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INTER-HALOGEN COMPOUNDS
By Dr. D. M. Patel
Introduction:
Halogen elements have different electro-negativity. Due to this they combine
with each other to form covalent compounds (binary).
“The binary compounds formed by halogens amongst themselves are known as
Inter-halogen compounds”. These compounds have general formula; XYn, where n =
1, 3, 5 & 7.
Ternary compounds of halogens are not known; as such a complex molecule
might be unstable.
Classification:
Table 3.1 Various types of inter-halogen compounds
Element Fluoride Chloride Bromide Iodide
Fluorine ------ ------ ------ ------
Chlorine ClF, ClF3, ClF5 ------ ------ ------
Bromine BrF, BrF3, BrF5 BrCl ------ ------
Iodine IF, IF3, IF5, IF7 ICl, ICl3 IBr ------
From table 3.1, the following points may be noted.
 The inter-halogen compounds may be regarded as the halide of the more
electronegative halogen. Thus, since the electro positive character of halogens is
in the order F < Cl < Br < I, fluorine cannot form any inter-halogen compounds,
while iodine has the maximum tendency to form inter-halogen compounds.
 Since F has the least electropositive character, amongst inter-halogen compounds,
the fluorides are maximum in number.
 Inter-halogens can be grouped into four categories: XY, XY3, XY5, and XY7. Here
X halogen atom is more electropositive and larger in size than Y halogen atom.
 The oxidation state of atom X in XY, XY3, XY5, and XY7 molecules is equal to
+1, +3, +5 and +7 respectively.
 As the ratio between the radii of X and Y atoms increases, the number of halogen
atoms per molecule increases.
I. Inter-halogen compounds of XY type(Diatomic inter-halogens):
Preparation:
 These are generally prepared by the direct combination of halogens e.g.,
Br2 (g) + F2 (g) → 2 BrF; Br2 + Cl2 → 2 BrCl
I2 + Cl2 (l) (in equal amount) → 2 ICl; I2 + F2 → 2 IF (at -450C)
0
Cl2 + F2 (in equal amounts) 250 C 2 ClF
Cu-vessel
 Some of them can be prepared by other methods,
3000 C
Cl2 + ClF3 3 ClF

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0
Cl2 + ClF3 300 C 3 ClF; Br 2 + BrF3 3BrF

I2 + AgF IF + AgI; I 2 + KClO3 ICl + KIO2

Properties:
i. These are covalent gases because of small difference in electro-negativities
between the two halogen atoms.
ii. Stability: They differ in thermal stability. For example, ClF is extremely stable
and dissociate when heated strongly:
2 ClF → Cl2 + F2, while IBr dissociate to a small extent into I2 and Br2 when
heated.
BrF and IF are unstable and undergo disproportionation rapidly.
3 BrF → Br2 + BrF3; 5 IF → 2 I2 + IF5
The stability of XY type inter-halogen compounds with respect to
disproportionation is in the order:
ClF > ICl > IBr > BrCl >BrF

iii. Hydrolysis: Generally hydrolysis of these compounds give oxy acids and
hydrohalic acid. For example:
BrCl + H2O → HOBr + HCl
5ICl + 3H2O → HIO + 5HCl + 2I2; ICl + H2O → HOI + HCl
iv. Action of metals and non-metals:
Se + 4 ClF→ SeF4 + 2 Cl2; ICl + 2Na → NaI + NaCl
W + 6 ClF → WF6 + 3 Cl2
v. Action of alkali metal halides and olefins: With alkali metal halides, polyhalides
are formed while inter-halogens add to olefins at double bond sites.
KCl + ICl → K[ICl2]; NaBr + IBr → Na[IBr2]
CH CH + ICl CH CH

I Cl
:
vi. Lewis acid strength: The Lewis acid strength of these compounds decreases in
the order: ICl >> BrCl > IBr > I2 Reactivity: These compounds are more
reactive than each of the halogen molecules because X-Y bond dissociation
energy is less than that of X-X bond.
1. Iodine monochloride, ICl:
Pretaration:
 It is formed by mixing I2 and Cl2 in equal amounts.
I2 + Cl2 (equal amounts) → 2 ICl
 By heating I2 with KClO3
KClO3 + I2 → KIO3 + ICl
 By heating ICl3 at 680 C
Properties:
i. It is dark liquid with b. p. 97.40 C.
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ii. ICl exists in two solid form as given below:

 Solid form: This form melts at 27.20 C and is obtained as needle like crystals on
cooling the liquid rapidly.
 Metastable form: This form melts at 140 C and is obtained as a black solid on
cooling the liquid slowly at 1000 C.
iii. Hydrolysis: ICl dissolve in water and gets hydrolyzed as:
ICl + H2O IOH + HCl
3 ICl + 3 H2O HIO3 + 3 HCl + 3 HI
5 ICl + 3 H2O HIO3 + 5 HCl + 2 I2
The hydrolysis can be prevented adding HCl
iv. ICl decomposed by excess of KOH as:
3 ICl + 6 KOH → 3 KCl + 2 KI + KIO3 + 3 H2O
v. In liquid state ICl undergoes auto-ionization as:
2 ICl I+ (Solvent cation) + ICl2- (Solvent anion)
Metal halide give I+ ions in liquid ICl hence it behaves as Lewis acid.
+ -
AlCl3 + ICl I + AlCl4 ; TiCl4 + ICl I + TiCl5-
+

