Lewis Dot Structure Rules:

 Treat ions separately (e.g. NH4Cl)

 Count only valence electrons
 Assemble bonding framework
 Fill up non-bonding electrons on
 outer atoms
 Fill up bonding electrons on inner atoms
 Calculate Formal Charge
 Minimize Formal Charge
To do Lewis Structures:

 Must be able to recognize polyatomic

ions
 Must be able to identify valence
electrons
 Must be able to construct Bond
framework

Periodic Table : Column numbers!

 Hints on Lewis Dot Structures
1. Octet “rule” is the most useful guideline.
2. Carbon forms 4 bonds.
3. Hydrogen typically forms one bond to other
atoms.
4. When multiple bonds are forming, they are
usually between C, N, O or S.
5. Nonmetals can form single, double, and
triple bonds, but not quadruple bonds.
6. Always account for single bonds and lone
pairs before forming multiple bonds.
7. Look for resonance structures.
PCl3
5+(3*7)=26 e-

Bonding Pairs

Lone Pairs
(a.k.a. nonbonding electrons)
Formal Charge
Difference between the # of valence electrons in the free atom and the #
of electrons assigned to that atom in the Lewis structure.

FC = formal charge; G.N. = Group Number

#BE = bonding electrons; #LPE = lone pair electrons

If Step 4 leads to a positive formal charge on an inner atom beyond the

second row, shift electrons to make double or triple bonds to minimize
formal charge, even if this gives an inner atom with more than an octet of
electrons.
 MUATAN FORMAL
H2SO4 → dua struktur Lewis yang memenuhi :
O O
H O S O H H O S O H
O O
(1) 4 ikatan S-O (2) 2 ikatan S-O
2 ikatan S=O

Eksperimen:
Ada 2 jenis ikatan antara S dan O pada H2SO4 → 157 pm
(S–O) & 142 pm (S=O) → Struktur (2) yang realistis
Alat bantu untuk memilih : Muatan formal
MF = Σ e- valensi – Σ e- nonikatan – ½ Σ e- ikatan
Struktur (1) Struktur (2)
H = 1 – 0 – ½ (2) = 0 H = 1 – 0 – ½ (2) = 0
Okiri = 6 – 4 – ½ (4) = 0 Okiri = 6 – 4 – ½ (4) = 0
Okanan = 6 – 4 – ½ (4) = 0 Okanan = 6 – 4 – ½ (4) = 0
Oatas = 6 – 6 – ½ (2) = –1 Oatas = 6 – 4 – ½ (4) = 0
Obawah = 6 – 6 – ½ (2) = –1 Obawah = 6 – 4 – ½ (4) = 0
S = 6 – 0 – ½ (8) = +2 S = 6 – 0 – ½ (12) = 0
Muatan bersih = 0 Muatan bersih =0

Struktur (1) memiliki 3 atom bermuatan

→ energi sangat tinggi (tidak stabil)
CONTOH
Gunakan konsep muatan formal untuk menentukan mana
struktur hidroksilamina, NH3O, yang terbaik.
Penyelesaian:
H
H N O H N O H
H H
(1) (2)
H = 1 – 0 – ½ (2) = 0 H = 1 – 0 – ½ (2) = 0
N = 5 – 0 – ½ (8) = +1 N = 5 – 2 – ½ (6) = 0
O = 6 – 6 – ½ (2) = –1 O = 6 – 4 – ½ (4) = 0

Struktur (2) terbaik karena muatan formal semua atomnya nol.

 Covalent Bonding
Multiple Bonds
• It is possible for more than one pair of electrons to
be shared between two atoms (multiple bonds):
• One shared pair of electrons = single bond (e.g. H2);
• Two shared pairs of electrons = double bond (e.g. O2);
• Three shared pairs of electrons = triple bond (e.g. N2).
H H O O N N Octet in each case

• Generally, bond distances shorten with multiple

bonding.
 Odd Number of Electrons…
NO Number of valence electrons = 11

N O N O
Resonance occurs when more than one valid Lewis structure can be
written for a particular molecule (i.e. rearrange electrons)

NO2
Number of valence electrons = 17

O N O O N O O N O
Molecules and atoms which are neutral (contain no formal charge) and with an
unpaired electron are called Radicals

O2 O O O O
Oxygen is a ground state
"diradical"
Beyond the Octet
 Elements in the 3rd period or higher can
have more than an octet if needed.
 Atoms of these elements have valence d
orbitals, which allow them to
accommodate more than eight
electrons.
 More than an Octet…
Elements from the 3rd period and beyond, have ns, np and
unfilled nd orbitals which can be used in bonding

Cl
PCl5 P : (Ne) 3s2 3p3 3d0 Cl
Number of valence electrons = 5 + (5 x 7) = 40 Cl P
Cl
Cl
SF4 S : (Ne) 3s2 3p4 3d0
Number of valence electrons = 6 + (4 x 7) = 34 F F
S
F F
The Larger the central atom, the more atoms
you can bond to it – usually small atoms such
as F, Cl and O allow central atoms such as P
and S to expand their valency.
 Less than an Octet…

BCl3 Cl
Group 3A atom only has six electrons
B around it
Cl Cl

However, Lewis acids “accept” a pair of electrons readily

from Lewis bases to establish a stable octet

Cl H Cl H
_ +
Cl Al + N H Cl Al N H
Cl H Cl H
Lewis acid Lewis base salt
VSEPR Definitions
Electron group –set of electrons that occupies a
particular region around an atom.
Ligand – an atom or a group of atoms bonded to
an inner atom
Steric number – the sum of the number of ligands
plus the number of lone pairs; in other words, the
total number of groups associated with that atom.
KNOW THESE!
Lone Pairs Take up a Bit More Space…

