Molecular Geometry

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 Molecular Geometry
Three theories to explain:
• VSEPR: Valence shell electron pair
repulsion theory.
• Valence Bond Theory: Hybridization
theory
• Molecular Orbital Theory: advanced
course

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 Importance of Molecular Shape
Three dimensional structure of a molecule can have a profound
effect on its reactivity and biological activity.
These two molecules have identical formulas and shape, but
they are mirror images of each other and they have different
pharmacological activity (PA) .
Enantiomers and optical isomers

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Hemoglobin

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 VSEPR
• Lewis structures tell us how the atoms are connected to
each other.
• They don’t tell us anything about shape.
• The shape of a molecule can greatly affect its properties.
• Valence Shell Electron Pair Repulsion Theory allows us
to predict geometry

• Electron Pair Repulsion Theory: electron pairs (both

shared and unshared) try to orient themselves as far
away as possible in the space around the central
atom.

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 VSEPR Theory
• Uses Lewis structures and shared and
unshared pair of electrons to predict
geometry.
• All electrons are in their original atomic
orbitals.
• Predicts three dimensional geometry of
molecules. Can predict the angles of
bonds.

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 Properties of Shared and Unshared
Electron Pairs
• Shared pair of electron: the electron pair is attracted
by both nuclei – shape slender, like a cigar.

• Unshared pairs: take a lot of space as electrons

repulse each other. Shaped like a pear, or Mickey
Mouse ears.
• The strength of repulsions between pair of electrons:
unshared-unshared > shared - unshared>
shared - shared

• Molecular shape: repulsions between charge cloud

determines the arrangement
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 VSEPR
• Molecules take a shape that puts electron pairs as far
away from each other as possible.
• Draw the Lewis structure to determine electron pairs.
• Determine:
– bonding
– nonbonding lone pair
• Lone pair take more space.
• Multiple bonds count as one pair.
• The number of pairs determines
– bond angles
– underlying structure
• The number of atoms determines
– actual shape
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Electron Domains
 We can refer to the
directions to which
electrons point as
electron domains.
This is true whether
there is one or more
electron pairs pointing
in that direction.
 The central atom in
this molecule, A, has
four electron
domains.
 Electron-Group Geometries

• Differentiate between electron-group geometries and

molecular geometry
• 2 electron groups: linear
• 3 electron groups: trigonal planar
• 4 electron groups: tetrahedral
• 5 electron groups: trigonal bipyramidal
• 6 electron groups: octahedral

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 Electron Group Geometries

Electron Bond Underlying

pairs Angles Shape
2 180° Linear
3 120° Trigonal Planar
4 109.5° Tetrahedral
90° & Trigonal
5
120° Bipyramidal
6 90° Octagonal
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 Geometry Using VSEPR Theory

• Vocabulary:
– A: central atom
– B: bonded atom
– E: unshared pair of electrons
 Valence shell electron pair repulsion (VSEPR) model:
NO LONE Electron Pairs around the Central Atom
Predict the geometry of the molecule from the electrostatic
repulsions between the electron (bonding and nonbonding) pairs.

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

B B

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Two electron-group geometries

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Molecular Geometry

No Lone Pairs of Electrons on

Central Atom

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 VSEPR: all pairs are shared (0 lonely pairs)
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar

10.1 16
 3 electron-group geometry

Other examples: SO3

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10.1
 VSEPR: all pairs are shared
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral

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10.1
Tetrahedral Structure

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 4 electron-group geometry

Other examples: NH4+1, SO4-2

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10.1
 VSEPR: All electron pairs are shared
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal

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10.1
5 electron-group geometry

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10.1
 VSEPR: all electron pairs are shared
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB2 2 0 linear linear

trigonal trigonal
AB3 3 0
planar planar
AB4 4 0 tetrahedral tetrahedral
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
AB6 6 0 octahedral octahedral

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10.1
6 electron-pair geometry

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10.1
Tetrahedral Structure

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5 electron-group geometry

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10.1
6 electron-pair geometry

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10.1
 Molecular Geometry

Lone Electron Pairs on Central

Atom

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 VSEPR: THREE ELECTRON-GROUPS
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

trigonal trigonal
AB3 3 0
planar planar
AB2E 2 1 same bent

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10.1
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 VSEPR: FOUR ELECTRON-GROUPS
# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

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10.1
 VSEPR: FOUR ELECTRON-GROUPS