MCl5 + ICl I+ + MCl6-; (M=Sb, Rb)

Alkali metal chloride gives ICl2- ion in liquid ICl and therefore acts as bases.
MCl + ICl M+ + ICl2-, (M=K, Rb)
vi. Bromide like KBr, [(CH3)4N]Br etc. , reacts with ICl, polyhalide ion is
produced.
ICl + KBr K+[ClBrI]-
ICl + [(CH3)4N]Br [(CH3)4N]+[ClBrI]-
vii. Excess of Cl2 convert ICl into ICl3
Cl2 (excess) + ICl → ICl3
viii. When molten ICl is electrolyzed, a mixture of I2 and Cl2 is liberated at anode
and I2 is liberated at cathode. This suggests that ICl ionizes as:
2 ICl I+ (Solvent cation) + ICl2- (Solvent anion)
Reaction at cathode: 2I+ + 2 e- → I2 (reduction)
Reaction at anode : 2 ICl2 → I2 + 2 Cl2 + 2 e- (oxidation)
-

Uses:
 A solution of ICl is used as catalyst in the oxidation of As(III) oxide by ceric
sulphate and for preparation of polyhalides.
 The solution of ICl in glacial acetic acid is used for determining the iodine value
of oil by Wiz’s method.
2. Chlorine monofluoride, ClF:
Preparation:
 It is prepared by the action of Cl2 on F2 or ClF3.
0
Cl2 + F2 2500 C 2 ClF; Cl 2 + ClF3 300 C 3 ClF

Properties:
i. It is colourless gas having m. p. -1560 C.
ii. On heating it dissociate as: 2ClF Cl2 + F2
iii. Fluorination reactions: Metals are converted in their fluorides.
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Se + 4 ClF → SeF4 + 2 Cl2; W + 6 ClF → WF6 + 3 Cl2

iv. ClF acts as a chorofluorinating agent as under.
CO + ClF → COFCl; SF4 + ClF → SF5Cl
SO2 + ClF → SO2FCl
3. Iodinemonobromide, IBr:
Preparation:
 It is prepared by direct combination of the elements.
I2 + Br2 → 2 IBr
Properties:
i. It is hard crystalline solid of grey-violet colour.
ii. Its vapour dissociate to small extent on heating:
2 IBr I2 + Br2
iii. IBr is an electrical conductor in molten state.
IBr → I+ + Br-
Structure and geometry of XY type Inter-halogen compounds:
Examples of such compounds are ClF, BrF, IF, BrCl, ICl abd IBr. Let us consider
example of ICl molecule in which I-atom is the central atom. All these molecules
have linear geometry which arises because of sp3 hybridisation of the central halogen
atom, iodine.
.. .. Lewis structure of this molecule shows that the central
:I. . Cl
..: I-atom is surrounded by three lone pairs of electrons ane one
Lewis strucure -bonding elctron pair. Thus I-atom is sp3 hybridised in ICl
of ICl molecule
molecule.

Fig. 3.1 Zig-zag chain of ICl

molecule in its  and form
I-Cl σ-bond results by the head-to-head overlap between the singly-filled 3pz
orbital of Cl-atom and singly filled sp3 hybrid orbital on I-atom. Although the spatial
arrangement of 4-electron pairs round I-atom is tetrahedral, due to the presence of
three lone pairs of electrons, the shape of ICl molecule gets distorted and becomes
linear. ICl molecule form zig-zag chains in both α and β-form. Both forms differ only
whether Cl-branches are cis (α) or trans (β).
II. Inter-halogen compounds of XY3 type (Tetra-atomic inter-halogens):
Preparation:
 These are generally prepared by direct combination of elements under suitable
conditions.

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Cl2 + 3 F2 (excess) 200-3000 C 2 ClF3;

Br2 (vapour) + 3 F2 In presence of N2 2 BrF3 ;

