CHE2107: Inorganic Chemistry

Chapter 3. Simple Bonding Theory

박계현 (Jesse Park)

Yonsei University
 3.1 Lewis Electron-Dot Diagrams
• This chapter provides an overview of Lewis dot structures, valence shell
electron-pair repulsion (VSEPR), and related topics.

• When using various models to describe bonding within a molecule, they must
be consistent with experimental data (bond lengths, bond angles, and bond
strengths).
• For example, angles and distances are most frequently determined by diffraction
(X-ray crystallography, electron diffraction, neutron diffraction) or spectroscopic
(microwave, infrared) methods.
 3.1 Lewis Electron-Dot Diagrams
• Lewis electron-dot diagrams provide a good starting point for analyzing the
bonding in molecules.
• It was devised by G. N. Lewis, an American chemist who contributed much to the
understanding of thermodynamics and chemical bonding in the early twentieth
century.
 3.1 Lewis Electron-Dot Diagrams
• In Lewis diagrams, bonds between two atoms exist when they share one or
more pairs of electrons.
• In addition, some molecules have nonbonding pairs, or lone pairs, of electrons
on atoms.
• These electrons contribute to the shape and reactivity of the molecule but do
not directly bond the atoms together.
 3.1 Lewis Electron-Dot Diagrams
• Most Lewis structures are based on the concept that eight valence electrons,
form a particularly stable arrangement.
• These 8 electrons correspond to electrons in s and p orbitals, providing stable s2
p6 configurations found in noble gases.
• Yes, there are many exceptions to the octet rule.
• Hydrogen is an exception (stable with two valence electrons).
• Some molecules require more than eight electrons around a given central atom
• Some molecules require fewer than eight electrons.
 3.1 Lewis Electron-Dot Diagrams
• Water follow the octet rule, and eight electrons surround the central atom.
• Each hydrogen atom shares two electrons with the oxygen, forming two bonds.
• The O atom accommodates two bonding pairs and two lone pairs:

• The electron pairs shared by H and O in the water molecule are counted toward
both the 8-electron requirement of oxygen and the 2-electron requirement of
hydrogen.

• The Lewis model defines double bonds as containing four electrons and triple
bonds as containing six electrons:
 3.1.1 Resonance
• In many Lewis structures, the choice of which atoms are connected by multiple
bonds is arbitrary.
• When alternate locations for single bonds and multiple bonds are possible
that all afford valid Lewis structures, a structure demonstrating each option
should be drawn.
• For example, three drawings (resonance structures) of CO32− are needed to
show the double bond in each of the three possible C-O positions.
 3.1.1 Resonance
• In fact, experimental evidence shows that all three C-O bonds are equivalent,
with bond lengths (129 pm) between typical C-O double-bond and single-bond
distances (116 pm and 143 pm, respectively).
• All three drawings are necessary to describe the structure, with each drawing
contributing equally to describe the bonding in the actual ion.
• This is called resonance.
• There is more than one possible way in which the valence electrons can be
placed in a Lewis structure.
• Note that in resonance structures, such as those shown for CO32−, the electrons
are arranged differently, but the nuclei remain in fixed positions.
 3.1.1 Resonance
• When a molecule has several resonance structures, its overall electronic
energy is lowered, making it more stable.
 3.1.2 Higher Electron Counts
• When it is impossible to draw a structure consistent with the octet rule
because additional valence electrons remain to be assigned after the octet rule is
satisfied on all atoms, it is necessary to increase the number of electrons
around the central atom.
• An option limited to elements of the third and higher periods is to use d
orbitals for this expansion, although theoretical work suggests that expansion
beyond the s and p orbitals is unnecessary for most main group molecules.
 3.1.2 Higher Electron Counts
• For example, 10 electrons are required around chlorine in ClF3 and 12 around
sulfur in SF6.
• The increased number of electrons is often described as an expanded shell or
an expanded electron count.
• The term hypervalent is used to describe central atoms that have electron
counts greater than the atom’s usual requirement.
 3.1.3 Formal Charge
• Formal charge is the apparent electronic charge of each atom in a molecule,
based on the electron-dot structure.
• Formal charges help assess resonance structures.
• They are presented here as a simplified method of describing structures.
• Formal charge is useful but has many limitations.
 3.1.3 Formal Charge
• Formal charges can help determine resonance structures consistent with the
true electronic ground state of the molecule.
• However, note that formal charge is only a tool for assessing Lewis structures,
not a measure of any actual charge on the atoms.
• Formal charge on the atom can be found using the following equation

