01

NOTE
C H E M I S T R Y

CHEMICAL BONDING
VSEPR: DEVIATIONS FROM STANDARD
GEOMETRIES (PART 1)

What you already know What you will learn

• Hybridization • sp hybridization • Hybridization: sp3d2

• Sigma and pi bonds • sp2 hybridization • Hybridization: sp3d3

• Geometry and shape • sp3 hybridization • Hybridizations in hydrocarbons

• Axial and equatorial bond • sp3d hybridization • Order of repulsion

• Expanded octet • Bond angle

BOARDS MAIN ADVANCED

Hybridization: sp3d

4 bp + 1 lp

Example: SF4 (Distorted Seesaw)

• SF4 molecular geometry is trigonal bipyramidal but due to the presence of one lone pair on the
equatorial position, the expected shape will be like that of a distorted seesaw (Fig. 1).
• Lone pair can occupy either axial or equatorial position. If the lone pair is in an axial position, it
forms an angle of 90°, but in the equatorial position, it form an angle of 120° with the equatorial
bond pair electrons. Greater the bond angle, lesser is the repulsion between the lone pair and
the bond pair electrons. Therefore the lone pair lies preferably in the equaorial position to form
a distorted seesaw structure.
• Due to the repulsion between the lp and bp electrons the equatorial fluorine atoms have 102°
bond angles instead of the expected 120° angle. Similarly, the repulsion of lp with bp of axial
fluroine atoms also decreases the axial F-S-F angle from 180°, to 173°, resulting in a distorted
seesaw structure.
• SCl4 also has the same geometry as Cl and F belong to the same group (Fig. 2).
F Cl

F F Cl Cl
F S S Cl S S
F F Cl Cl

F F Cl Cl
Axial lp Equatorial lp Axial lp Equatorial lp
Fig. 1: Structure of SF4 Fig. 2: Structure of SCl4

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4 bp + 1 lp (With 1 pi bond)

Example: IOF3 (Distorted Seesaw)

F
• The mlecular geometry of IOF3 is trigonal
F
bipyramidal with lp occupying the equatorial
position giving rise to an expected shape of O O
distorted seesaw. I
I F
• The bivalent oxygen forms a pi-bond with iodine
F
and double bond has more electron density, so
oxygen also occupies equatorial position. F F
• Repulsion of lp with equatorial oxygen and
fluorine decreases the O-I-F bonds from 120°. Fig. 3: Structure of IOF3
• Repulsion of lp with bp of axial Fluorine atoms
decreases the F-I-F 180° angles also. So IOF3
has distorted seesaw structure.

4 bp + 1 lp (With 2 pi bonds)

Example: XeO2F2 (Distorted Seesaw)

The molecular geometry of XeO2F2 is trigonal
bipyramidal, but the presence of one lone pair is on F F
the equatorial position and thus, the actual shape
will be that of a distorted seesaw (Fig. 4). O
• The lone pair are situated on the equatorial O
Xe Xe
positions due to less number of repulsions O
between the bond pairs and lone pairs. If the O
lone pair are in axial positions, there will be three
bond pairs, lone pair repulsions at the angle F
F
of 90°, while here, there will be only two bond
pair-lone pair repulsions. Fig. 4: Structure of XeO2F2
• Fluorines are axially placed and oxygens are
equatorially because according to Bent’s rule,
more electronegative atoms lie in the axial
positions.

3 bp + 2 lp

Example: ICl3 (T-shape)

Cl
• The molecular geometry of ICl3 is trigonal Cl
bipyramidal. However, due to the presence of
two lone pairs on the equatorial positions, the
actual shape will be T-shape (Fig. 5). I Cl
I Cl
• The lone pairs are situated on the equatorial
position due to less number of repulsions
between the bond pairs and lone pairs. If the lone Cl Cl
pairs are in axial positions, there will be six bond
pair-lone pair repulsions, while here, there will be Fig. 5: Structure of ICl3
only four bond pair-lone pair repulsions.