3 Cl2 (excess) + I2 1000 C 2 ICl3

 Some of them may be prepared by other methods like:
ClF3 + Br2 → BrF3 + BrCl; ICl + Cl2 → ICl3
Dispropo-
3 BrF rtionation BrF3 + Br2; I2O5 + 10 HCl 2 ICl3 + 5 H2O
Properties: Among these compounds, ClF3 is the most reactive. All have high
electrical conductivity and hence undergoes self-ionisation
2 ClF3 ClF2+ + ClF4-; 2 BrF3 BrF2+ + BrF4-
1. Chlorine trifluoride, ClF3:
Preparation:
 It is prepared by action of Cl2 and F2 at 200-3000C in Cu vessel.
Cl2 + 3 F2 (excess) → 2 ClF3
Properties:
i. It is colourless gas which condenses to give a pale green liquid of b. p. -120 C.
ii. It is the most reactive of all XY3 type compounds and reacts with inert
substance also. It ignites material like wood, asbestos etc.
iii. Liquid ClF3 is electrical conductor which suggest its auto-ionisation.
2 ClF3 ClF2+ + ClF4-
It is obvious from the following reaction that MF5 (M=As, Sb, V) acts as an
acid in liquid ClF3.
MF5 + ClF3 ClF2+ (Solvent cation) + MF6-
It acts as fluorinating agent as follow.
U(s) + 3 ClF3 50-900 C UF6(l) + 3 ClF
6 NiO + 4 ClF3 → 6 NiF2 + 2 Cl2 + 3 O2
2 AgCl + ClF3 → 2 AgF + Cl2 + ClF
v. It hydrolysed by water, forming ClOF.
ClF3 + H2O → ClOF + 2 HF
vi. It produced HF with NH3 and N2H4.
2 NH3 + 2 ClF3 → 6 HF + N2 + Cl2;
2 N2H4 + 4 ClF3 → 12 HF + 3 N2 + 2 Cl2
vii. With F2 gives higher inter-halogens.
ClF3 + F2 h ClF5
Uses: ClF3 is used as fluorinating agent for preparation of number of metal fluoride,
for preparation of metallic polyhalides and in cutting oil well tubes.
2. Iodine trichloride, ICl3:
Preparation:
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 It is obtained by action of excess of Cl2 on I2 or on ICl at 1000 C.

3Cl2 (excess) + I2 → 2 ICl3; Cl2 (excess) + ICl → ICl3
 It is formed when dry ICl gas reacts with heated I2O5
I2O5 + 10 HCl → 2 ICl3 + 5 H2O + 2 Cl2
Properties:
i. It is lemon-yellow solid which fumes readily, soluble in organic solvent, liquid
NH3 and liquid SO2.
ii. With metal halide it gives crystalline additive products.
MCl + ICl3 MICl4
iii. With alkali halide it gives polyhalides of MICl3F type.
iv. ICl3 is completely hydrolysed by water.
2 ICl3 + 3 H2O → 5 HCl + HIO3 + ICl
v. It dissociate at 680 C giving ICl and Cl2.
ICl3 → ICl + Cl2
vi. Molten ICl3 has high electrical conductivity. The liberation of I2 and Cl2 at
both electrodes indicates that ICl3 is ionized into ICl2+ and ICl4- ions as follow.
2 ICl3 ICl2+ + ICl4-
Reaction at anode : 2 ICl4- → I2 + 4Cl2 + 2e- (oxidation)
Reaction at cathode: 2ICl2+ + 2 e- → I2 + 2 Cl2 (reduction)
Uses: Used in medicines and for preparation of polyhalides.
3. Bromine trifluoride, BrF3:
Preparation:
 It is obtained by mixing Br2 vapour with F2 in presence of N2
Br2(g) + 3 F2 N2 2 BrF3
 By action of ClF3 on Br2 at 100 C.
ClF3 + Br2 100 C BrF3 + BrCl
Properties:
i. It is fuming liquid with b. p.125.80 C, is very reactive and non corrosive liquid.
ii. It reacts with Br2 to form BrF : BrF3 + Br2 → 3 BrF
iii. Auto-ionisation: 2 BrF3 BrF2+ + BrF4-
The substance making available BrF2+, due to above mode of auto-ionisation;
acts as acids.
Examples: AuF3 + BrF3 BrF2+ + AuF4-
MF4 (M=Ge, Sn, Ti) + 2 BrF2+ 2 BrF2+ + MF62-
The substance making available BrF4- acts as bases.
Examples: MF (M=Li, K, Ag) + BrF3 M+ + BrF4-
iv. Neutralisation reactions: These reactions are those in which a compound
containing BrF2+ ion reacts with that having BrF4- ion and salt and solvent are
formed.

Acid Base Salt Solvent

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[BrF2]2+[SnF6]2- + 2 Ag+[BrF4]- → Ag2[SnF6] + 4 BrF3

