SHAPES OF

MOLECULES
Chemistry

Recall that:
Covalent

bonds are formed from the

overlap of two atomic orbitals

Each

pair of covalent bond contains a pair

of electrons

Two
1.
2.

types of covalent bonds:

Sigma () bonds
Pi bonds () bonds

Electron Pairs
In molecules there

are 2 types of
electron pairs
1.
2.

Bonding Pairs
Non-bonding or
lone pairs

.The bonding pair

may be
represented by a
line

What is the shape of the

molecule?

We will use the geometric arrangement

of atoms around a central atom in a

covalent compound (or charged ion) to
determine the shape of the molecule
pi - bonds have a very limited impact on

shape
sigma-bonds have a much more important

effect

Valence Shell Electron Pair

Repulsion (VSEPR) Theory
The VSEPR theory proposes that shape of the
molecule is determined solely by the
repulsions between electron pairs present in
the valence shell of the central atom
The number of electron pairs around the central

atom can be determined by writing the Lewis

structure for the molecule
VSEPR theory is a model that helps us to

understand the 3-D structure of molecules

The VSEPR Model

VSEPR theory can be used to predict the shapes

and bond angles of molecules and molecular ions

Pairs of electrons that surround the central atom of

a molecule or ion are arranged as far apart as

possible to minimize electron-electron repulsion
Applicable only to covalent compounds (Ionic

bonds are non-directional while covalent bonds

have a preferred direction in space)

VSEPR Theory and Repulsion

Electrostatic force of repulsion between

electron pairs
Repulsion occurs to attain most
comfortable arrangement
Three types of repulsion to consider:
1. Bonding pair - Bonding pair repulsion
2. Lone pair - Lone pair repulsion
3. Bonding pair Lone pair repulsion

Strength of Repulsion
Depends on proximity of electron pairs to central atom
Bonding pair
located between two nuclei
Lone pairs
closer to central atom
they are delocalized
have no other nucleus to attract them
Lone pairs push bond pairs closer
As bonds are pushed closer together the bond angle decreases

LP-LP REPULSIONS > LP-BP REPULSIONS > BP-BP REPULSIONS

Molecular Geometries
Two Electron Pairs

Three Electron Pairs

Four Electron Pairs

Five Electron
Pairs

Six Electron
Pairs

Molecular Geometries (Contd)

Seven Electron Pairs

Using VSEPR theory to predict the shape

of the molecule
1. Decide which is the central atom in a molecule.

In cases of ambiguity, pick the least

electronegative atom (aside from hydrogen) as
this atom will be better able to share its
electrons with the other atoms in the molecule
2. Count up the valence electrons on the central

atom.
3. Count up the electrons used by the outer atoms

to make bonds with the central atom

Using VSEPR theory to predict the shape

of the molecule
4. The sum of steps (2) + (3) divided by two gives

the Valence Shell Electron Pair (VSEP) count

The VSEP count gives the number of electron
pairs around the central atom
5. Assign one electron pair for each bond (or two

pairs for each double bond). Any unassigned

electron pairs are lone pairs and are placed on
the CENTRAL atom.

VSEP Count
The predicted geometry of the molecule is based

on the number of VSEP count i.e. the arrangement

of EP around the central atom (both lone pair and
bonded pair)

1. Central Atom is Oxygen

2. Number of valence electrons = 6 eEg.
Calculate
the VSEP
count
3.
Number
of electrons
used
by for the water
molecule
peripheral atoms to bond to central
atom = 2 (1) = 2 eVSEP count = (6 e-) + (2 e-) /2 = 4 epairs
The O central atom has 4 e- pairs
around it
2 bonding pairs and 2 non-bonding

Predicting the Shapes of

Molecules
BeCl
2

What is the VSEP count? How many bonding pairs

and lone pairs?
Central Atom is Beryllium
Number of valence electrons = 2 eNumber of electrons used by peripheral atoms to

bond to central atom = 2 (1) = 2 eVSEP count = (2 e-) + (2 e-) /2 = 2 e- pairs

The Be central atom has 2 e- pairs around it
2 bonded pairs and NO non-bonded or lone pairs

Predicting the Shapes of

Molecules
BeCl
2

What is the shape of the

molecule? Bond angle?

In general
molecules , AX2, with
2 bonding pairs
and no lone pairs
are Linear.
Bond Angle = 1800
Linear Shape

Linear Molecules (AX2)

When applying the VSEPR model, we count a double or
triple bond as a single electron domain
Double and triple bonds are linear, and behave very much
like a single bond when it comes to repulsions

What is the structure of C2H2?