Experiments show
that sulfur
tetrafluoride has
bond angles of 86.9°
and 101.5 °. Give an
interpretation of
these bond angles

NOTE: Sizes and electronegativities of

exterior atoms also affect bond angles!!!
VSEPR.
The familiar VSEPR (Valence Shell
Electron Pair Repulsion) approach
to molecular structure was
developed by Ronald Gillespie. The
basic idea is that lone pairs of
electrons occupy space around a
central atom in much the same way
as do atoms that are bonded to the
central atom. The lone pairs and
bonded atoms then assume that
geometry that minimizes
Ronald Gillespie.
electrostatic repulsion
between them.
Electron domains and molecular geometry:

each lone pair of electrons

observed geometry is
plus each atom bonded to the that where the electron
central atom constitute an domains are as far apart
electron ‘domain’ as possible

lone pair
of electrons

N H
H
H

Lewis dot diagram Ammonia

of ammonia trigonal pyramidal
(derived from tetrahedral geometry)
 Using VSEPR
In order to use VSEPR to predict molecular structure:

1) Draw up Lewis dot diagram for the molecule or ion. The first atom
(e.g. Br in BrF5) is always the central atom. Place the other atoms
around the central atom.

place 5 F
atoms around red = 7 valence
central Br electrons for Br

If these are single bonds, contribute one electron per attached atom.
Then add the valence electrons for the central atom = 7 for Br.

2) Work out number of electron domains = valence electron pairs (‘n’)

plus attached atoms on central atom. For BrF5 n = 6.

3) Relate n to the type of structure predicted for that value of n. n = 6 =

octahedral.

4) Place lone pairs in expected positions, maximizing separation of lone

pairs. For BrF5, there is one lone pair, so mol. structure = square
pyramidal.
The structure of BrF5 from VSEPR:

Lewis dot diagram parent structure molecular structure =

square pyramidal

lone pair

n = 6 from five n = 6, parent structure molecular or final

attached atoms = octahedral, but one site structure – disregard
plus one electron occupied by a lone pair the lone pair
pair
Parent shapes for EXn molecules (n = 2-5)

Formula n shape shapes of structures

EX2 2 linear

EX3 3 trigonal planar

EX4 4 tetrahedral

EX5 5 trigonal
bipyramidal
Parent shapes for EXn molecules (n = 6-8)

Formula n shape shapes of structures

EX6 6 octahedral

EX7 7 pentagonal
bipyramidal

EX8 8 square
antiprismatic
Final structures for VSEPR theory.
More final structures for VSEPR.
 A series of derivatives of the EX4 geometry (all
with n = 4) but with increasing numbers of lone
pairs:

lone
pairs

Methane ammonia water hydrogen

fluoride
Tetrahedral trigonal pyramid bent linear diatomic
Structures derived from trigonal geometry (n = 3):
lone pair

trigonal planar bent

boron trifluoride nitrite anion, NO2-

trigonal planar bent
 Ozone – a bent molecule:
The structure of the O3 (ozone) molecule can be predicted using
VSEPR. First draw up the Lewis dot diagram:
Note that two pairs For the valence shell of
of e’s still count as the
only one electron central oxygen atom n = 3,
domain = one so parent geometry =
attached O-atom trigonal. The final structure
is thus two-coordinate
Central atom bent, as seen for the
(red valence ozone molecule below:
electrons)

Structure of the ozone

molecule (oxygens =
red atoms) ozone
Structures derived from TBP (n = 5):
(Note: Lone pairs go in the plane:)
Structures derived from the octahedron (n
= 6):
Structures derived from the pentagonal
bipyramid (n = 7) (Note: lone pairs go axial)
Example: Negative charge adds a valence electron to iodine.

Note: The way the number of valence electrons (= 12) on the iodine is
derived is from the seven valence electrons for iodine (group 7
in the periodic table), plus one each from the F-atoms, and one from
the negative charge on the complex.
Example: Chlorine trifluoride

NOTE: in structures derived from a TBP parent structure, the lone pairs
always lie in the plane, as seen here for the T-shaped structure of ClF 3.
The structure of [IF5(C6H5)]-:
Note: an aliphatic or aromatic group is equivalent to an F.

phenyl group

fluorine

iodine

S.Hoyer, K.Seppelt (2004) J. Fluorine Chem. ,125, 989

Diphenyl(acetato)iodine(V)oxide

carbon atoms
from phenyls oxide
oxygen

iodine

phenyl group

two pairs
of electrons
oxygen from = double bond
acetato group
The structure of bis(pentafluorophenyl)xenon. VSEPR
explains this type of structure, which is linear like XeF2.
(explain the latter in terms of VSEPR)

xenon

pentafluoro
phenyl group

H.Bock, D.Hinz-Hubner, U.Ruschewitz, D.Naumann

(2002) Angew.Chem.,Int.Ed. , 41, 448
The [I(C6H5)2]+ cation:

iodine

phenyl group
Bis(trifluoroacetato)phenyl-iodine(III)

iodine

trifluoroacetate
group

phenyl group
The effect of lone pairs on bond angles:

In VSEPR the lone pairs appear to occupy more space than

electron pairs in bonds, with the result that bond angles are
compressed away from the lone pairs. For example, in
structures derived from tetrahedral parent geometry, such as
water or ammonia, the H-O-H and H-N-H angles are compressed
to be less than the 109.5º expected for a regular tetrahedron:

lone pairs

water O N ammonia
H
H oH H o H
104.5 106.7
Effects of lone pairs on bond angles
in ClF3 and ClF5.

87.5o 86.0o

chlorine trifuoride chlorine pentafluoride

 Try Lewis Structure of
Some Examples:
CH3CH2NH2
Cl2CO
Ozone (O3)
NO2 vs. N2O

SPENT LOTS O’ TIME PRACTICING…