[BrF2]2+[VF6]2- + K+[BrF4]- → K[VF6] + 4 BrF3
[BrF2]2+[AuF6]2- + Ag+[BrF4]- → Ag[AuF4] + 3 BrF3
VF5 (Acidic anhydride) + Ag+[BrF4]- (base)
Ag+[VF6] (salt) + BrF3 (solvent)
v. BrF3 is useful fluorination agent as follow.
6 M + 2 BrF3 → 6 MF + Br2; 3 MCl + BrF3 → 3 MF + BrCl3
WO3 + 4 BrF3 → 2 WF6 + 2 Br2 + 3 O2
6 CuO + 4 BrF3 → 6 CuF2 + 3 Br2 + 3 O2
vi. Redox reactions and complex formation:
3 K + 4 BrF3 → 3 K+[BrF4]- + ½ Br2
zxc
vii. Solvolysis reaction: In these reaction the concentration of [BrF2]+ and [BrF4]- is
increased.
4 BrF3(l) + K2[TiF6] [BrF2]2[TiF6] + 2 K[BrF4]
2 BrF3(l) + K[PF6] [BrF2][PF6] + K [BrF4]
viii. Formation of adducts:
XeF2 + MF5 →XeF2.MF5 (In BrF3 solution)
BrF3 hydrolysed by water with formation of bromine oxy-fluoride.
BrF3 + H2O → BrOF3 + H2
Uses:
 For preparation of polyhalides.
 For preparation of complex compounds by acid-base reaction, are difficult to
prepare by other methods.
 As fluorinating agent.
 For preparation of fluorocomplexes of many metals like Au, Ge, As etc.
Structure and geometry of XY3 type Inter-halogen compounds:
Examples of such compounds are ClF3, BrF3 and IF3. All these molecules have
bent T-shaped structure which is due to sp3d hybridization of the central bigger atom.
Let us discuss the geometry of ClF3 molecule in which Cl-atom is the central
atom. Lewis structure of ClF3 molecule shows that the central Cl-atom is surrounded
by three σ-bps and two lone pairs of electrons and hence Cl-atom is sp3d hybridized
in ClF3 molecule.
Each of the three Cl-F σ-bonds results by the overlap of singly-filled sp3d
hybrid orbital on Cl-atom and singly-filled 2pz orbital of F-atom.

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Lewis structure
Fig. 3.2 Bent T-shaped structure of ClF 3 molecule
of ClF3 molecule

F iv e s p 3 d h yb rid o rb ita ls

Although the spatial arrangement of five electron pairs round the central Cl-
atom in space is trigonal bipyramidal, due to presence of two lone-pairs of electrons,
the shape of ClF3 molecule gets distorted and becomes slightly bent T-shaped. The
repulsion between two lps of electrons reduces F(a)-Cl-F(b) bond angle from 900 to
87.50. The basal Cl-F(b) bond length is equal to 1.60 A0 while each of two axial Cl-F(a)
bond length is equal to 1.70 A0.
Structure of (ICl3)2 dimeric molecule: ICl3 is dimeric molecule (ICl)2,
in the solid state and has a
chlorine-bridged structure in which
C l-atom m akes a bridge between two IC l 2
units. It m ay be seen from strucure that
Fig. 3.3 C hlorine-bridged each I-atom is surrounded by four  -bps
structure of (IC l 3 ) 2 dim er and two lps and is sp 3 d 2 hybridized.

Two lps of electrons are residing in the axial sp3d2 hybrid orbital of the
octahedron. Each of the three Cl-I σ-bonds results from the overlap between the
singly-filled 3pz orbital of Cl-atom and singly filled sp3d2 hybrid orbital on I-atom
while Cl→I bond arises by the do--nation of an electron pair on bridging Cl-atom to
vacant sp3d2 hybrid orbital on I-atom. Formation of 8 bonds between two I-atoms and
six Cl-atom in (ICl3)2 dimeric molecule has been shown in fig. 3.4.

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I-a to m
:
3 2
I-atom in sp d hybridised
state in IC l 4 unit :

S ix sp 3 d 2 hybrid orbitals

Fig. 3.4 Formation different bonds in dimeric (ICl3)2 molecule.

Fig. 3.5 Two ICl4 squares

sharing two bridging Cl-atom
in the structure of (ICl3)2 dimer

Due to presence of two lps in axial position of the octahedron, each ICl 4 unit
has square planar structure as shown in fig. 3.5
III. Inter-halogen compounds of XY5 type (Hexa-atomic inter-halogens):
Preparation:
 These are prepared by direct combination of elements, e.g.,
0
350 C
Cl2 + 5 F2 250 atm.
2 ClF5; Br2 + 5 F2 (excess) > 1500 C 2 BrF5
I2 + 5 F2 (excess) → 2 IF5
 These can also be prepared by other methods, e.g.,
0
ClF3 + F2 h ClF5 ; KBr +3 F2 25 C
KF (s) + BrF5
1. Chlorine pentafluoride(ClF5) and bromine pentafluoride(BrF5):
Preparation:
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i. ClF5 is prepared by the action of F2 on Cl2 or ClF3

0
350 C h
Cl2 + 5 F2 250 atm.
2 ClF5; ClF3 + F2 ClF5
ii. BrF5 is obtained by the action of F2 on Br2 or KBr.
0
25 C
Br2 + 5 F2 (excess) > 1500 C 2 BrF5 ; KBr +3 F2 KF (s) + BrF5
Properties:
i. ClF5 is gas having m. p.= -1030 C. It is fluorinating agent and hydrolyzed by
water to liberate HF and FClO2.
ClF5 + 2 H2O → FClO2 + 4 HF
ClF5 ionises as: 2 ClF5 ClF4+ + ClF6-
ii. With AsF5 and SbF5 it form adducts: ClF5.AsF5 and ClF5.SbF5 which are ionic.
iii. BrF5 reacts very violently. Therefore, generally it is diluted with N2. BrF5 is
hydrolysed by water as:
BrF5 + 3 H2O → 5 HF + HBrO3
Uses:
 BrF5 is used in organic synthesis.
 It is also recommended as an oxidizer for propellants.
2. Iodine pentafluoride, IF5:
Preparation:
 It is formed by direct combination of I2 and F2 (excess):
I2 + 5 F2 (excess) → 2 IF5
 By the action of F2 on I2O5: 10 F2 + 2 I2O5 → 4 IF5 + 5 O2
 By heating I2 with AgF: I2 + 10 AgF → 2 IF5 + 10 Ag