Predicting the Shapes of

Molecules
BF
3

What is the VSEP count? How many bonding pairs

and lone pairs?
Central Atom is Boron
Number of valence electrons = 3 eNumber of electrons used by peripheral atoms to

bond to central atom = 3 (1) = 3 eVSEP count = (3 e-) + (3 e-) /2 = 3 e- pairs

The B central atom has 3 e- pairs around it
3 bonding pairs and NO non-bonding or lone

pairs

Predicting the Shapes of

Molecules
BF
In general
What is the shape of the
molecule? Bond angle?
molecules ,
AX3, with 3
bonding
pairs and no
lone pairs
are Trigonal
Bond Angle = 120
Planar
Trigonal Planar
3

Trigonal Planar (AX3)

Examples include NO3-, SO3, CO32- and
C2H4

Q. Show that (a) NO3- and (b) SO3

display a trigonal planar
arrangement

Predicting the Shapes of

Molecules
CH
4

What is the VSEP count? How many bonding pairs

and lone pairs?
Central Atom is Carbon
Number of valence electrons = 4 eNumber of electrons used by peripheral atoms to

bond to central atom = 4 (1) = 4 eVSEP count = (4 e-) + (4 e-) /2 = 4 e- pairs

The C central atom has 4 e- pairs around it
4 bonding pairs and NO non-bonding or lone

pairs

Predicting the Shapes of

Molecules
In general molecules ,
CH4
What is the shape of the
molecule? Bond angle?

Bond Angle = 109.50

Tetrahedral

AX4, with 4 bonding

pairs and no lone
pairs are Tetrahedral

Trigonal Planar (AX4)

Q. Show that the following molecules
have a tetrahedral structure?
a) NH4+
b) SO42c) PO43d) Ni(CO)4
e) CH4

Predicting the Shapes of

Molecules
NH
3

What is the VSEP count? How many bonding pairs

and lone pairs?
Central Atom is Nitrogen
Number of valence electrons = 5 eNumber of electrons used by peripheral atoms to

bond to central atom = 3 (1) = 3 eVSEP count = (5 e-) + (3 e-) /2 = 4 e- pairs

The N central atom has 4 e- pairs around it
3 bonding pairs and 1 non-bonding or lone pair

Predicting the Shapes of

Molecules
NH3
What is the shape of the
molecule?

Bond Angle = 1070

Trigonal Pyramidal

In general molecules ,
AX3E, with 3 bonding
pairs and 1 lone pair
are Trigonal Pyramidal

Trigonal Pyramidal
Q. Show that the following molecules
have a trigonal pyramidal structure?
a) PH3
b) SO32-

Predicting the Shapes of

Molecules
HO
2

What is the VSEP count? How many bonding pairs

and lone pairs?
Central Atom is Oxygen
Number of valence electrons = 6 eNumber of electrons used by peripheral atoms to

bond to central atom = 2 (1) = 2 eVSEP count = (6 e-) + (2 e-) /2 = 4 e- pairs

The O central atom has 4 e- pairs around it
2 bonding pairs and 2 non-bonding or lone pairs

Predicting the Shapes of

Molecules
H2 O
What is the shape of the
molecule? Bond angle?

Bond Angle = 104.50

Bent (or V-shaped)

In general
molecules , AX2E2,
with 2 bonding
pairs and 2 lone
pairs are Bent or Vshaped

Bent or V-shaped molecules

Q. Show that the following molecules
have a bent structure?
a) H2S
b) SO2
c) H2O

Predicting the Shapes of

Molecules
PCl
5

What is the VSEP count? How many bonding pairs

and lone pairs?
Central Atom is Phosphorus
Number of valence electrons = 5 eNumber of electrons used by peripheral atoms to

bond to central atom = 5 (1) = 5 eVSEP count = (5 e-) + (5 e-) /2 = 5 e- pairs

The P central atom has 5 e- pairs around it
5 bonding pairs and NO non-bonding or lone

pairs

Predicting the Shapes of

Molecules
PCl5
What is the shape of the
molecule? Bond angle?

