Etherate, pyridine and aniline compounds of mixed complex halogen acids of indium (III)

INORG.NUCL.CHEM.LETTERS Vol.16, pp. 377-384. Pergamon Press Ltd. 1980. Printed in Great Britain.

ETHERATE, COMPLEX

P Y R I D I N E AND A N I L I N E C O M P O U N D S OF M I X E D H A L O G E N A C I D S OF INDIUM

(III)

Th.F.Zafiropoulos,S.P.Perlepes,J.K.Kouinis D e p a r t m e n t of I n o r g a n i c Chemistry, 231Korinthou

str.,Patras,

and A . G . G a l i n o s

U n i v e r s i t y of Patras,

Greece

(Received for publication 23 April ]980) ABSTRACT In this c o m m u n i c a t i o n the p r e p a r a t i o n , of etherate,

HInCI3I and H I n B r 3 I are described. UV)

Analytical,

and data from X - r a y p o w d e r spectra,

of the new complexes. symbolized

for the first time, and the p r o p e r t i e s

p y r i d i n e and a n i l i n e c o m p o u n d s of the m i x e d complex h a l o g e n conductometric,

spectral

acids (IR

and

have been used for the c h a r a c t e r i z a t i o n

The o r g a n i c bases diethyl ether,

p y r i d i n e and aniline

are

in the text as Et20 , Py and An r e s p e c t i v e l y . INTRODUCTION

Although

salts of the type R + l ~ n X ~ -

tion and X a halogen)

(where R is u s u a l l y a large o r g a n i c ca-

are k n o w n and have been investigated,

r e s p e c t to the p a r e n t acids is far from clear; special

interest,

reactions(1).

the s i t u a t i o n w i t h

the study of these acids

is

of

since a great number of them is used in c e r t a i n F r i e d e l - C r a f t s

The c a t a l y t i c action of the c o m p o u n d H A I C I 4 - 2 E t 2 0 has been inve-

stigated(2) . In the past we have p r e p a r e d and studied c o m p o u n d s of v a r i o u s Lewis bases with the h a l o g e n acids HInCI4(3) , HInBr4(3) , HInI4(4) Br,

and H I n X 3 S C N

(5-7), w h e r e X = CI,

I. We have shown, w i t h a v a r i e t y of p h y s i c o c h e m i c a l methods,

lid state,

the pyridine,

that in the so-

aniline and a great number of q u i n o l i n ~ c o m p o u n d s of the

a f o r e m e n t i o n e d c o m p l e x h a l o g e n acids are m o n o m e r i c and their c o o r d i n a t i o n c o n s i s t s of the c o m p l e x anions

~nX4B ~-

etc. An a n a l o g o u s c o o r d i n a t i o n

sphere ham been shown for the solid

E t 4 N ~ n C I 4 L ~ , w i t h L = urea or t h i o u r e a Since there I~nX4L ~ of In(III)

and

(8) , and

is an a b s e n c e of i n f o r m a t i o n

complexes

and generally,

sphere

~nX3(SCN)B2Z.- , w h e r e B = Py, An, complexes

(C6H 5)4Asl~nCl 4 ( P y ) ~

in the c h e m i c a l

(9) .

l i t e r a t u r e on

on the m i x e d l i g a n d - h a l i d e anionic c o m p l e x e s

(10), we p r e p a r e d and studied the etherate,

p y r i d i n e and a n i l i n e com-

p o u n d s of H I n C I 3 I and HInBr3I. EXPERIMENTAL Materials:

G a s e o u s HI was o b t a i n e d

InCl 3 and InBr 3 w e r e o b t a i n e d

from M a t h e s o n G.P. (>98.0% pure). A n h y d r o u s

from F l u k a A.G. (purum). Diethyl

377

ether was treated

378

Etherate, Pyridine and Aniline Compounds

as usual

for the removal of p e r o x i d e s and moisture.

P y r i d i n e and aniline were

d o u b l y d i s t i l l e d under a t m o s p h e r i c pressure. P r e p a r a t i o n of the E t h e r a t e C o m p l e x e s : T h i s was a c h i e v e d by the " e t h e r o h a l o g e n o sis" m e t h o d

(11).

In a typical experiment,

ml ether in a special vessel, out at -50 ° C

(acetone-dry ice bath).

0.20 M. T h e n 2.06 g

gaseous HI was p a s s e d slowly into 150

in the a b s e n c e of light. The p a s s a g e was c a r r i e d

(5.8 mmol)

The HI c o n c e n t r a t i o n of the s o l u t i o n was

of InBr 3 were s u s p e n d e d in 30 ml Et20. To

this

s u s p e n s i o n were added slowly 32 ml of v e r y f r e s h l y p r e p a r e d e t h e r a t e s o l u t i o n of HI,

0.20 M

(6.4 mmol).

