Molecular shapes of compounds

While the hybridized orbitals were introduced, in the foregoing discussion,

Valence-shell Electron-pair Repulsion (VSEPR) Model were included to
suggest the shapes of various molecules. Specifically, the VSEPR model
counts unshared electron pairs and the bonded atoms as the VSEPR number.
A single-, double- and tripple-bond is considered as 1. After having
considered the hybridized orbitals and the VSEPR model, we can not take a
systematic approach to rationalize the shapes of many molecules based on
the number of valence electrons. A summary in the form of a table is given
here to account for the concepts of hybrid orbitals, valence bond theory,
VSEPR, resonance structures, and octet rule. In this table, the geometric
shapes of the molecules are described by linear, trigonal planar, tetrahedral,
trigonal bypyramidal, and octahedral. The hybrid orbitals use are sp, sp2, sp3,
dsp3, and d2sp3. The VSEPR number is the same for all molecules of each
group. Instead of using NH3E, and OH2E2, we use :NH3, ::OH2 to emphasize
the unshared (or lone) electron pairs.
To determine shape of molecule
Trigonal Trigonal
Linear Tetrahedral Octahedral
planar bipyramidal
sp sp2 sp3 dsp3 d2sp3
BeH2 BH3 CH4 PF5 SF6
BeF2 BF3 CF4 PCl5 IOF5
CO2 CH2O CCl4 PFCl4 PF6-
HCN (>C=O) CH3Cl :SF4 SiF62-
HC CH >C=C< NH4+ :TeF4 :BrF5
CO32- :NH3 ::ClF3 :IF5
benzene :PF3 ::BrF3 ::XeF4
graphite :SOF2 :::XeF2
fullerenes ::OH2 :::I3-
•NO2 ::SF2 (:::I I2-)
N3-
:::ICl2-
:OO2 (O3) SiO44-
:SO2 PO43-
SO3 SO42-
ClO4-
• a lone odd electron : a lone electron pair
This table correlates a lot of interesting chemical concepts in order to
understand the molecular structures of these compounds or ions. There are
some intriqueing chemical relationships among the molecules in each column
for you to ponder.

Only Be and C atoms are involved in linear molecules. In gas phase, BeH 2 and
BeF2 are stable, and these molecules do not satisfy the octet rule. The
element C makes use of sp hybridized orbitals and it has the ability to form
double and triple bonds in these linear molecules.

Carbon compounds are present in trigonal planar and tetrahedral molecules,

using different hybrid orbitals. The extra electron in nitrogen for its
compounds in these groups appear as lone unpaired electron or lone electron
pairs. More electrons in O and S lead to compounds with lone electron pairs.
The five-atom anions are tetrahedral, and many resonance structures can be
written for them.

Trigonal bipyramidal and octahedral molecules have 5 and 6 VSEPR pairs.

When the central atoms contain more than 5 or 6 electrons, the extra
electrons form lone pairs. The number of lone pairs can easily be derived
using Lewis dot structures for the valence electrons.

In describing the shapes of these molecules, we often ignore the lone pairs.
Thus, •NO2, N3-, :OO2 (O3), and :SO2 are bent molecules whereas :NH3, :PF3,
and :SOF2 are pyramidal. You already know that ::OH2 (water) and ::SF2 are
bent molecules.

The lone electron pair takes up the equatorial location in :SF4, which has the
same structure as :TeF4 described earlier. If you lay a model of this
molecule on the side, it looks like a butterfly. By the same reason, ::ClF3
and ::BrF3 have a T shape, and :::XeF2, :::I3-, and :::ICl2- are linear.

Similarly, :BrF5 and :IF5 are square pyramidal whereas ::XeF4 is square
planar.