4−0−4
=0

6−4−2 5−4−2
• Further, =0 = −1

Charge on molecule or ion = sum of formal charges

−1 0+0−1 = −1
 3.1.3 Formal Charge
• Resonance structures consistent with electronic ground state of the species
generally (a) have smaller formal charges, (b) place negative formal charges
on more electronegative elements (in the upper right-hand part of the periodic
table), and (c) have smaller separation of charges.

One negative charge on

less electronegative S

One negative charge Large formal charge on

on electronegative N both S and N

Correct
No answer. All of these are unstable.

C most reasonable with -1 charge

on most electronegative oxygen,
but large separation of charge
 3.1.3 Formal Charge
• Some molecules have satisfactory electron-dot structures with octets but
have more reasonable formal charge distributions with expanded electron
counts.
• The actual molecules
and ions are consistent
with electron counts
greater than 8 on the
central atom and with a
large contribution from
the resonance
structure that uses
multiple bonds to
minimize formal
charges.
• The multiple bonds may
also influence the
shapes of the
molecules.
 3.1.4 Multiple Bonds in Be and B Compounds
• A few molecules may seem to require multiple bonds to satisfy the octet
rule for Be and B.
• However, multiple bonds for F and Cl are generally unexpected on the basis
of their high electronegativities.
• Structures minimizing formal charges for these molecules have only four
electrons in the valence shell of Be and six electrons in the valence shell of B, in
both cases fewer than the usual octet.

• Alternatively, eight electrons on the central atom predicts multiple bonds.

1+

1+ 2− 1+ 1+ 2− 1+ 1−
•
• These structures, however, result in nonideal formal charges.
 3.1.4 Multiple Bonds in Be and B Compounds
• In actual solid BeF2, a complex network is formed with a Be atom coordination
number of 4.

• BeCl2 dimerizes to a 3-coordinate structure in the vapor phase.

• The linear monomer can be formed at high temperatures but is unstable due to
the electronic deficiency at Be.
• In the actual dimer and the network formed in the solid-state, the halogen
atoms share lone pairs with the Be atom in an attempt to fill beryllium’s valence
shell.
• Still, the monomer is frequently drawn as a singly bonded structure.
 3.1.4 Multiple Bonds in Be and B Compounds
• For BF3, actual bond lengths are shorter than expected for single bonds, so
the partial double-bond character predicted may first seems correct.

• While a small double bonding is possible, the strong polarity of the B–halogen
bonds actually accounts for the short bonds.
• The BF3 combine readily with other electron donating molecules (Lewis
bases), forming a roughly tetrahedral structure with four bonds.
 3.1.4 Multiple Bonds in Be and B Compounds
• Because of this tendency, boron trihalides are frequently drawn with only six
electrons around the boron.

• Other boron compounds that cannot be adequately described via simple electron-
dot structures include hydrides such as B2H6, and many more complex molecules.
 3.2 Valence Shell Electron-Pair Repulsion
• Valence shell electron-pair repulsion (VSEPR) is an approach that provides a
method for predicting the shape of molecules based on the electron-pair
electrostatic repulsion described by Sidgwick and Powell in 1940 and further
developed by Gillespie and Nyholm in 1957.
• Based on Lewis electron-dot structures, the VSEPR method predicts shapes
that compare favorably with those determined experimentally.
• The most common method of determining the actual structures is X-ray
diffraction, although electron diffraction, neutron diffraction, and many
spectroscopic methods are also used.
 3.2 Valence Shell Electron-Pair Repulsion
• The basis of the VSEPR approach is that electrons repel each other because
they are negatively charged.
• According to the VSEPR model, molecules adopt geometries such that valence
electron pairs position themselves as far from each other as possible to minimize
electron–electron repulsions.
 3.2 Valence Shell Electron-Pair Repulsion
• A molecule can be described by the generic formula AXmEn, where A is the
central atom, X stands for any atom or group of atoms surrounding the central
atom, and E represents a lone pair of electrons.