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB4 4 0 tetrahedral tetrahedral

trigonal
AB3E 3 1 tetrahedral
pyramidal

AB2E2 2 2 tetrahedral bent

O
H H

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10.1
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 Effect of Unshared Electron Pair on Bond Angles

lone-pair vs. lone pair lone-pair vs. bonding bonding-pair vs. bonding
repulsion
> pair repulsion
> pair repulsion 34
 VSEPR: FIVE ELECTRON-GROUPS

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron

See-saw
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10.1
 VSEPR: FIVE ELECTRON-GROUPS

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
F

F Cl

F
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10.1
VSEPR: FIVE ELECTRON-GROUPS ( LONE PAIRS)

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry
trigonal trigonal
AB5 5 0
bipyramidal bipyramidal
trigonal distorted
AB4E 4 1
bipyramidal tetrahedron
trigonal
AB3E2 3 2 T-shaped
bipyramidal
trigonal
AB2E3 2 3 linear
bipyramidal
I

I
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I 10.1
Five Electron Pairs on Central Atom

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VSEPR: SIX ELECTRON-GROUPS ( LONE PAIRS)

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
F
F F
Br
F F

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10.1
VSEPR: SIX ELECTRON-GROUPS ( LONE PAIRS)

# of atoms # lone
bonded to pairs on Arrangement of Molecular
Class central atom central atom electron pairs Geometry

AB6 6 0 octahedral octahedral

square
AB5E 5 1 octahedral
pyramidal
square
AB4E2 4 2 octahedral
planar
F F
Xe
F F

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10.1
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Angles in the Different Geometries

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Angles in the Different Geometries

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 VSEPR
Electron Bond Underlying
pairs Angles Shape
2 180° Linear
3 120° Trigonal Planar
4 109.5° Tetrahedral
90° & Trigonal
5
120° Bipyramidal
6 90° Octagonal
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 Actual shape
Non-
Electron Bonding Bonding
Pairs Pairs Pairs Shape
2 2 0 linear
3 3 0 trigonal planar
3 2 1 bent
4 4 0 tetrahedral
4 3 1 trigonal pyramidal
4 2 2 bent 50
 Actual Shape
Non-
Electron Bonding Bonding
Pairs Pairs Pairs Shape
5 5 0 trigonal bipyrimidal
5 4 1 See-saw
5 3 2 T-shaped
5 2 3 linear

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 Actual Shape
Non-
Electron Bonding Bonding
Pairs Pairs Pairs Shape
6 6 0 Octahedral
6 5 1 Square Pyramidal
6 4 2 Square Planar
6 3 3 T-shaped
6 2 1 linear
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 VSEPR: Examples

• CH4 - draw the structural formula

• Determine the number of shared and

unshared pairs of electrons.
• Write the Lewis structure

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 VSEPR
• Single bonds fill all
atoms.
H • There are 4 pairs of
electrons pushing
H C H away.
• The furthest they
can get away is
H 109.5º
(REMEMBER:
three dimensional
space.
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 4 atoms bonded
• Basic shape is
tetrahedral.
• A pyramid with a
triangular base. H
• Same shape for 109.5º
everything with 4
pairs.

H C H
H 55
 3 bonded - 1 lone pair
• Still basic tetrahedral but you can’t see the
electron pair.
• Shape is called
trigonal pyramidal.

H N H H N H
<109.5º
H H 56
 2 bonded - 2 lone pair

• Still basic tetrahedral but you can’t see the

2 lone pair.
• Shape is called
bent.

H O O H
<109.5º
H H 57
 Linear Geometry ( 3 atoms)

B A B

Designation: AB2
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 Three Electron Densities

B
B

A A
B B E

AB3, trigonal planar AB3E, Bent 59

Four Electron Densities

AB4 AB3E AB2E2

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 Five Electron Densities

AB5 AB4E

AB3E2 AB2E3

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 Six Electron Densities

AB6 AB5E

AB4 E2

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 3 Atoms No Lone Pair (double Bond)

• The farthest you can the electron pair

apart is 120º

H
C O
H
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 3 atoms no lone pair

• The farthest you can place the electron

pairs apart is 120º.
• Shape is flat and called
trigonal planar.
H
120º
H C
C O H O
H
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 2 atoms no lone pair

• With three atoms the farthest they can get

apart is 180º.
• Shape called linear.

180º

O C O
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