STRUCTURE AND BONDING 39

H
/°\
The basic tetrahedral shape is even more distorted producing an

H bond angle of 105°:

SX-'
If the spatial arrangement of atoms is required this can be deduced
from the basic structure by neglecting the positions occupied by
lone pairs of electrons. Water, for example, can be described as a
V shape whilst ammonia is a trigonal pyramid.

MULTIPLE COVALENT BONDS

Double and triple covalent bonds can be formed between elements

by the sharing of two or three electron pairs respectively. Consider
the formation of ethene (ethylene), C 2 H 4 :
X

H . x
x x
H H ^H
>. f~^ X /-* /^ /-**
+ _ C x C or C=C
X X
4H- » "H H' "H

The two kinds of covalent bond are not identical, one being a simple
covalent bond, a sigma (a) bond, the other being a stronger (but
more reactive) bond called a n bond (p. 56). As in the formation
of methane both elements attain noble gas configurations. We can
consider the formation of ethene as the linking of two tetrahedral
carbon atoms to form the molecule C 2 H 4 represented as:
H

this approach implying repulsion between the two bonding pairs.

Careful consideration of this model correctly indicates that all the
atoms lie in one plane. Spatially the double bond is found to behave
as a single electron pair and reference to Table 2.8 then (correctly)
suggests that each carbon has a trigonal planar arrangement.
The modern quantum-mechanical approach to bonding indicates
40 STRUCTURE AND BONDING

that these two 'models' for the ethene structure are identical, so that
we may use whichever is the more convenient.
Double bonds also occur in other covalent compounds. By
considering each double bond to behave spatially as a single bond
we are able to use Table 2.8 to determine the spatial configurations
of such compounds.
Triple bonds are formed by the sharing of three pairs of electrons
to form a a and two n bonds. Spatially these three bonds behave
as a single bond. Consequently acetylene (ethyne) C 2 H 2 has the
linear configuration often represented as H —C^C — H.
In each of the examples given so far each element has 'achieved'
a noble gas configuration as a result of electron sharing. There are,
however, many examples of stable covalent compounds in which
noble gas configurations are not achieved, or are exceeded. In the
compounds of aluminium, phosphorus and sulphur, shown below,
the central atoms have 6, 10 and 12 electrons respectively involved
in bondin

:
•rr
••

aluminium chloride phosphorus sulphur hexafluonde

(vapour) pentafluoride

(The spatial configurations of each of these compounds can be

deduced by reference to Table 2.8.)
These apparent anomalies are readily explained. Elements in
Group V, for example, have five electrons in their outer quantum
level but with the one exception of nitrogen, they all have unfilled
d orbitals. Thus, with the exception of nitrogen. Group V elements
are able to use all their five outer electrons to form five covalent
bonds. Similarly elements in Group VI, with the exception of
oxygen, are able to form six covalent bonds for example in SF6. The
outer quantum level, however, is still incomplete, a situation found
for all covalent compounds formed by elements after Period 2. and
all have the ability to accept electron pairs from other molecules
although the stability of the compounds formed may be low*. This
* Phosphorus pentafluoride PF5 will readily accept an electron pair from a fluoride
ion F~ to form the stable hexafluorophosphate (V) anion PF<~. This ion is isoelectronic
with SF6, and neither SF6 nor PF^ show any notable tendency to accept further
electron pairs, though there is some evidence for the existence of an SF^ ion.
 STRUCTURE AND BONDING 41

'donor-acceptor bonding' is very marked in Group HI, for when

elements in this group form three covalent bonds by sharing, they
have only six outer electrons. Consider for example the trichlorides
of boron and aluminium :
Cl Cl Cl Cl
\B/ and \\K

Cl Cl
Both these molecules exist in the gaseous state and both are trigonal
planar as indicated by reference to Table 2.8. However, in each, a
further covalent bond can be formed, in which both electrons of the
shared pair are provided by one atom, not one from each as in
normal covalent bonding. For example, monomeric aluminium
chloride and ammonia form a stable compound :

H:CI: H ci
x x * * . . \ /
H x N x Al : Cl : i.e. H—N
X X ..
H C1
H : Cl:
In this molecule, the aluminium receives a pair of electrons from
the nitrogen atom. The nitrogen atom is referred to as a donor atom
and the aluminium as an acceptor atom. Once the bond is formed
it is identical to the covalent bond of previous examples ; it differs
only in its origin. It is called a co-ordinate or dative bond, and can be
+ -
expressed either as H3N->A1C13 or H 3 N—A1C13. In the latter
formula the positive and negative charges are not ionic charges ; they
are merely formal charges to show that in forming the co-ordinate
link, the nitrogen lost a half share in its original electron pair which
is now shared with the aluminium, the latter having gained a half
share in the electron pair.
The formation of a fourth covalent bond by the aluminium atom
results in spatial rearrangement from the trigonal planar, for three
bonding electron pairs, to tetrahedral, for four bonding electron
pairs.
Other compounds containing lone pairs of electrons readily form
co-ordinate links and in each case a change in spatial configuration
accompanies the bond formation. The oxygen atom in dimethyl
ether, CH3 — O—CH3, has two lone pairs of electrons and is able to
donate one pair to, for example, boron trichloride :