E E
AX2E2

A SN = 4
X X

• The steric number (SN = m + n) is the total number of positions occupied by

atoms or lone pairs around a central atom.
• Lone pairs and bonding pairs both influence the molecular shape.
 3.2 Valence Shell Electron-Pair Repulsion
• Carbon dioxide is a molecule with two atoms attached (SN = 2) to the central
atom via double bonds.

• The electrons in double bonds repel and forces a linear structure.

• Sulfur trioxide has three atoms bound to the sulfur (SN = 3), with equivalent
partial double bond character between sulfur and each oxygen.

• Electron–electron repulsion can be minimized when the oxygens are at the

corners of an equilateral triangle, with O-S-O bond angles of 120°.
 3.2 Valence Shell Electron-Pair Repulsion
• Similarly, Lewis structures and geometries that minimizes the repulsive
energy can be found for steric numbers 4, 5, 6, 7, and 8.
 3.2 Valence Shell Electron-Pair Repulsion
• Bond angles and distances are uniform in these structures with two, three,
four, and six electron pairs.
 3.2 Valence Shell Electron-Pair Repulsion
• However, 5- nor 7-coordinate structures have nonuniform angles and
distances.
• The 5-coordinate molecules have a trigonal bipyramidal structure, with a
central triangular plane of three positions plus two other positions above and
below the center of the plane.

• The 7-coordinate molecules have a pentagonal bipyramidal structure, with a

pentagonal plane of five positions and positions above and below the center of
the plane.
 3.2 Valence Shell Electron-Pair Repulsion
• Lastly, square antiprism structure (SN = 8) is like a cube that has had the top
face twisted 45° into the antiprism arrangement.
• It has three different bond angles for adjacent atoms.
• [TaF8]3− has square antiprismatic geometry with slight distortion.
 3.2.1 Lone-Pair Repulsion
• Predictions of overall shapes can be made by considering some important
differences between lone pairs and bonding pairs.
• As a general guideline, the VSEPR model predicts that electron-pair repulsions
involving lone pairs (lp) are stronger than those involving bonding pairs (bp) in
the order:
lp-lp repulsions > lp-bp repulsions > bp-bp repulsions
 3.2.1 Lone-Pair Repulsion (SN = 4)
• The isoelectronic molecules CH4, NH3, and
H2O illustrate the effect of lone pairs on
molecular shape.
• Methane has four identical bonds between
carbon and each of the hydrogens.
• When the four pairs of electrons are arranged as
far from each other as possible, the result is
the familiar tetrahedral shape.
• The tetrahedron, with all H-C-H angles
measuring 109.5°, has four identical bonds.
 3.2.1 Lone-Pair Repulsion (SN = 4)
• Ammonia also has four pairs of electrons around
the central atom, but three are bonding pairs
between N and H, and the fourth is a lone pair
on the nitrogen.
• The nuclei form a trigonal pyramid with the
three bonding pairs.
• The lone pair occupies the fourth region in
space resulting in a tetrahedral arrangement of
the four electron groups.
 3.2.1 Lone-Pair Repulsion (SN = 4)
• Three bonding pairs are located between H
and N atoms.
• In contrast, the lone pair is attracted only by
the nitrogen nucleus.
• Consequently, the lone pair tends to spread
out and to occupy more space around the
nitrogen than the bonding pairs.
• As a result, the H-N-H angles are 106.6°, nearly
3° smaller than the angles in methane.
 3.2.1 Lone-Pair Repulsion (SN = 4)
• In a water molecule, two lone pairs and two
bonding pairs repel each other.
• Electron pairs adopt a tetrahedral arrangement.
• Now, we have lp–lp and lp–bp repulsions that
are stronger than the bp–bp repulsion.
• Lone pairs are able to spread out and occupy
more space.
• So, the H-O-H bond angle is only 104.5°, a 2.1°
decrease from the ammonia angles.
 3.2.1 Lone-Pair Repulsion (SN = 5)
• For the trigonal bipyramidal geometry, there are two
unique locations (axial and equatorial) for electron pairs.
• If there is a single lone pair, for example in SF4, the
lone pair occupies an equatorial position.
• This position provides the lone pair with the most
space and minimizes the interactions between the
lone pair and bonding pairs.
• If the lone pair were axial, it would have three 90°
interactions with bonding pairs. Favored
• In an equatorial position, it has only two 90°
interactions.

