝟔 = 𝒄𝟔𝟔 . 𝝈𝟔𝒉 = 𝑬. 𝑬 = 𝑬

 Elements of Symmetry

Relationships with Other Symmetry Elements

If a molecule possesses a rotation axis Cn and a horizontal mirror plane σh (a plane perpendicular to Cn) exists

then an improper rotation axis Sn must also exist.

Sn =cn σh

Importance

defines more complex symmetry operations, often found in chiral and achiral molecules.

the molecular classification of point groups and is significant in determining the molecule's optical activity.
 Elements of Symmetry

Improper Rotation Axis

Improper axes of even orders,

There must also be a proper rotational axis with an order n/2.

𝑆 = 𝑐 .𝜎 = 𝑐 .𝐸 = 𝑐

After n rotation-reflections the identity is produced

𝑺𝟔𝟔 = 𝒄𝟔𝟔 . 𝝈𝟔𝒉 = 𝑬. 𝑬 = 𝑬

n is always 3 or larger because S1 = σ and S2 = i

 Elements of Symmetry
Classification of symmetry operations

Based on operation can be carried out two types: proper and improper symmetry operations

Proper symmetry operations

Can be really carried out on a molecule.

Identity, E and rotations, Cn

Improper symmetry operations

Can only be imagined

Reflections, inversions and improper rotations

 Elements of Symmetry

Convention

z axis: Along the principal axis of the molecule,

x axis: In planar molecule lies in the plane of the molecule

Non-planar in a plane containing the largest number of atoms,

y axis: Perpendicular x and y axis in a right handed axis system.