In general
molecules , AX5, with
5 bonding pairs
and 0 lone pairs
are Trigonal
Bipyramidal
Bond Angle = 900 and 1200
Trigonal Bipyramidal

Predicting the Shapes of

Molecules
SF
6

What is the VSEP count? How many bonding pairs

and lone pairs?
Central Atom is Sulphur
Number of valence electrons = 6 eNumber of electrons used by peripheral atoms to

bond to central atom = 6 (1) = 6 eVSEP count = (6 e-) + (6 e-) /2 = 6 e- pairs

The S central atom has 6 e- pairs around it
6 bonding pairs and NO non-bonding or lone

pairs

Predicting the Shapes of

Molecules
SF6
What is the shape of the
molecule? Bond angle?

The F-S-F Bond Angles are

all 900
Octahedral

In general molecules , AX6,

with 6 bonding pairs and 0
lone pairs are Octahedral

SHAPES AND BOND

ANGLES OF SIMPLE
ORGANIC COMPOUNDS

Organic
Compounds
Organic compounds belong to a large class
of chemical compounds whose molecules
contain carbon (except CO2 and carbonates)
The simple picture of overlap of half-filled

atomic orbitals cannot be used to explain the

geometry of all molecules especially organic
molecules
We use a concept known as hybridization to

explain bonding in carbon compounds

Methane (CH4)
Carbon needs to have four single

bonds

Needs four single electrons

Promotion of an electron from the 2s

orbital to the 2p orbital

Mixing the 2s and 2p orbitals

(hybridization)

Hybridisation
2s electrons

spontaneously promoted
to empty 2p orbital
s orbital and the

THREE p orbitals mix

to form FOUR hybrid
orbitals (sp3) with four
single electrons
number of orbitals is conserved

during hybridisation

Excited Carbon Atom

Four identical sp3 orbitals formed

All the same shape, size and energy

sp Hybrid Orbitals
3

Each hybrid orbital contains 25% s

character and 75 % p character.

The FOUR sp3 hybrid orbitals each

contains one electron

Hybrid orbitals arrange themselves in a

three dimensional space to get as far

apart as possible (to minimize repulsion)

Arrangement gives rise to a tetrahedral

structure bond angle of 109.5

Sp3 Hybridization (Methane)

Overlapping of sp3 orbitals on carbon

with s orbital of hydrogen gives rise to a
sigma bond

Sp3 Hybridization (Ethane)

sp3 orbitals of

carbon overlap
with s orbital
of hydrogen to
give a sigma
bond
sp3 orbitals on

both carbons
overlap to give
a sigma bond

Sp Hybridization
2

Sp Hybridization
2

Sp hybridization
2

Found in compounds such as alkenes (eg ethene)

Each carbon needs to form three bonds (two

hydrogens and one carbon)

Electron promotion still occurs in carbon followed by

mixing of the 2s and 2p orbitals

However, only two of the p orbitals are mixed with

the s orbital to form three sp2 hybrid orbitals

The unused p orbital remains pure (unhybridized)

sp2 Hybridization (C2H4)

Two sp2 orbitals will overlap with hydrogen 1s

orbital; the third sp2orbital will overlap with a

similar sp2 orbital on the other carbon atom
Each carbon has a pure, unused p orbital

containing an electron

The unused p orbitals are perpendicular to the

plane of the sp2 orbitals; projects above and below

the plane
close proximity of p orbitals causes sideways

overlap forming a pi bond; Pi bonds are weaker

than sigma bonds

Sp2 Hybridization (Ethene)

Ethene

Benzene
Six carbon atoms in a ring
Shows resonance hybrid
Hexagonal in shape - at each apex there is a

carbon bonded to a hydrogen

Each carbon is bonded to three other atoms; a
hydrogen and two other carbon atoms
Each carbon uses sp2 hybrid orbitals
Each carbon contains a pure p orbital perpendicular

to the plane of the ring

Benzene
Each unhybridized p orbital overlaps with two

other p orbitals, one on each of the two

neighbouring carbon atoms

A large circular pi-type bond is formed above

and below the plane

Electrons are delocalized in the benzene ring

Benzene
Overlapping of p orbitals

Benzene

Benzene
Canonical forms

Benzene
Hybridized structure

IB Chemistry Power Points

Topic 4
Bonding
www.pedagogics.ca

LECTURE
Shapes of Molecules

Much taken from

AN INTRODUCTION TO

BONDING
and
SHAPES OF
MOLECULES
Great thanks to
JONATHAN HOPTON & KNOCKHARDY PUBLISHING
www.knockhardy.org.uk/sci.htm