• The actual structure is distorted by the lone pair as it

spreads out in space and effectively squeezes the rest
of the molecule together.
Not favored
 3.2.1 Lone-Pair Repulsion (SN = 5)
• ClF3 has a steric number of 5 but now also has
two lone pairs.
• There are three possible structures for ClF3.
 3.2.1 Lone-Pair Repulsion (SN = 5)
• To determine the favorable structure, lp–lp
interactions should be considered first,
followed by lp–bp interactions.
• These interactions at angles of 90° or less are
generally considered destabilizing.
• We want maximal separation between lone
pairs.
• For example, in ClF3, structure B can be
eliminated quickly because of the 90° lp-lp angle.
 3.2.1 Lone-Pair Repulsion (SN = 5)
• While A has the largest 180° separation six 90° lp-bp
between lone pairs, C has a pretty large lp-lp interactions
angles of 120°.
• So, you may think the correct structure is A.
• However, C has only four 90° lp-bp
interactions, while A has six such interactions.
• Experiments have confirmed that the
structure is consistent with C.
• Structure exhibits slight distortions due to the
lone pairs, making lp–bp angles to be larger
than 90°.

four 90° lp-bp

interactions
 3.2.1 Lone-Pair Repulsion (SN = 5)
• The structures based on
a trigonal bipyramidal
arrangement always
place any lone pairs in
the equatorial plane, as
in SF4, BrF3, and XeF2.
• The resulting shapes
minimize both lp–lp
and lp–bp repulsions.
• The shapes are called
seesaw (SF4), distorted
T (BrF3), and linear
(XeF2).
 3.2.1 Lone-Pair Repulsion (SN = 6 and 7)
• In octahedral structures, all six positions are equivalent.

• When a single lone pair is present, it typically repels adjacent bonding pairs,
reducing bond angles accordingly, as for IF5.

• With two lone pairs, lp-lp repulsion is minimized if these pairs are trans, and
this is the shape that is adopted.
• Square planar XeF4 is an example.
 3.2.1 Lone-Pair Repulsion (SN = 6 and 7)
• The shape that minimizes electron-pair repulsions for a
steric number of 7 is the pentagonal bipyramid.
• IF7 exhibit this shape, with both axial and equatorial
fluorines.

• If a single lone pair is present, in some cases the lone

pair causes distortion.
• But, the nature of this distortion is not always easy to
ascertain.
• XeF6 is a classic example.

• With the lone pairs, they minimize their repulsions by

adopting axial trans positions, with the atoms all in the
equatorial plane.
• Two known examples are XeF5− and IF52−.
 3.2.2 Multiple Bonds
• The VSEPR model considers double and triple bonds to have slightly greater
repulsive effects than single bonds because of the repulsive effect of p
electrons that increase the electron density between the bonded.
• For example, the H3C-C-CH3 angle in (CH3)2C=CH2 is smaller, and the H3C-
C=CH2 angle is larger than the trigonal 120°
 3.2.2 Multiple Bonds
• Comparing to the previous figure,
we see that multiple bonds tend
to occupy the same positions as
lone pairs.
• Let’s consider examples from
steric number 5.
• The double bonds to oxygen in
SOF4 , ClO2F3, and XeO3F2 are all
equatorial, as are the lone pairs in
SF4, BrF3, and XeF2.

