Molecular Structures

John W. Moore
C2H6O structural isomers:
Conrad L. Stanitski
Peter C. Jurs
H H H H
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http://academic.cengage.com/chemistry/moore
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.. – H
H–C–C–O
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..
H–C–O –C–H
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H H H H

ethanol dimethyl ether

Chapter 9
m.p./ °C -114 -142
Molecular Structures b.p./ °C +78 -25

Molecular shape is important!

Small structural changes cause large property
Stephen C. Foster • Mississippi State University changes.

Using Molecular Models Using Molecular Models

Physical models of 3D-structures: Hand-drawn molecules:
Going back into
the screen
ball and stick space filling H
In the plane of
the screen

C
Computer versions: H H
H Coming out of
the screen

Predicting Molecular Shapes: VSEPR Predicting Molecular Shapes: VSEPR

The Valence Shell Electron Pair Repulsion model is
used to predict shapes. Key ideas:

1. e- pairs stay as far apart as possible.

• Repulsions are minimized.
2. Molecule shape is governed by the number of Linear Triangular planar Tetrahedral

bond pairs and lone pairs present.

3. Treat multiple bonds like single bonds.
• Each is a single e- group.
4. Lone pairs occupy more volume than bonds.

Triangular bipyramidal Octahedral

1
Predicting Molecular Shapes: VSEPR Predicting Molecular Shapes: VSEPR
Shapes that minimize repulsions: If a molecule contains:
• bonding pairs only – these angles are correct:

linear triangular tetrahedral triangular octahedral

planar bipyramidal

• These angle change (a little) if any “X” is replaced by a

Bonds and lone pairs determine shape. lone pair:
Use the notation AXnEm • lone pair/lone pair repulsions are largest.
m lone pairs on • lone pair/bond pair are intermediate in strength.
n atoms bonded to central atom A • bond/bond interactions are the smallest.
central atom A

Predicting Molecular Shapes: VSEPR Predicting Molecular Shapes: VSEPR

AXnEm: 2 e- group central atoms (m + n = 2)
Molecules may be described by their:
• electron-pair (e- pair) geometry Linear e- pair geometry
• molecular geometry (molecular shape)
2 e- groups
bond lone
pairs pairs
These geometries may be different. 2 0 AX2E0
linear
• Atoms can be “seen”, lone pairs are invisible.
1 1 AX1E1

..
linear

molecular geometry

Predicting Molecular Shapes: VSEPR Predicting Molecular Shapes: VSEPR

AX2E0 examples: AXnEm: 3 e- group central atoms (m + n = 3)
180.0°
Triangular planar e- pair geometry
Cl Be Cl Linear.
3 e- groups
bond lone
pairs pairs
180.0° 3 0 AX3E0
“2” bonds, 0 lone pairs on C.
O C O (treat double bonds as 1 bond) triangular planar
Linear.
2 1 AX2E1
..

angular (bent)
180.0°

1 2 AX1E2
H C C H Each H-C-C unit is linear.
..

linear
180.0°
molecular geometry

2
Predicting Molecular Shapes: VSEPR Predicting Molecular Shapes: VSEPR
AX3E0 examples: AXnEm: 4 e- group central atoms (m + n = 4)
Tetrahedral e- pair
4 e- groups geometry
bond lone
120° pairs pairs

Cl B Cl Triangular planar. 4 0 AX4E0

tetrahedral
Cl
..
3 1 AX3E1
molecular
triangular pyramidal
geometry
..
H C C H Each C is AX3E0 = triangular planar. AX1E3? 2 2 AX2E2
H H All molecules with only angular (bent)
1 bond are linear!

Predicting Molecular Shapes: VSEPR Predicting Molecular Shapes: VSEPR

H VSEPR applies to each atom in a molecule.
AX4E0
H C H All angles = tetrahedral angle.
• Alkanes: each C is tetrahedral.
H

AX3E1
H N H Lone-pair/bond > bond/bond
H repulsion: H-N-H angle is
reduced.

AX2E2
H O Two lone pairs: H-O-H angle is
H even smaller.

Predicting Molecular Shapes: VSEPR Expanded Octets

Lactic acid: Central atoms with five or six e- pairs:
Bond pairs Lone pairs Shape
Tetrahedral O 5 0 Triangular bipyramidal
H
Triangular planar C 4 1 Seesaw
H O
..
..

3 2 T-shaped
..
H C C C O
.. 2 3 Linear
..

O
..

H H
H 6 0 Octahedral
Tetrahedral C
Tetrahedral C 5 1 Square pyramidal
4 2 Square planar
Tetrahedral O
3 3 T-shaped
• lone pairs repel the most.
• they get as far apart as possible.