VALENCE SHELL ELECTRON PAIR

REPULSION (VSPER) THEORY
THE SHAPE ADOPTED BY A SIMPLE MOLECULE OR ION IS
THAT WHICH KEEPS REPULSIVE FORCES TO A MINIMUM

Molecules contain
covalent bonds. As
covalent bonds consist
of a pair of electrons,
each bond will repel
other bonds.
Bonds
will therefore
push each other as far
apart as possible to
reduce the repulsive
forces.
Because the repulsions
are equal, the bonds will
also be equally spaced.
A lone pair of electrons

Bonds are closer

together so repulsive
forces are greater

Al

Al

Bonds are further

apart so repulsive
forces are less
All bonds are
equally spaced
out as far apart
as possible
Note you must
think of spacing
in 3D not just 2D

ADDING ANOTHER ATOM - ANIMATION

ADDING ANOTHER ATOM - ANIMATION

2 regions of electron density

2 Bonding Pairs- BERYLLIUM CHLORIDE

Be

Cl

Cl

Be

Cl

Beryllium - has two electrons to pair up

Two covalent bonds are formed

Chlorine - needs 1 electron for octet

Beryllium still has an incomplete shell

BOND PAIRS

LONE PAIRS

BOND ANGLE...
Geometry ...

180
LINEAR

180

Cl

Be

Cl

MOLECULES WITH DOUBLE BONDS

Treat as a single region of electron density
The shape of a compound with a double bond is calculated in the same way. A
double bond repels other bonds as if it was single e.g. carbon dioxide

Carbon - needs four electrons to complete its shell

The atoms share two electrons

Oxygen - needs two electron to complete its shell

each to form two double bonds

DOUBLE BOND PAIRS 2

LONE PAIRS

Double bonds behave exactly as single

bonds for repulsion purposes so the
shape will be the same as a molecule with
two single bonds and no lone pairs.

180

BOND ANGLE... 180

Geometry ... LINEAR

3 regions of electron density

3 Bonding Pairs - ALUMINIUM CHLORIDE

Al

Cl

Cl

Cl
Al

Aluminium - has three electrons to pair up

Cl

Chlorine - needs 1 electron to complete octet

Three covalent bonds are formed; aluminium
still has an incomplete outer shell.

BOND PAIRS

LONE PAIRS

Cl
BOND ANGLE...
Geometry ...

120
TRIGONAL PLANAR

Cl

120

Al
Cl

4 regions of electron density

4 Bonding Pairs- METHANE

H
H

H
Carbon - has four electrons to pair up

Four covalent bonds are formed

Hydrogen - 1 electron to complete shell

C and H now have complete shells

BOND PAIRS

LONE PAIRS

H
109.5

C
BOND ANGLE...
Geometry ...

109.5
TETRAHEDRAL

H
H

4 regions of electron density - AMMONIA

H
N

BOND PAIRS

LONE PAIRS

TOTAL PAIRS

The shape is based on a tetrahedron but not all the repulsions are the same

LP-BP REPULSIONS > BP-BP REPULSIONS

The N-H bonds are pushed closer together

Lone pairs are not included in the shape!

H

N
H

107
H

ANGLE... 107
SHAPE... PYRAMIDAL

4 regions of electron density - WATER

H
H

BOND PAIRS

LONE PAIRS

TOTAL PAIRS

The shape is based on a tetrahedron but not all the repulsions are the same

LP-LP REPULSIONS > LP-BP REPULSIONS > BP-BP REPULSIONS

The O-H bonds are pushed even closer together

Lone pairs are not included in the shape

O
H

O
H
H

104.5
H

ANGLE... 104.5
SHAPE... BENT

HOW TO DETERMINESHAPES OF IONS

H

NH3

BOND PAIRS

PYRAMIDAL

LONE PAIRS

H-N-H 107

BOND PAIRS

TETRAHEDRAL

LONE PAIRS

H-N-H 109.5

BOND PAIRS

BENT

LONE PAIRS

H-N-H 104.5

NH4+

N+

N+

NH2

5 Bonding Pairs (HL only) - PHOSPHORUS(V) FLUORIDE

F

F
F

Phosphorus - has five electrons to pair up

Fluorine - needs one electron to complete octet

Five covalent bonds are formed; phosphorus can

make use of d orbitals to expand its octet

BOND PAIRS

LONE PAIRS

F
F

120

BOND ANGLE...
Geometry ...

120 & 90
TRIGONAL BIPYRAMIDAL

90

P
F

6 Bonding Pairs (HL only) - SULPHUR(VI) FLUORIDE

F
F

S
Sulphur - has six electrons to pair up

Fluorine - needs one electron to complete octet

Six covalent bonds are formed; sulphur can make

use of d orbitals to expand its octet

BOND PAIRS

LONE PAIRS

F
90

S
BOND ANGLE...
Geometry ...