Double bonds
Lone pairs
 3.2.2 Multiple Bonds
• Multiple bonds also tend to occupy more space
than single bonds, causing distortions that
squeeze the rest of the molecule together.
• In molecules that have both lone pairs and
multiple bonds, these features may compete for
space.
• Examples are shown at the right.
• As a generalization, lone pairs often have a
greater influence than multiple bonds in dictating
molecular geometry.
 3.2.3 Electronegativity Scales
• Linus Pauling introduced the concept of electronegativity in the 1930s as a
means of describing bond energies.
• Pauling recognized that polar bonds have higher bond energies than nonpolar
bonds formed from the same elements.
• For example, he observed that the bond energy of HCl , 432 kJ/mol, was much
higher than the average of the bond energies of H2 (436 kJ/mol) and Cl2 (243
kJ/mol).
• He related the difference between actual and average bond energies to the
electronegativity difference between the elements involved.
 3.2.3 Electronegativity Scales
• Some early Pauling electronegativity values are in Table 3.3.
• He made adjustments for the sake of convenience, most notably to give the
elements C through F equally spaced values of 2.5 through 4.0.
• The value of 4.0 for fluorine is still commonly used as a reference point for
other electronegativity scales.
 3.2.3 Electronegativity Scales
• More recent values have been derived from other molecular and atomic
properties, such as ionization energies and electron affinities.
• Table 3.4 summarizes approaches used for a variety of electronegativity scales.
• Examining differences among these is beyond the scope of this text.
 3.2.3 Electronegativity Scales
• In most cases the different methods give similar electronegativity values.
• Values reported by Mann, Meek, and Allen (Table 3.5) is based on
configuration energies (CE), the average ionization energies of valence
electrons in ground state free atoms.
 3.2.3 Electronegativity Scales
• For s- and p-block elements the configuration energies are defined as
follows:

• For comparisons with the Pauling scale, the configuration energies are multiplied
by a constant to give values comparable to the Pauling scale.
 3.2.3 Electronegativity Scales
• Pauling’s calculation of electronegativities from bond energies requires
averaging over a number of compounds to minimize experimental
uncertainties.
• Methods that use ionization energies and other atomic properties can be
calculated more directly.

• In any case, it is important to emphasize that all electronegativities are

measures of an atom’s ability to attract electrons from a neighboring atom to
which it is bonded.
 3.2.3 Electronegativity Scales
• Fluorine has one of the largest electronegativity values, and electronegativity
decreases toward the lower left corner of the periodic table.
• Although usually classified with Group 1, hydrogen is quite dissimilar from the
alkali metals in its electronegativity, as well as in many other chemical and
physical properties.
• Hydrogen’s chemistry is distinctive from all the groups.
 3.2.3 Electronegativity Scales
• Electronegativities of the noble gases can be calculated more easily from
ionization energies than from bond energies.
• The noble gases have higher ionization energies and electronegativity than
the halogens.
 3.2.3 Electronegativity Scales
• Also, the noble gas exhibits a greater effective nuclear charge than
neighboring halogen.
• Indeed, atom sizes are somewhat smaller.
• As the result of this nuclear charge, noble gas nucleus may attract its own
electrons and electrons of neighboring atoms, resulting in a high
electronegativity.
 3.2.3 Electronegativity and Bond Angles
• By the VSEPR approach, trends in bond angles can be explained by
electronegativity.
• Consider the bond angles in the following molecules:

• As the electronegativity of the halogen increases, the halogen exerts a

stronger pull on electron pairs it shares with the central atom.
• This effect reduces the concentration of electrons near the central atom and
decreases the repulsion between the bonding pairs near the central atom.
• Lp-bp repulsion compresses the halogen–central atom–halogen angles.
• Consequently, the molecules with the most electronegative outer atoms, PF3
and OSF2, have the smallest angles.
 3.2.3 Electronegativity and Bond Angles
• Similarly, other examples can be found in Table 3.6.
• The compounds containing fluorine have smaller angles than those containing
chlorine, which in turn have smaller angles than those containing bromine.
• As the electronegativity of the outer atom increases, the lone pair exerts a
larger lp-bp repulsion, and forces smaller bond angles.
 3.2.3 Electronegativity and Bond Angles
• An alternative explanation for this trend is size.
• As the size of the outer atom increases in the order F < Cl < Br, the bond
angle increases.
 3.2.3 Electronegativity and Bond Angles
• In situations where the outer atoms remain the same but the central atom is
changed,