3
Expanded Octets Expanded Octets
AXnEm: m + n = 5
Triangular bipyramidal e- pair geometry. F F F
F Cl F F Xe F
F P F F S F
F F
F

Triangular Seesaw T-shaped Linear

bipyramidal

The atoms are non-equivalent.

Green atoms are axial
axial; blue atoms are equatorial
equatorial.

Expanded Octets Expanded Octets

AXnEm: m + n = 6 Octahedral e- pair geometry:

All atoms are F F F F Cl

equivalent in
AX6E0 F S F F Br F Cl I Cl
F F F Cl

Octahedral Square pyramid Square planar

Orbitals Consistent with Molecular Shapes Valence Bond Theory

Lewis dot + VSEPR predict molecular shapes, but…
but This works for H2 and HF, but why does…
How do atomic orbitals (s, p…) lead to these shapes? • Be form compounds?
• Be (1s2 2s2).
Valence bond theory:
theory: bonds occur when partially- • No unpaired e- to share.
occupied atomic orbitals overlap. • Experiments show: linear BeH2, BeCl2, …

H2 – H(1s) overlaps H(1s) HF – H(1s) overlaps F(2p) • C form 4 bonds at tetrahedral angles?
• C (1s2 2s2 2p2).
• 2px1 2py1 Two bonds?
• p orbitals are at 90° to each other
• Experiments show: tetrahedral CH4, CCl4, …
74 pm 109 pm

4
Orbitals Consistent with Molecular Shapes sp Hybrid Orbitals
Atomic orbitals (AOs) can be hybridized (mixed). Be compounds (BeH2, BeF2 …):
• Sets of identical hybrid orbitals form identical bonds.
• Number of hybrids formed = number of AOs mixed.

One s orbital + one p orbital → two sp hybrids.

Each sp hybrid (180° apart) holds one e-.

Two equivalent covalent bonds form.

sp2 Hybrid Orbitals sp2 Hybrid Orbitals

B forms three sp2 hybrid orbitals: B compounds (BH3, BF3 …):
• One s orbital mixes with two p orbitals.
• One p orbital remains unmixed.

Each sp2 hybrid (120° apart) holds one e-.

Three equivalent covalent bonds form.

sp3 Hybrid Orbitals sp3 Hybrid Orbitals

C forms four sp3 hybrid orbitals: N and O compounds (NH3, H2O…) have more e-:
• One s orbital mixes with three p orbitals.
• All p orbitals are mixed.

In C, each sp3 hybrid (109.5° apart) holds one e-.

Four equivalent covalent bonds form.

5
sp3 Hybrid Orbitals Hybridization
“Octet rule” molecules have tetrahedral e- pair
shape. Summary:
• sp3 hybridized (CH4, NH3, H2O, H2S, PH3, …)
Mixed Hybrids (#) Remaining Geometry
s+p sp (2) p+p Linear
σ bond).
Head-to-head bond = a sigma bond (σ bond s+p+p sp2 (3) p Triangular planar
There are: s+p+p+p sp3 (4) Tetrahedral
H
• 4 σ bonds in CH4 σ bond
d orbitals can also form hybrids:
• 3 σ bonds in NH3
• 2 σ bonds in H2O Mixed Hybrids (#) Remaining Geometry
C
s+p+p+p+d sp3d (5) d+d+d+d Triangular bipyramid
H H s+p+p+p+d+d sp3d2 (6) d+d+d Octahedral
H

Hybridization in Molecules with Multiple Bonds Hybridization in Molecules with Multiple Bonds

Carbon atoms form: H H

C (sp2) + C (sp2) overlap (σ bond):
C C
• tetrahedral centers (CH4, CHF3 , C2H6…) = sp3
H H
• triangular-planar centers (H2CO, C2H4 …) = sp2
Unhybridized C p orbitals each contain one e-.

H C C H
H H H H
C σ bond C overlap C C
The double bond in ethene is composed of: H H H H
• a σ bond – head-to-head overlap of sp2 on each C atom.
• a π bond – sideways overlap of p AOs on the C atoms.
Sideways overlap forms one π bond
• the lobes above and below the plane together equal 1 bond

Hybridization in Molecules with Multiple Bonds Hybridization in Molecules with Multiple Bonds

Formaldehyde is similar: C also forms linear centers:

• C2H2 (acetylene) = sp hybridized

H C C H

The triple bond is:

• one σ bond
• two π bonds
• sp hybridization leaves two unmixed p orbitals
on each C.