90

OCTAHEDRAL

F
F

HL only - XENON TETRAFLUORIDE

Xe

Xe

BOND PAIRS

LONE PAIRS

TOTAL PAIRS

As the total number of electron pairs is 6, the shape is BASED on an octahedron

There are two possible spatial arrangements for the lone pairs

The preferred shape has the two lone pairs opposite each other

F
F

Xe
F

Xe
F

ANGLE... 90
SHAPE ... SQUARE PLANAR

SUMMARY
FUNDAMENTAL SHAPES no lone pairs
Molecules, or ions, possessing ONLY
BONDING PAIRS of electrons fit into
a set of standard shapes. All the
bond pair-bond pair repulsions are
equal.

C
A covalent bond will repel
another covalent bond

All you need to do is to count up the

number of bond pairs and chose one
of the
following
examples...BOND
BOND
ELECTRON
PAIRS

GEOMETRY

ANGLE(S)

180

EXAMPLE

LINEAR

BeCl2

TRIGONAL PLANAR

120

AlCl3

TETRAHEDRAL

109.5

CH4

HL ONLY
5

TRIGONAL BIPYRAMIDAL

OCTAHEDRAL

90

90 & 120
SF6

PCl5

Effect of Lone Pairs on Molecular Shape

If a molecule, or ion, has lone pairs on the central atom, the shapes are slightly
distorted away from the regular shapes. This is because of the extra repulsion
caused by the lone pairs.
BOND PAIR - BOND PAIR < LONE PAIR - BOND PAIR < LONE PAIR - LONE PAIR

As a result of the extra repulsion, bond angles tend to

be slightly less as the bonds are squeezed together.

SUMMARY - CALCULATING THE SHAPE OF IONS

The shape of an ion or molecule is determined by...

calculating the number of electrons in the outer shell of the central species *

pairing up electrons, making sure the outer shell maximum is not exceeded

calculating the number of bond pairs and lone pairs (regions of e - density)

using ELECTRON PAIR REPULSION THEORY to calculate shape and bond

angle(s)

Note for ions

*
*
*

the number of electrons depends on the charge on the ion

if the ion is positive you remove as many electrons as there are positive
charges
if the ion is negative you add as many electrons as there are negative charges
e..g. for PF6-

add one electron to the outer shell of P

for PCl4+ remove one electron from the outer shell of P

OTHER EXAMPLES TO TRY

O

SO42O

BOND PAIRS
LONE PAIRS
SHAPE
ANGLE

BrF3
F

BOND PAIRS
LONE PAIRS
SHAPE
ANGLE

Br
F

BrF5

F
Br
F

F
F

BOND PAIRS
LONE PAIRS
SHAPE
ANGLE

OTHER EXAMPLES TO TRY

O

SO42O

BOND PAIRS 4
LONE PAIRS
0
TETRAHEDRAL
ANGLE 109.5

BrF3
F

BOND PAIRS
LONE PAIRS
T SHAPED
ANGLE <90

Br

3
2

F
Br
F

F
F

Br
F

F
BrF5

BOND PAIRS 5
LONE PAIRS
1
SQUARE PYRAMID
ANGLES 90 <90

F
F

Br
F

F
F

TEST QUESTIONS
For each of the following ions/molecules, state the number of bond pairs
state the number of lone pairs
state the bond angle(s)
state, or draw, the shape

BF3
SiCl4
PCl

+
4

PCl6SiCl62H2S

TEST QUESTIONS
For each of the following ions/molecules, state the number of bond pairs
state the number of lone pairs
state the bond angle(s)
state, or draw, the shape

BF3

3 bp 0 lp 120 trigonal planar boron pairs up all 3 electrons in

its outer shell

SiCl4

4 bp 0 lp 109.5

tetrahedral
silicon pairs up all 4 electrons in
its outer shell

PCl

4 bp 0 lp 109.5

tetrahedral
as ion is +, remove an electron
in the outer shell then pair up

+
4

PCl6-

6 bp 0 lp 90

octahedral

as the ion is - , add one electron to

the 5 in the outer shell then pair up

SiCl62-

6 bp 0 lp 90

octahedral

as the ion is 2-, add two electrons

to the outer shell then pair up

H2S

2 bp 2 lp 92 bent planar
sulphur pairs up 2 of its 6
electrons in its outer shell 2 lone pairs are left