Properties:
i. It is courless liquid with m. p. = 9.60 C.
ii. It is good conductor of electricity as it ionizes as:
2 IF5 IF4+ + IF6-
Thus, the substances that give IF4+ ions in liquid IF5, acts as acid and those
which produce IF6- ions behave as bases in this solvent. The following acid-base
reaction takes place in liquid IF5.
[IF4]+[SbF6]-(Acid)+K[IF6]- (Base)
K+[SbF6]- (Salt) + 2 IF5 (Solvent)
iii. IF5 reacts with I2O5 to form iodine oxy-fluoride, IOF5 which is solid and
decomposes on heating at 1100 C.
3 IF5 + I2O5 5 IOF3; 2 IOF3  IF5 + IO2F
i. Hydrolysis of IF5 gives halogen acid and oxy-halic acid.
IF5 + 3 H2O → 5 HF + HIO3
v. With F2 at 2500-3000 C temperature gives IF7.

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IF5 + F2 0
250 -300 C
0
IF7
Structure and geometry of XY5 type Inter-halogen compounds:
Examples of such compounds are ClF5, BrF5 and IF5. All these molecules have
distorted octahedral (square pyramidal) structure which arises from sp3d2
hybridization of the central atom. Let us discu
-ss the shape of IF5 molecule in which bigger I-atom is
the central atom. The Lewis structure of this molecule
shows that the central I-atom is surrounded by five bps
and one
3 2
lp of electrons hence I-atom is sp d hybridized in IF5 molecule.
Out of six sp3d2 hybrid orbitals, one axial hybrid orbital contains lone pair of
electrons while remaining five orbitals are singly-filled. The lone pair occupies the
axial orbital, since in this case (lp-lp) repulsion is minimum. Each of five F-I σ-bonds
result by the overlap of singly-filled sp3d2 hybrid orbital in Cl-atom and singly-filled
2pz orbital of F-atom.
Although the spatial arrangement of six electrons pairs round I-atom in space
is octahedral, due to the presence of one lone pair electrons the shape of molecule
gets distorted and hence IF5 assumes square pyramidal shape.
A recent study of this molecule shows that all four basal F-atom are slightly
displaced up wards from the base of the square pyramid and hence molecule assume
the structure as shown in fig. 3.5
1 .7 3 A 0
Fb Fa 1 .8 7 A 0 Fb
0
8 1 .9

Fb Fb
I

lp

F ig . 3 .6 S q u a re p yra m id s tru c tu re o f IF 5 m o le c u le

Six sp 3d 2 hybrid orbitals

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IV. Inter-halogen compounds of XY7 type (Octa-atomic inter -halogens):

Only one compound, IF7 of this type has been found and characterized. The
reason is that an iodine atom has largest size among halogens, while F-atom has the
smallest size.
Iodine heptafluoride, IF7:
Preparation:
It is prepared by the action of F2 on IF5, KI or PbI2.
F2 + IF5 2500-3000 C IF7; 4 F2 + KI 2500 C KF + IF7

8 F2 + PbI2 PbF2 + 2 IF7

Properties:
i. It is gas at room temperature and highly reactive.
ii. At 2500 C, with SiO2 and Pyrex glass it gives SiF4.
IF7 + SiO2 → 2 IOF5 + SiF4
iii. Vapour of IF7 hydrolyzed by water, giving HF and H5IO6
IF7 + 6 H2O → H5IO6 + 7 HF
i. It form adducts with SbF5 and AsF5. These adducts are ionic compounds
having the structure [IF6]+[SbF6]- and [IF6]+[AsF6]- respectively.
Structure and geometry of XY7 type Inter-halogen compounds:
IF7 is the only inter-halogen compound of this type. The Lewis structure of this
molecule shows that the central I-atom is surrounded by seven σ-bps and hence I-
atom in its excited state is sp3d3 hybridized in IF7 molecule.
Each of the seven I-F σ-bonds is formed by the overlap between the singly-
filled sp3d3 hybrid orbital on I-atom and singly-filled 2pz orbital in F-atom. Since
there is no lone pair of electrons in any of the hybrid orbital, IF7 molecule has
expected pentagonal bipyramidal shape. IF7 molecule has two equal axial, I-Fa bonds
and

Fig. 3.8 (a) Lewis structure of IF 7 (b) Pentagonal bipyramida geometry of IF 7 molecule

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I-atom
1
( 5s
I-atom
state in