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F
3 bp + 2 lp (with 1 pi bond) F

Example: XeOF2 (T-shape) Xe O

Xe O
• The molecular geometry of XeOF2 is trigonal
bipyramidal. However, due to the presence of
two lone pairs on the equatorial positions, the F F
actual shape will be T-shape (Fig. 6).
Fig. 6: Structure of XeOF2

2 bp + 3 lp -
- I

Example: I3- (Linear)

• The molecular geometry of I3- is trigonal I
I I I
bipyramidal. However, due to the presence of
three lone pairs on the equatorial positions, the
actual shape will be linear (Fig. 7). I

Fig. 7: Structure of I3-

Note

We cannot have a combination of 1 bp + 4 lp that will have 1 + 8 = 9 electrons in the valence shell
of the central atom, which is not possible.

BOARDS MAIN ADVANCED

Hybridization : sp3d2

• Steric number = 6
• Geometry: Octahedral
• When we view the geometry from any direction,
it looks exactly the same.

Fig. 8: Ball and stick illustration

Consider the Fig. 10. In the given three-dimensional of octahedral
geometry, if we connect the atoms that are
horizontal, we get a square. Now, on joining the F
corners of the so formed square with the atoms
present along the axis, we obtain two square based F F
pyramids. We can call this a square bipyramidal S
that has a total of eight faces, four on the top and F
four on the bottom of the square base. Therefore, F
it can also be known as a regular octahedron or
an octahedral geometry. The square bipyramidal’s F
representation of SF6 is shown in the given figure. Fig. 9: Octahedral Fig. 10: Arrangement
The solid black lines specify square bipyramidal or geometry of SF6 of six bond pairs
octahedral geometry (Fig. 9).

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A front view and a top view of an octahedron is shown in Fig. 11. The angle between the adjacent
bonds is 90°.

90°
90°

90°

Fig. 11: Front view and top view of octahedron

6 bp + 0 lp F
F
Example: SF6 (Octahedral)
F F F F
• Here, all the six valence electrons are involved S S
in sigma bonding. F F F F
• No electrons are involved in pi bonding.
F
• For sulphur, after bond formation with six fluorine F
atoms there is an expansion of octet as the
Fig. 12: Lewis representation and ball and
number of valence electrons is increased to 12.
stick model for SF6

6 bp + 0 lp
- F -
PF6 - (Hexa fluoro phosphate ion) - Octahedral F
• There is an overall negative charge on this F F F F
structure and it can be regarded as a negative P P
formal charge over phosphorus making a total F F F F
of 6 valence electrons.
F
• All the six valence electrons are involved in F
bonding and thus, the hybridization is sp3d2 with Fig. 13: Lewis representation and ball and
square bipyramidal geometry. stick model for PF6 -

6 bp + 0 lp (with 1 pi bond) O
O
Example: IOF5 (Octahedral)
F F I
• The position of the pi bond does not matter as it F F
I
can occupy both equatorial and axial positions F F
F F
because it depends on the direction of the
observation (perspective). F F
Fig. 14: Lewis representation and ball and
stick model for IOF5

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6 bp + 0 lp (with 2 pi bonds)

Example: XeO2(OH)4 (Octahedral)

O
• Here, there are two pi bonds present. So, the O H
axial and the equatorial positions of the double
bond have a certain effect on repulsion. HO OH H O O
Xe H
• In order to minimise repulsion, we keep the Xe O O
second pi bond opposite to the first one. HO OH H
• One important thing to be noted here is that O O
there is a relative representation of Xe-O and
H. Fig. 15: Lewis representation and ball
• This is because of the bent arrangement of and stick model for XeO2(OH)4
O-H due to the presence of two lone pairs on
oxygen.

Note

Octahedral geometry cannot have 3 pi bonds as it would cause Xe to have 9 valence electrons
even before the formation of bonds, which is not possible.

F F
5 bp + 1 lp
F F F
Example: BrF5 (Square pyramidal) Br F Br
F
• Lone pairs can occupy either the axial or the F
F F
equatorial positions as it depends on the
observer’s perspective.
Fig. 16: Lewis representation and ball
• The shape of BrF5 is a square based pyramidal.
and stick model for BrF5
5 bp + 1 lp (with 1 Pi bond) O O
F F F
Example: XeOF4 (Square pyramidal) F
Xe F Xe
• The double bond-lone pair repulsion is greater F
F F
than the single bond-lone pair repulsion.
• So, the pi bond and the lone pair are oriented in
the opposite directions. Fig. 17: Lewis representation and
ball and stick model for XeOF4
4 bp and 2 lp
F F
Example: XeF4 - Square planar F F
Xe Xe
• Here, there are 2 lone pairs. In order to minimise
F F
the repulsion, both the lone pairs are oriented F F
in the opposite direction as lp-lp repulsion is
greater than lp-bp repulsion.
Fig. 18: Lewis representation and
• The shape obtained in this case is square planar. ball and stick model for XeF4