• As the central atom becomes more electronegative, it pulls bonding pairs

more strongly toward itself, increasing the concentration of electrons near the
central atom.
• The net effect is that an increase in bp–bp repulsions near the central atom
increases the bond angles.
• In these situations the molecule with the most electronegative central atom has
the largest bond angles.
 3.2.3 Electronegativity and Bond Angles
• Additional similar examples can be found in Table 3.6.
 3.2.3 Effects of Size
• So far, the most electronegative atoms have also been the smallest, and they had
the same effect on the bond angle.
• In other situations, size and electronegativity may have opposite effects,
where a smaller outer group is less electronegative than a larger group attached
to a central atom.
 3.2.3 Effects of Size
• More electronegative CF3 groups should result in withdrawal of more bonding
electrons, larger lp-bp repulsion, and a smaller bond angle.
• Alternatively, larger CF3 groups should lead to a larger bond angle.
• Crystal structure suggests that size is the more important factor in this case,
with the bond angle in N(CF3)3 larger by 7°.

• However, it is difficult to predict whether the atomic size or electronegativity

dominates.
 3.2.3 Summary
• Outer atoms
• Electronegativity increase → Repulsive effect of BP electrons decrease → bond
angle decrease
• Size increase → steric repulsion increase → bond angle increase

• Central atom (containing a lone pair)

• Electronegativity increase → Electron density near the central atom increase →
Repulsive effect of BP electrons increase → bond angle increase
• Size increase → lp-bp repulsion increase → bond angle decrease
 3.2.3 Molecules Having Steric Number = 5
• In molecules with SN = 5, less electronegative groups typically occupy
equatorial positions.
• In compounds below, less electronegative chlorines favor equatorial positions.

• Similarly, less electronegative CH3 groups favor equatorial.

• Less electronegative group results in concentrated electron density near P.

• To minimize electron repulsion, this electronegative group prefers for
equatorial position (120º between equatorial groups).
 3.2.3 Molecules Having Steric Number = 5
• Despite a similar reasoning, relative effects on bond angles by less
electronegative atoms are typically less than for lone pairs and multiple
bonds.
• For example, the bond angle to equatorial positions opposite the Cl atom in PF4Cl
is only slightly less than 120°, in contrast to the greater reduction in comparable
angles in SF4 and SOF4.
 3.2.3 Molecules Having Steric Number = 5
• In some cases, predicting structures is challenging.
• Let’s consider phosphorus compounds that contain fluorine and CF3 groups.
• CF3 is only slightly less electronegative than halogens.
• At first, we may expect CF3 to favor equatorial positions.
• However, due to the small difference in electronegativities, trigonal bipyramidal
phosphorus compounds containing varying numbers of F and CF3 groups with
both axial and equatorial CF3 groups are found.
 3.2.3 Molecules Having Steric Number = 5
• When two or three CF3 groups are present, the orientations are difficult to
explain.
• These groups are axial in PF3(CF3)2 but equatorial in PF2(CF3)3.
• Perhaps, more symmetrical structure is preferred.
 3.2.3 Group Electronegativities
• As in the case of individual atoms, numerous approaches have been taken to
estimate electron-attracting abilities of groups containing multiple atoms (such as
CH3, CF3, and OH).
• Despite wide variation in electronegativity values calculated using different
methods, trends emerge when examining sets of values that follow
expectations.
• Examples in order of decreasing group electronegativity include the following:
 3.2.4 Ligand Close Packing
• The ligand close-packing (LCP) model developed by Gillespie uses the
distances between outer atoms in molecules to predict molecular shapes.
• For molecules having the same central atom, the nonbonded distances between
the outer atoms are consistent, but the bond angles and bond lengths change.
 3.2.4 Ligand Close Packing
• For example, it was found that in a series of boron compounds, BF2X and BF3X,
the fluorine–fluorine distance remained nearly constant for a wide variety of X
groups, even if the steric number changed from 3 to 4, as shown in Table 3.7.
 3.2.4 Ligand Close Packing
• In the LCP model, ligands (outer atoms) are viewed as exhibiting a specific radius
when bonded to a certain central atom.
• If the outer atoms pack tightly together, the distance between the nuclei of the
atoms will then be the sum of these ligand radii.