S even sp 3 d 3 hybrid orbitals

five
equal equatorial, I-Fb bonds. I-Fa bond length is longer than I-Fb bond length.
Polyhalide ions and Polyhalides:
What are polyhalide ions and polyhalides?
The ions (catons or anions) composed of similar halogen atoms (e.g., Cl 2+,
Br2+, I5+ etc.) or dissimilar halogen atoms (e.g., ICl2+, IBrCl- etc.) are called
polyhalide ions. These ions may be regarded as positively or negatively charged
inter-halogen ions.
The formation of these ions observed during self-ionization of some inter-
halogen compounds,e.g.,
2 ICl I+ + ICl2- 2 BrF3 BrF2+ + BrF4-
2 ClF5 ClF4+ + ClF6- 2 ICl3 ICl2+ + ICl4-
IF7 IF6+ + F- 2 IF5 IF4+ + IF6-
The ionic compounds containing either polyhalide cations or polyhalide anions
are called polyhalides.
Examples of polyhalides, containing polyhalide anions, are:
K [Cl3]-, NH4+[I5]-, Cs+[ClBrI]-, [N(C2H5)4]+[I3]-, [As(C6H5)4]+[I3]-, Na+[IBr2]-,
+

H+[ICl4]-.4 H2O etc.

Examples of polyhalides, containing polyhalide cations, are:
[X2] [Sb3F16]-, (X=Cl,Br, I); [Cl3]+[AsF6]-, [BrF2]+[SbF6]- (M=Sb, As).
+

Iodine has maximum tendency to form polyhalide ions. Cl, Br and I-atoms can
form triatiomic anions, while F-atom is not able to form F3- ion.
Preparation:
i. By direct action of halogen on metallic halides or on other polyhaide.
Cl2 + KCl → K[Cl3]; Br2 + KBr → K[Br3]
I2 + KI → K[I3] 2 I2 + NH4I → NH4[I5]
Cl2 + K[ICl2] → K[ICl4]; Cl2 + K[IBr2] → K[ICl2] + Br2
ii. By the action of inter-halogens on metals, metallic halides or other polyhalides.
4 BrF3 + 3 K → 3 K[BrF4] + ½ Br2
ICl + MCl (M=K, Rb, NH4+) → M[ICl2]; ICl + KCl → K[ICl2]
ICl + KBr → K[ClBrI]; BrCl + CsI → Cs[IBrCl]
BrF3 + MF (M=Li, K, Ag) M[BrF4];
+ -
ClF5 + AsF5 → [ClF4] [AsF6]
IF7 + MF5 (M=As, Sb) → [IF6]+[MF6]-
ICl + K[ClBrI] → K[ICl2] + IBr
iii. By action of I2 or Cl2 on solution of metallic chlorides in HCl.
I2 + 3 Cl2 + 2 MCl (Li, Na) → 2 M+[ICl4]-
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I2 + Cl2 + 2 RbCl (in HCl) → 2 Rb+[ICl2]-

iv. By action of an appropriate gaseous halogen on metallic halide in absence of
solvent.
F2 + CsCl → Cs[ClF4]
v. I2 dissolve in highly acidic oxidizing media to give I2+ ion. The salts of X2+ are
best prepared by action of S2O6F2 on X2 molecule and then SbF5 is added.
X2 + S2O6F2 (then add SbF5) → [X2]+[Sb3FI6]-
vi. Salts of X3+ ions can be prepared by a number of methods. For example:
2 I2 + ICl + AlCl3 → [I5]+[AlCl4]-
Cl2 + ClF + AsF5 -780 C [Cl3]+[AsF6]-

3 I2 + 3 AsF5 in SO2 2 [I3]+[AsF6]- + AsF3

Properties:
i. All polyhalides are coloured compounds and depth of colour increases with the
increase of the atomic number of halogen atoms.
ii. Polyhalides are highly soluble in water and get dissociated in water. The
stability of metallic trihalides of MX3 type having the same cation in the same
oxidation state is in the order: MI3 > MBr3 > MCl3. And the stability of
metallic trihalides, having the same trihalide anion and different cation
increases with the increase in size of the cation. For example:
NaI3 < KI3 < RbI3 < CsI3.
The polyhalides, containing ICl4- anion, dissociate in aqueous solution
followed by hydrolysis to iodate, IO3-.
5 [ICl4]- → 5 Cl- + 5 ICl3
5 ICl3 + 9 H2O → 3 H+ + 3 IO3- + 15 H+ + 15 Cl- + I2
5 [ICl4]- + 9 H2O → 20 Cl- + 18 H+ + 3 IO3- + I2
iii. Polyhalide ions form complexes with organic donor molecules. Examples:
LiI3.4 C6H5CN, MI3.2 C6H5CN (M=Na or K)
iv. They undergo thermal decomposition when heated. The ease of dissociation
decreases with the increase of the size of the cation. On thermal dissociation,
the polyhalides give metal monohalides and halogen molecule or inter-halogen
molecule.
CsI3  CsI + I2; RbICl2  RbCl + ICl
The stability of trihalide ions formed by the same metal, decrea -ses in the
order: I3- > IBr2- > ICl2- > I2Br- > Br2- > BrCl2- > Br2Cl-
v. When polyhalide is allowed to react with halogen molecule, it undergoes
substitution reaction.
KIBr2 + Cl2 → KICl2 + Br2; CsBr3 + I2 → CsIBr2 + IBr
Sometimes a higher polyhalide is formed. KICl2 + Cl2 → KICl4
vi. Polyhalides may dissolve in liquid halogen or in inter-halogen to give solution
from which original polyhalide may be crystallised by evaporation.