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sp3d2 hybridization - Octahedral geometry Shape of the molecule

6 bp + 0 lp (0 pi bond) - SF6

6 bp + 0 lp (1 pi bond) - IOF5 Octahedral

6 bp + 0 lp (2 pi bond) - XeO2(OH)4

5 bp + 1 lp (0 pi bond) - BrF5
Square base pyramidal
5 bp + 1 lp (1 pi bond) - XeOF4

4 bp + 2 lp (0 pi bond) - XeF4 Square planar

BOARDS MAIN ADVANCED

Hybridization: sp3d3

• Steric number = 7
• Geometry: Pentagonal bipyramidal
• The angle between the bond pairs are 72°

Fig. 19: Pentagonal bipyramidal

7 bp + 0 lp geometry
F
Example: IF7 (Pentagonal bipyramidal) F
F F
• Here, both I and F have 7 valence electrons F
F
F F I
and they will form 7 bond pairs. The resultant I F
F
hybridization will be sp3d3 with both the shape
and the geometry being pentagonal bipyramidal. F F
F F
Fig. 20: Lewis representation and
6 bp + 1 lp ball and stick model for IF7
Example: XeF6 (Distorted octahedral) F
• If we introduce a lone pair at the axial position, F
then it will have Five lp-bp repulsions. F F F
• If we introduce a lone pair at the equatorial F Xe
Xe F F
position, then it will have two repulsions at 72°
and the two axial bonds cause a 90° repulsion. F F
• It is difficult to find a stable position for a lone F F
pair. So, this lone pair will keep moving around Fig. 21: Lewis representation and
the structure to attain stability. ball and stick model for XeF6

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• Hence, we cannot explain the structure of XeF6 using hybridization. Three centre four electron
bonds are used to study the structure of XeF6.
• Thus, XeF6 has a distorted octahedral geometry.

- -
6 bp + 1 lp (with 1 pi bond) O O

F F F F

Example: XeOF5- (Pentagonal pyramidal) F

Xe F Xe
F
• In order to minimise the repulsion, the F
F
lone pair and the pi bonds are oppositely F
directed.
• This has a shape of the pentagonal
Fig. 22: Lewis representation and
ball and stick model for XeOF5-
pyramidal.

sp3d3 hybridization - Pentagonal bipyramidal geometry

7 bp + 0 lp (0 pi bond) - IF7 Pentagonal bipyramidal

6 bp + 1 lp (0 pi bond) - XeF6 Distorted octahedral

6 bp + 1 lp (1 pi bond) - XeOF5- Pentagonal pyramidal

BOARDS MAIN
Hybridizations in Hydrocarbons

Ethane
• During the formation of C2H6, 1s-orbital and px, py C2H6
and pz-orbitals undergo sp3 hybridization.
CGround state : 1s22s22p2
• This results in the formation of four hybridized
orbitals for each carbon atom.
• Among the four sp3 hybrid orbitals, one hybrid ↑↓ ↑↓ ↑ ↑
orbital of one carbon atom will overlap with the 1s 2s 2p
1s-orbital of the hydrogen atom to produce 3
sigma bonds. C2H6
• In addition, the last orbital will overlap with one
CExcited state : 1s22s12p3
sp3 orbital of another carbon atom forming a 1s 2s 2p
sigma bond between the two C-atoms.
↑↓ ↑ ↑ ↑ ↑
• As there is a single bond between 2 carbon
atoms, rotation around a single bond is possible
in this case. sp3

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H σ H
σ

H H
σ C C σ
σ
σ σ
H H

Fig. 23: sp3 hybridization in ethane

Ethene

• Only 2px, 2pz, and 2s take part in hybridization.

C2H4
• One 2py orbital remains unchanged and will
undergo pi bond formation. CGround state : 1s22s22p2
• This leads to the formation of three sp2 hybridized
orbitals.
↑↓ ↑↓ ↑ ↑
• The hybrid orbitals look like sp3 orbitals but they
are sp2 orbitals as they are fatter and shorter. 1s 2s 2p
• One sp2 orbital of one carbon atom overlaps
with one sp2 orbital of another carbon atom to
form a sp2 – sp2 sigma bond. unhybridized
• The other two sp2 hybrid orbitals overlap with C2H4 p-orbitals
two hydrogen atoms containing unpaired CExcited state : 1s22s12p3
electrons. 1s 2s 2p
• A pi bond is formed by the unhybridized 2py ↑↓ ↑ ↑ ↑ ↑
orbitals of each carbon atom. This pi overlap will
happen above and below the carbon-carbon sp2
sigma bond.

