Structure of Borazine

•Isoelectronic with benzene

•In Borazine both Boron and Nitrogen are sp2
hybridised
•Each N-atom has one lone pair of electrons while each
B-atom has an empty p-orbital
•B3N3 ring of borazine molecule is partially delocalised
•Eletron drift from N to B is less than the -
electron drift from B to N

• Partial delocalisation
 Structure of S4N4

•SN adopts an unusual “extreme cradle” structure

• It can be viewed as a derivative of a hypothetical eight-membered
ring of alternating sulfur and nitrogen atoms.
•The nature of the "transannular" S–S interactions remains a
matter of investigation because it is significantly shorter than the
sum of the van der Waal's distances[4] but has been explained in
the context of molecular orbital theory.
• The bonding in SN is considered to be
delocalized, which is indicated by the fact that
the bond distances between neighbouring
sulphur and nitrogen atoms are nearly
identical. SN has been shown to co-crystallize
with benzene and the C molecule.
 Clathrates
Clathrates According to Powell, clathrate
compounds consist of atoms or molecules of
one substance called the 'guest' held in the
crystalline cages formed by the molecules of a
second substance called the 'host'.
 Geometries of the small and the large cages

Small dodecahedral (512) cage Large hexakaidecahedral (51264) cage

20 H2O molecules 28 H2O molecules
 The only type of interaction in these "cage
compounds" is the relatively weak van der Waals
forces and there is no chemical bonding.
 A simple clathrate may be designated by a
maximum composition formula nHmG where, H
and G are host and guest components,
respectively; n is the number of host molecules
per unit cage cell and m is the maximum number
of guest molecules that can be held in a single
cage.
 It is not necessary that all the cavities in the host
structure are filled. As a result, the clathrates . are
normally non-stoichiometric compounds.
Essential Conditions for Clathrate Formation
• Presence of cavities of appropriate size in the crystal lattice of the
'host'.
• Size of the `guest' particle should be such as to fit in the cavities of the
'host' without bringing any atoms closer together than which
correspond to the van der Waals' radii of the atoms.

Stability of Clathrate Compounds

Clathrate compounds once formed are quite stable due to the
following reasons :
• The 'guest' molecules tightly fit in the cavities of the 'host' molecules.
• The 'guest' molecules within the cages are at a minimum potential
energy.
• The 'guest' can escape from the 'host' only when the forces holding the
molecular cages together are overcome. This can be achieved by the
following two methods :
i) By heating the crystals.
ii)By dissolving them in a suitable solvent such as alcohol.
Preparation of Clathrates
• Clathrate compounds of argon, krypton and
xenon have been isolated by locking up these
gases in the cages of water, phenol or quinol.
• However, clathrate compounds of helium and
neon have not yet been prepared because
helium atoms are thought to be too small and
difficult to deform or Polarize as required by
van der Waals bonding to be Imprisoned in
the cages. The neon is border line and its
Clathrate could possibly be formed at
pressures in pressure in excess of 160 atm.
Types of Clathrates
(i) Gas hydrates
• Clathrates of argon, krypton and xenon in which water forms the cage, are known as
"gas hydrates". These gas hydrates have been prepared by solidifying water in
presence of these noble gases.
• The stability of 'gas hydrates' increases as the atomic number of the 'guest atom
increases. In noble gas hydrates the water molecules are linked to one another by
hydrogen bonds leaving roughly spherical voids which are occupied by gas atoms.
(ii)Quinol clathrates
• Clathrates of argon, krypton and xenon have been isolated by dissolving any one of
these in aqueous saturated solution of quinol, under pressure of 19-40 atm followed
by slow cooling.
• These clathrates are stable and can be stored for years together. It may be pointed out
that quinol molecules which form the cavities are held amongst themselves by
hydrogen bonds.
(iii) Phenol and p-hydroquinone clathrates Clathrates of phenol as well as 13-
hydroquinone with argon, krypton and xenon have been prepared by dissolving any
one of these gases in phenol or 8-hydroquinone followed by slow crystallization.
These clathrates are also quite stable. The usual composition of the rehydroquinone
clathrates is G • 43 05H 4 (OW2 where, C is Ar, Kr or Xe.
• Uses of Clathrates
• In the separation of noble gases. For example, neon can be
separated from argon, krypton and xenon because neon is the
only gas that does not form clathrates with quinol.
• Krypton-85 clathrate provides a safe and useful source of beta
radiations which are useful for measuring thickness of gases.
• Xenon-133 clathrate provides a compact source for gamma
radiations.
• The clathrates are a convenient form of handling, processing
and shipping of rare gas isotopes.
• Clathrates play an important role in some physiological actions.
e.g., it is thought that the anaesthetic action of xenon and
many other anesthetics is due to aqueous clathrates formation
in physiological strategic spots. When the anesthetic is no
longer administered, the clathrates equilibrium is destroyed,
the clathrates decompose and consciousness returns.
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