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Structure of Polyhalide ions:

1. Geometry of Tri-atomic inter-halogen cations:

+ 4 1
ion
++
ion
ion+ 1
+ion 1
2
ion

Four sp 3 hybrid orbitals

Examples of such cations are: ICl2+, IBr2+, BrF2+, ClF2+ etc. All these cations
have angular (V-shaped) geometry which arises from sp3 hybridisation of central
positively-charged bigger halogen atom and due to presence of two lps of electrons
on the central atom.
Let us discuss the geometry of ICl2+ ion. Here positively-charged I-atom is the
central atom and is surrounded by two σ-bps and two lps and is sp3 hybridised as
shown above.
Although the spatial arrangement of four sp3 hybrid orbitals is tetrahedral, due
to presence of two lone pairs of electrons, ICl2+ ion assumes angular shape as shown
in fig. 3.9

Fig. 3.9 : Angular (V-shaped) structure of ICl 2+ ion

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2 5
C l-a to m (3 s 3p )

2 5
C l-a to m (3 s 3p )
(a ) (b )
+ 3 +
F ig . 3 .8 : ( a ) L e w is s tr u c tu r e o f IC l 2 io n , ( b ) s p h y b r id is a tio n o f I
+
in IC l2 io n a n d fo r m a to n o f d iffe r e n t b o n d s .

2. Geometry of Penta-atomic inter-halogen cations:

Examples of such cations are: IF4+, ClF4+, BrF4+ etc. All these cations have
distorted-tetrahedral or see-saw structure. This structure arises from sp3d
hybridisation of central positively-charged bigger halogen atom and due to presence
of one lone pair of electrons on the central atom.
Let us discuss the geometry of IF4+ ion. Here positively-charged I-atom is the
central atom and is surrounded by four σ-bps and one lone pair and is sp3d hybridised
as shown below.
The Lewis structure of ICl4+ ion can be written as shown in fig. 3.10 (a). Sp3d
hybridisation scheme indicate that ICl4+ ion is AB4(lp)

3
F ive sp d hybrid orbitals
type species. Formation of four (I+-F) σ-bonds have been shown at fig. 3.10 (b).
As discuss earlier the lone pair prefer to occupy the basal hybrid orbital and
due to the presence of lone pair in the basal position, the shape of ICl4+ gets distorted
and becomes distorted octahedral or see-saw (fig. 3.11).

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2 5 2 5
F-atom (2s 2p ) F-atom (2s 2p )

2 5 2 5
F-atom (2s 2p ) F-atom (2s 2p )
(a) (b)
Fig. 3.10 : (a) Lewis structure of IF 4+ ion (b) Formatin different bonds in IF 4+ion

+
F ig . 3 .1 1 : D isto rte d te tra h e d ra l o r se e -sa w stru ctu re o f IF 4 io n
3. Geometry of Hepta-atomic inter-halogen cations:
Examples of such cations are: IF6+, BrF6+ etc.
All these ions have octahedral structure
corresponding to sp3d2 hybridisation of the central
positively-charged bigger halogen atom and due
to absence of lp of electrons on the central atom.
Lewis structure of IF6+

Let us discuss the geometry of IF6+ ion. Lewis structure of IF6+ shows that the
central atom is surrounded by six σ-bps and is sp3d2 hybridised as shown below.
Sp3d2 hybridisation scheme given above shows that IF6+ ion has no lone pair of
electrons and hence this ion has octahedral geometry as shown below in fig. 3.12

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S ix sin g ly-fille d sp 3 d 2 h yb rid o rb ita ls

+
Fig. 3.12 : Octahedral structure of IF 6 ion
4. Structure of Tri-atomic inter-halogen anions:
Examples of such anions are: ICl2-, IBr-, BrCl2-, ClF2-, I3-, ClBrI- etc. All these
ions have linear structure which due to sp3d hybridisation of central atom and
presence of three lps of electrons on the central atom. Let us discuss the structure and
geometry of ICl2- and I3- ions.
(a) Structure and geometry of ICl2- ion:The negative charge on this
ion shows that the central I-atom is
surrounded by two -bps and three
lps of electrons and hence I-atom
Lewis structure of ICl 2- is sp 3d hybridised as shown below.