π
H H H σ σ H
π
C C C σ C
H σ π
H H σ H
π

Fig. 24: sp2 hybridization in ethene

Ethyne

• The electronic configuration of carbon in its

ground state will be represented as 1s2 2s2 2p2 . C2H2
When it gets excited, the electronic configuration CGround state : 1s22s22p2
will change to 1s2 2s1 2px1 2py1 2pz1 .
• In C2H2, each carbon is attached to one hydrogen
atom and therefore the 2s1 and the 2pz1 orbitals ↑↓ ↑↓ ↑ ↑
get hybridized. This further leads to the formation
1s 2s 2p
of four sp-hybridized orbitals, wherein each
carbon will form two hybridized sp-orbitals.

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• C-C sigma bond is formed when one sp-orbital unhybridized

of one carbon overlaps with 1 sp-orbital of C2H2 p-orbitals
another carbon and two C-H bonds are created
when the second sp-orbitals on each carbon CExcited state : 1s22s12p3
overlaps with 1s orbital of hydrogen.
↑↓ ↑ ↑ ↑ ↑
• The carbon atom will have two half-filled
2p-orbitals. These two pairs of p-orbitals do not 1s 2s 2p
participate in the hybridization and instead form sp
two pi bonds resulting in the creation of a triple
bond.
π 2px
2px
π
2py
σ
H C σ C H
H C C H
π σ
2py
π

Fig. 25: sp hybridization in ethyne

BOARDS MAIN
Order of Repulsion

Lone pair-lone pair repulsion is greater than that of the lone pair-bond pair, which is greater than
bond pair-bond pair repulsion.

bp - bp < lp - bp < lp - lp

Order of repulsion with various bond pair - lone pair combinations.

BOARDS MAIN
Bond Angle

• The angle between the bonds of any two of the 180°

non-central atoms with the central atom is the
bond angle.
• Bond angle is considered between adjacent
bonded pairs.
• So, if there is a molecule ABC in which both B B A B
and C are bonded (attached) to A, then the angle
between the lines AB and AC is the bond angle. Fig. 26: Representation
The same case holds true if there are more than of bond angle
two non central atoms.

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Factors affecting the bond angle

Hybridization

Number of lone pairs on

the central atom

Size and electronegativity

Bond angle of the central atom

Size and electronegativity

of the terminal atom

Steric repulsions

Factors affecting bond angle

• Hybridization: Bond angle increases with increase in the s-character of a bond.
• Number of lone pairs on the central atom: Lone pairs cause the bond angle between the
bonded pair to shrink inwards to a greater extent to minimise repulsion and to attain maximum
stability (as in the case of ammonia). When there are two lone pairs, bond pairs will end up
closer and at a point lone pairs will stay at the maximum distance possible to reduce repulsion
and bond pairs at a distance where they cannot be brought further closer together. Thus, the
molecule will attain an optimised geometry.
• Size and electronegativity of the central atom: Electronegative central metal atom pulls the
bond pair electron cloud towards it, causing the bond pairs to come closer and that will cause
increased repulsion.
• Size and electronegativity of the terminal atom: With increase in the electronegativity of
peripheral atom the bond pair electron clouds will be more distant to each other leading to less
bond pair - bond pair repulsion as a consequence to which the bond angle decreases. Also if
the peripheral groups are bulky then due to steric repulsion the bond angle increases.
• Steric repulsion: If there is a bulky atom (larger size), it will experience more repulsion when
compared to tiny atoms (smaller size) that cause less repulsion.