F
B
F F

• For example, a fluorine atom attached to a central boron has a radius of 113 pm.
• When two fluorines are attached to a central boron, the distance between their
nuclei will be the sum of the ligand radii (226 pm).
• This value matches the F···F distances of the examples in the table.
 3.2.4 Ligand Close Packing and Bond Distances
• The LCP model predicts that nonbonded atom–atom distances in molecules
remain approximately the same, even if the bond angles around the central
atom are changed.
• For example, the fluorine–fluorine distances in NF4+ and NF3 are both 212 pm,
even though the F-N-F bond angles are significantly different.
 3.2.4 Ligand Close Packing and Bond Distances
• So, we may predict that NF3 has a smaller bond angle, and it does!
• 102.3° in comparison with the tetrahedral angle of 109.5° in NF4+.
 3.2.4 Ligand Close Packing and Bond Distances
• Because the F···F distance remains unchanged, the N-F distance in NF3 must
be longer than the 130 pm in NF4+.
• This can be illustrated using simple trigonometry.

• As expected, it has smaller the F-N-F angle, the longer the N-F bond.
 3.2.4 Ligand Close Packing and Bond Distances
• So, the LCP model complements the VSEPR approach.
• VSEPR predicts that a lone pair causes a smaller bond angle on the opposite
side.
• LCP predicts that the (outer atom)···(outer atom) distances should remain
essentially unchanged, requiring longer central atom–outer atom distances
and smaller bond angle.
 3.3 Molecular Polarity
• When atoms with different electronegativities are bonded, the resulting
molecule has polar bonds.
• The greater the difference in electronegativity, the more polar the bond.
• As a result, the bonds are dipolar, with relatively positive and negative ends.
• This polarity can cause specific interactions between molecules, depending on
the overall molecular structure.
 3.3 Molecular Polarity
• The polarity of molecules is determined indirectly by measuring the dielectric
constant (or relative permittivity with symbol εr or κ), which is the ratio of the
capacitance of a cell filled with a substance to the capacitance measured under
vacuum.
• Orientation of polar molecules in the electric field partially cancels out the
effect of the field and results in a larger dielectric constant. (bulk/macroscopic)
• Using data from different temperatures and Debye equation, we can find the
dipole moment (microscopic) for the molecule, defined as μ = Qr, where Q is
the difference in charges and r is the distance between these charges.

Polym. J. 1988, 20, 97.

 3.3 Molecular Polarity
• Theoretical dipole moments of diatomic molecules can be calculated easily.
• In theory, vector addition of the individual bond dipole moments gives the net
molecular dipole moment for complex molecules.

• However, it is usually not possible to calculate accurate molecular dipole

moments directly from bond dipoles.
• Table 3.8 shows experimental and calculated dipole moments of chloromethanes.
 3.3 Molecular Polarity
• The dipole moments of NH3, H2O, and NF3 reveal the often
dramatic effect of lone pairs.

• In ammonia, the averaged N-H bond polarities and the lone

pair point in the same direction, resulting in a large dipole
moment.

• Water has an even larger dipole moment.