6
Hybridization in Molecules with Multiple Bonds Hybridization in Molecules with Multiple Bonds

σ bond: C (sp) + C (sp) overlap: π bonds prevent bond rotation:

H C C H

Molecule C-C bonding C-C rotation

Two p orbitals on each C contain a single e-. ethane (CH3–CH3) σ yes
ethene (CH2=CH2) σ+π no
H C C H overlap H C C H
ethyne (HC≡CH) σ+π+π no

Non-rotating double bonds allow cis-trans isomerism

Two π bonds to occur.
• above and below overlaps are 1 bond.
• front and back overlaps are a second bond.

Molecular Polarity Molecular Polarity

• Most bonds are polar (e.g. C-O) • Water is polar (bond dipoles do not cancel)
• O is δ-, C is δ+ (ENO = 3.5, ENC = 2.5)
• But many molecules are nonpolar (e.g. CO2). O Net Dipole, μ = 1.85 D
dipole
+
arrow points to δ-,
H H
the + shows δ+
O=C=O
δ- 2δ+ δ-

• The dipoles cancel because of CO2’s shape.

• have equal size but point in opposite directions.

Molecular Polarity Molecular Polarity

Molecule μ (D) A molecule is nonpolar if it is:
Dipole moment (μ) is a measure of
H2 0 • AXnE0 and all X are identical.
molecule polarity:
HF 1.78 CO2 AX2E0 linear
Units: coulomb meter (Cm)
HCl 1.07 CH4 AX4E0 tetrahedral
Debye (D)
HBr 0.79 CCl4 AX4E0 tetrahedral
weakly polar HI 0.38 PF5 AX5E0 triangular bipyramidal
CH4 0
• “divisible” into nonpolar AXnE0 shapes
highly polar CH3Cl 1.92
CH2Cl2 1.60 PCl3F2 triangular planar (PCl3) + linear (PF2 )
CHCl3 1.04 XeF4 linear (XeF2) + linear (XeF2 )
nonpolar (μ=0) CCl4 0

7
Molecular Polarity Molecular Polarity
AXnEm molecules are polar if they don’t divide into
nonpolar shapes, and:: F H +
No net dipole Net
• m ≠ 0: C C dipole
F F F F
H2O AX2E2 bent polar F F

NH3 AX3E1 pyramidal polar CF4 is non polar CHF3 is polar

• The X in AXnE0 differ:

CH2Cl2 AX4E0 tetrahedral polar
PF4Cl AX5E0 triangular bipyramidal polar

How polar? It depends on the number, type, and

geometry of the polar bonds.

Molecular Polarity Noncovalent Interactions

Non polar Molecules attract each other.
AX5E0 and “X” differ.
BUT divisible into Intermolecular forces:
nonpolar shapes:
linear + triangular • also called noncovalent interactions.
planar
+ • are small (compared to bonding forces).
PCl5 PCl3F2
• do not include ionic or metallic-bonding forces.
Non polar
AX5E0; identical X

Three types:
PCl4F
Polar • London forces.
AX5E0 Polar
“X” differ AX5E0 and “X” differ. • dipole-dipole attraction.
Doesn’t divide into
nonpolar shapes
• hydrogen bonding.
PF3Cl2

London Forces London Forces

Also called dispersion forces.
• Random e- motion produces a temporary dipole in Noble Gas Halogen Hydrocarbon
one molecule which induces a dipole in another. # of e- bp (°C) # of e- bp (°C) # of e- bp (°C)
He 2 −269 F2 18 −188 CH4 10 −161
Ne 10 −246 Cl2 34 −34 C2H6 18 −88
Ar 18 −186 Br2 70 +59 C3H8 26 −42
Kr 36 −152 I2 106 +184 C4H10 34 0

• Strength (0.05↔ 40 kJ/mol):

Small molecule = few e- = weak attraction.
Large molecule = many e- = stronger attraction. More e- = larger attraction = higher b.p.
• Occur between all atoms and molecules.
The only force between nonpolar molecules.

8
Dipole-Dipole Attractions Dipole-Dipole Attractions
Nonpolar Molecules Polar Molecules
# of e- bp (°C) # of e- bp (°C)
Polar molecules attract each other. SiH4 18 −112 PH3 18 −88
GeH4 36 −90 AsH3 36 −62
Br2 70 +59 ICl 70 +97

Relative importance of dipole/dipole and London is

Strength: 5 ↔ 25 kJ/mol. hard to predict:

Dipole London bp (°C)

stickier
HI small (0.38 D) large (54 e-) −36
HCl large (1.07 D) small (18 e-) −85

Hydrogen Bonding Hydrogen Bonding

An especially large dipole-dipole attraction.
• 10 ↔ 40 kJ/mol.
H on one molecule
• Occurs when H bonds directly to F, O or N. interacts with O on
another molecule.
F, O & N are small with large electronegativities.

• results in large δ+ and δ- values.

H-bonds are usually drawn as dotted lines.

Hydrogen Bonding

Water is a liquid at
room T (not a gas).