Summary sheet

• Steric Number = 5 (sp3d hybridization), Geometry - Trigonal bipyramidal

≫ Shape: Seesaw (4 bp + 1 lp) (0 pi bond) - SF4
≫ Shape: Seesaw (4 bp + 1 lp) (1 pi bond) - IOF3
≫ Shape: Seesaw (4 bp + 1 lp) (2pi bonds) - XeO2F2
≫ Shape: T shape (3 bp + 2 lp) - ICl3
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≫ Shape: T shape (3 bp + 2 lp) (1 pi bond) - XeOF2

≫ Shape: Linear (2 bp + 3 lp) - I3-
• Steric Number = 6 (sp3d2 hybridization), Geometry - Octahedral
≫ Shape: Octahedral (6 bp and 0 lp) (0 pi bond) - SF6
≫ Shape: Octahedral (6 bp and 0 lp) (1 pi bond) - IOF5
≫ Shape: Octahedral (6 bp and 0 lp) (2 pi bonds) - XeO2(OH)4
≫ Shape: Square pyramidal (5 bp and 1 lp) (0 pi bond) - BrF5
≫ Shape: Square pyramidal (5 bp and 1 lp) (1 pi bond) - XeOF4
≫ Shape: Square planar (4 bp and 2 lp) (0 pi bond) - XeF4
• Steric Number = 7 (sp3d3 hybridization), Geometry - Pentagonal bipyramidal
≫ Shape: Pentagonal bipyramidal (7 bp and 0 lp) (0 pi bond) - IF7 -
≫ Shape: Distorted octahedral (6 bp and 1 lp) (0 pi bond) - XeF6
≫ Shape: Pentagonal pyramidal (6 bp and 1 lp) (1 pi bond) - XeOF5
Hybridization in ethane
≫ 1s-orbital and px, py and pz-orbitals undergo sp3 hybridization.
≫ It results in the formation of four hybridized orbitals for each carbon atom.
≫A  mong the four sp3 hybrid orbitals, three hybrid orbitals of each carbon atom will overlap
with 1s orbital of three hydrogen atoms to produce three sigma bonds.
≫ The last orbital will overlap with one sp3-orbital of another carbon atom forming a sigma
bond between the two C atoms.
Hybridization in ethene
≫ 2px, 2pz and 2s-orbitals take part in hybridization.
≫ One 2py -orbital remains unchanged and will undergo pi bond formation.
≫ This leads to the formation of three sp2 hybridized orbitals.
≫ One carbon atom overlaps the sp2 orbital of another carbon atom to form sp2 - sp2 sigma
bond.
≫ The two sp2 hybrid orbitals get overlapped by two hydrogen atoms containing unpaired
electrons.
≫ A pi bond is formed by the unhybridized 2py orbitals of each carbon atom. This pi-overlap will
happen above and below of the carbon-carbon sigma bond.
Hybridization in ethyne
≫ The ground state and the excited state configuration for carbon are 1s2 2s2 2p2 and 1s2 2s1
2px12py1 2pz1 respectively.
≫ In C2H2, each carbon is attached to one hydrogen atom and therefore, the 2s1 and the
2pz1-orbitals get hybridized. This further leads to the formation of four sp hybridized orbitals,
wherein each carbon will form two hybridized sp-orbitals.
≫ C-C sigma bond is formed when one sp-orbital of one carbon overlaps with one sp-orbital
of another carbon and two C-H bonds are created when the second sp-orbital on each
carbon overlaps with 1s-orbital of hydrogen.
≫ The carbon atom will have two half-filled 2p-orbitals. These two pairs of p-orbitals do not
participate in the hybridization and instead form two pi bonds, resulting in the creation of a
triple bond.
• Order of repulsion: Lone pair - lone pair > lone pair - bond pair > bond pair - bond pair repulsion.

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• Bond angle: The angle between the bonds of any two of the non central atoms with the central
atom is the bond angle.
• Factors affecting the bond angle
≫H  ybridization: The bond angle increases with increase in the s-character of a bond.
≫N  umber of lone pairs on the central atom: The lone pairs cause the bond pairs to shrink
inwards to a greater extent to minimise repulsion and to attain maximum stability.
≫S  ize and electronegativity of the central metal atom: The electronegative central metal
atom pulls the bond pair electron cloud towards it. Thus, the bond pairs will come closer and
repulsion will increase.
≫S  ize and electronegativity of terminal atom: With increase in the electronegativity of
peripheral atom the bond pair electron clouds will be more distant to each other leading to
less bond pair - bond pair repulsion as a consequence to which the bond angle decreases.
Also if the peripheral groups are bulky then due to steric repulsion the bond angle increases.
≫S  teric repulsion: The bulky atom will experience more repulsion when compared to a non-
bulky atom.

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