3
F iv e s p d h y b r id o r b it a ls

3
The sp d hybrid orbital which is
-
vacant forms Cl I coordinate
bond. Hybridisation scheme
-
shows that ICl2 ion is AB2(lp)3 type
species and three lps prefer to sit
at the basal position of the tbp,
-
Fig. 3.13 : Linear shape of ICl2 ion since in this case the repulsion

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between electron pairs are minimum. Due to the presence of three lps in the basal
positions, the shape of ICl2- gets distorted and becomes linear as shown in fig. 3.13
(b) Structure of I3- :This ion also have linear structure in which I-atom
undergoes sp3d hybridisation. In order to differntiate
three I-atom, they have been designated as: Ic =
Lewis structure Central I-atom, Il = I-atom lying to the left of Ic-atom
of I3- ion and Ir = I-atom lying to the right of Ic-atom.
Molecular Orbital treatment of I3- ion:
If we take linear combination of the two singly-filled 5p orbitals of two I-
atoms (I=5s2 5p2 5p2 5p1) and one completely-filled 5p orbital of central I- ion (I-=5s2
5p2 5p2 5p2) gives three molecular orbitals which are bonding molecular orbital (ψ b),
non-bonding molecular orbital (ψnb) and antibonding molecular orbital (ψ*). The MO-
digram of I3- ion is shown below in fig. 3.14
The electrons involved in bond formation are occupy BMO (ψb) which spreads
out on either side of the negatively-charged central I-atom and thus two equivalent
bonds are formed.
D o u b ly -fille d 5 p M o le c u la r o rb ita ls T w o s in g ly -fille d 5 p
- -
o rb ita l o n I io n o n I3 io n o rb ita ls o n tw o I-a to m

-
F ig . 3 . 1 4 : M O - e n e r g y le v e l d ia g r a m o f I 3 io n

5. Structure of Penta-atomic inter-halogen anions:

Examples of such anions are: ICl4-, BrF4-, I5- etc. All these ions have square
planar geometry which arises due to sp3d2 hybridisation of central atom and presence
of two lps of electrons on this atom.
Let us discuss the geometry of ICl4-
ion. The negative charge on this ion is
supposed to be present on one of the four
Cl-atoms. Thus Lewis structure of this ion
-
Lewis structure ICl4 ion can be written as given in the margine.
Thus, Lewis structure shows that the central I-atom is surrounded by four σ-
bps and two lps. So I-atom is sp3d2 hybridised. One of the six sp3d2 hybrid orbital is
vacant and hence accepts an electron pair donated by Cl- ion and Cl-→I coordinate
bond is established.
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S ix s p 3 d 2 h y b rid o rb ita ls

sp3d2 hybridisation scheme shows that ICl4- ion is AB4(lp)2 type species.
Experiments have shown that the two lps prefer to sit in the axial positions of
the octahedron, since in this case (lp-lp) repulsion is minimum. Although the spatial
arrangement of six electron pairs round the central I-atom is octahedral, due to
presence of two lps, the shape of ICl4- ion becomes square planar as shown in fig. -
3.15
_ _

Fig. 3.15 - Square planar geometry on ICl4-

6. Structure of Hepta-atomic inter-halogen anions:

Examples of such anions are: IF6-, BrF6- etc. These ions have distorted
octahedral structure which is because of sp3d3 hybridisation of central atom and
presence of one lone pair of electrons on the central atom.
Let us discuss the structure and geometry of
IF6- ion. The negative charge on IF6- may be
supposed to be present on one of the six F-atoms.
Thus, Lewis structure of this ion is given in the
margine. This structure shows that the central
I-atom is surrounded by six -bps and one lone pair
Lewis structure
of electrons and is sp3d3 hybridised.
of IF6- ion

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3 3
seven sp d hybrid orbitals

One of the seven hybrid orbital is vacant and hence accepts an electron pair
donated by F- ion (F=2s2 2p2 2p2 2p2) to form F-→I coordinate bond. sp3d3
hybridisation of I-atom can be shown as above.
T heoretically the
lone pair of electrons
should occupy one of
the five basal position
of pentago nal
bipyram idal as shown
at fig. 3.16 (a).
H owever, experim ent
(a) (b) have shown that
distorted pentagonal
Fig. 3.16 : (a) D istorted pentagonal bipyra bipyram idal structure
m idal structure of IF 6 - ion (wrong), (b) D ist of IF 6 - ion is wrong. It
orted octahedral structure of IF 6 - ion (correct) is believed that IF 6 - ion

has distorted octahedral structure in which the six positions of octahedron are
occupied by six F-atoms and the lone pair of electrons is directed towards the centre
of one of the eight triangular face of octahedron as shown in fig. 3.16 (b).
7. Structure of I82- ion:
This ion is
found in [Cs+]2[I8]2-
which. I82- ion
contains two I3-
which are linked
together into
zig-zag chain by
one I2 molecule as
Fig. 3.17 : Zig-zag chain structure of I82- ion shown in fig. 3.17
8. Structure of I3+ and I5+ ions:
The structure of I3+ is bent as shown in fig. 3.19 (a) and that of I5+ ion is said to
be resonance hybrid of the two structures as shown in fig. 3.19

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(a) (b)
Fig. 3.19 : (a) Bent structure of I3+ ion, (b) Resonance in I5+ ion

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