• The polarities of the O-H bonds and the two lone pairs result
in polarities that reinforce each other.
 3.3 Molecular Polarity
• On the other hand, NF3 has a very small dipole moment,
the result of the polarity of the three N-F bonds opposing
the electron-rich lone pair.
• The sum of the three N-F bond moments is larger than the
lone pair effect, and the lone pair is the positive end of the
molecule.
 3.3 Molecular Polarity
• Molecules with dipole moments interact electrostatically with each other
and with other polar molecules.
• When the dipoles are large enough, the molecules orient themselves with the
positive end of one molecule toward the negative end of another, and higher
melting and boiling points result.
 3.3 Molecular Polarity
• On the other hand, if the molecule has a highly symmetric structure, or if the
bond dipoles cancel each other out, the molecule as a whole may have no net
dipole moment, even though the individual bonds are quite polar.
• Tetrahedral molecules such as CH4 and CCl4, trigonal molecules and ions such as
SO3, NO3−, and CO32−, and molecules having identical outer atoms for steric
numbers 5 and 6 such as PCl5 and SF6, are all nonpolar.
• In all these cases, the sum of all the polar bonds is zero because of the
symmetry of the molecules.
 3.3 Molecular Polarity
• Nonpolar molecules can also participate in intermolecular attractions.
• Small fluctuations in the electron density in such molecules create small
dipoles with extremely short lifetimes.
• These dipoles in turn attract or repel electrons in adjacent molecules.
• These attractive forces are called London forces or dispersion forces, and they
make liquefaction of the noble gases and nonpolar molecules—such as hydrogen,
nitrogen, and carbon dioxide—possible.
• Typically, London forces are more relevant for molecules with many electrons.
• The electron cloud becomes more polarizable and susceptible to perturbation
from external dipoles.
 3.4 Hydrogen Bonding
• Ammonia, water, and hydrogen fluoride all have much higher boiling points than
other similar molecules.
• These high boiling points are caused by hydrogen bonds, in which hydrogen
atoms bonded to nitrogen, oxygen, or fluorine also form weaker bonds to a
lone pair of electrons on another nitrogen, oxygen, or fluorine.
 3.4 Hydrogen Bonding
• With very polar bonds between hydrogen and
electronegative atoms, we get a partial positive charge
on the hydrogen.
• This partially positive hydrogen is strongly attracted to
the partially negative atoms of neighboring molecules.
• The strongly positive hydrogen and the strongly
negative lone pairs tend to line up and hold the
molecules together.
• Hydrogen bond is a strong form of non-covalent
interactions, and the definition of participating atoms has
expanded beyond the traditional atoms of N, O, and F.
• One other strong forms of non-covalent interaction due to
polarity is halogen bonding.
 3.4 Hydrogen Bonding
• In general, boiling points rise with increasing molecular weight, both
because the additional mass requires higher temperature for rapid movement
of the heavy molecules and because the larger number of electrons in the
heavier molecules provides larger London forces.
• The difference in temperature between the actual boiling point of water and the
extrapolated value is almost 200° C.
 3.4 Hydrogen Bonding
• Ammonia and hydrogen fluoride have similar but smaller differences from the
extrapolated values for their families.
• Water has a much larger effect, because each molecule can have as many as
four hydrogen bonds.
• Hydrogen fluoride can average no more than two hydrogen bonds, because
hydrogen fluoride has only one hydrogen.
 3.4 Hydrogen Bonding
• Water has other unusual properties
because of hydrogen bonding.
• For example, the freezing point of
water is much higher than that of
similar molecules.
• An even more striking feature is the
decrease in density as water freezes.
• The tetrahedral structure around each
oxygen atom, with two regular bonds to
hydrogen and two hydrogen bonds to
other molecules, requires a very open
structure with large spaces between
ice molecules.
• This makes the solid less dense than the
liquid water surrounding it, so ice floats.
 3.4 Hydrogen Bonding
• The same forces cause coiling of protein and
polynucleic acid molecules.
• A combination of hydrogen bonding with other
dipolar forces imposes considerable secondary
structure on these large molecules.
• Hydrogen bonds between carbonyl oxygen
atoms and hydrogens attached to nitrogen
atoms hold the molecule in a helical structure.
 3.4 Hydrogen Bonding
• Similar hydrogen bonds hold the parallel peptide chains together.
• The bond angles of the chains result in the pleated appearance of the sheet
formed by the peptides.
• These are two of the many different structures that can be formed from
peptides, depending on the side-chain groups R and the surrounding environment.
 3.4 Hydrogen Bonding
• Molecules trapped in holes in a solid, are
called clathrates.
• Similar structures of methane and water
hold large quantities of methane in the polar
ice caps.
• The amount of methane in such crystals can
be so great that they burn if ignited.