The c o m p l e t e d i s s o l u t i o n of InBr 3 was o b s e r v e d

tely and s i m u l t a n e o u s l y a v i s c o u s oil p r e c i p i t a t e d . stirred w i t h a m a g n e t i c

stirrer for 15 min at -25 ° C. The h e a v y o i l y layer was

s e p a r a t e d from the s u p e r n a t a n t was r e m o v e d by decantation. ping

(3 Torr)

solution and w a s h e d w i t h E t 2 0 ( 5 x 1 0 ml) ; the latter

The o i l y p r o d u c t was dried c o m p l e t e l y by v a c u u m pum-

for 10 min at r o o m temperature,

the final product.

immedia-

The r e a c t i o n m i x t u r e was

and the viscous oil o b t a i n e d was

A similar process was f o l l o w e d for the p r e p a r a t i o n of the

e t h e r a t e c o m p o u n d of HInCI3I. P r e p a r a t i o n of the P y r i d i n e and A n i l i n e Compounds:

In a typical experiment,

of the p r e p a r e d oil

were s u s p e n d e d in 30 - 40 ml

(very freshly p r e p a r e d

E t 2 0 . T h e n an excess of Py or An

sample)

(ca.10 ml)

was added d r o p w i s e and w i t h c o n t i n u o u s

stirring.

The r e a c t i o n taking place was v i g o r o u s and s l i g h t l y exothermic.

dissolved

immediately,

additional

and a solid p r e c i p i t a t e was,

small amount of p r e c i p i t a t e was formed,

The solid was taken up by filtration,

The h y d r o i o d i c

a c c o r d i n g to p r e v i o u s l y p u b l i s h e d m e t h o d s ve s p e c t r o s c o p i c Analyses,

simultaneously,

The oil

obtained.

(10 x 10 ml)

and placed

solid o b t a i n e d after r e p e a t e d pum-

(12), in order to be used for c o m p a r a t i -

studies.

apparatus,

procedures

in detail

The

for the q u a n t i t a t i v e a n a l y s i s of all c o m p o u n d s

p r e p a r e d and the s t a b i l i t y test for the p y r i d i n e and aniline c o m p o u n d s have described

in

salts of Py and An w e r e also prepared,

S t a b i l i t y Test of the C o m p o u n d s and P h y s i c o c h e m i c a l M e a s u r e m e n t s :

instruments,

An

u p o n the a d d i t i o n of 5 0 m i Et20.

w a s h e d w i t h Et20

a v a c u u m d e s i c c a t o r over P4010 . The c r y s t a l l i n e ping, was the final product.

1.5 g

been

(6,7,13).

The i n s t r u m e n t s and d e t a i l e d t e c h n i q u e s for the p h y s i c o c h e m i c a l have been m e n t i o n e d p r e v i o u s l y

measurements

(13,14). RESULTS AND D I S C U S S I O N

General:

The p a s s a g e of HI into ether was done at low t e m p e r a t u r e , t o avoid clea-

vage of ether by HI. ~he e t h e r a t e s are viscous, are i n s o l u b l e in n o n p o l a r

solvents.

o i l y liquids,

by the c o m p l e t e s u b s t i t u t i o n of the ether m o l e c u l e s the p y r i d i n e or a n i l i n e molecules, ether.

They are c r y s t a l l i n e

over a long p e r i o d of time.

fume in the air and

The p y r i d i n e and aniline c o m p o u n d s are formed in the e t h e r a t e c o m p l e x e s w i t h

since the latter are stronger Lewis bases than

solids and stable in the normal l a b o r a t o r y a t m o s p h e r e They are insoluble

in n o n p o l a r solvents,

luble in w a t e r and a l c o h o l s and soluble in CH3NO2,

C6H5N02,

s o m e w h a t so-

DMF and DMSO;

they are

Etherate, Pyridine and Aniline Compounds

also

decomposed

The

by d i l u t e

stability

test

appearing

ted to the

that all h a l i d e after

are g i v e n

results,

The A M v a l u e s

for c o m p l e t e l y

found

either

ionic m i g r a t i o n

ion-pair plexes

III,

C 6 H 5 N O 2 as 1:1 UV Spectra: quality The

and and

was done

place

(I). F r o m

an

hour

while

t h o s e of the a n i l i n e

solutions

the

sorption

maxima

spectra

The b r o a d is a s s i g n e d resulting

ption ting

being

present

b road

absorption 13

of a g iv e n intense

ion

maximum

pyridine

than

those

sh = s h o u l d e r

which

in small

and

since

ions,

at 290 and

263

is

360 nm;

286 nm. attributed (C.T.T.S~

at 239,

245,

252,

(17).

257 and The ab-

of III and VI are due to e l e c t r o also

(18). The

in the

which

come

(with slight

shifts)

shoulder

263

solution spectra

complex

from the

in the

solvent

interaction

ion as e l e c t r o n same

small

the m a x i m u m

used.

donor

complexes

at a b o u t

the a f o r e m e n t i o n e d

air,

between

product.

at

(13).

of I,II,

to the o u t e r - s p h e r e

an a u t o x i d a t i o n

complex

291

in the e t h a n o l i c

transitions

of An

360 nm for the

220,290 264,

solvent

and the 02 of the a t m o s p h e r i c

iodide

257,

(sh)* and

ions

they a p p e a r

concentrations

400-210nm.

at a b o u t

IV and V

test.

290 nm in the

is due

constitutes

or e t h e r a t e

spectroscopic scanned

ion and the

maxima

compounds

I

and the

at about

which

for the com-

252,

stability

spectra

to a c h a r g e - t r a n s f e r

acceptor

(19),

that some

of the compounds.

of iodide

of the A n H + ion

(III),

was

245,

at 233,

the I

from the

at about

of the

In

attributed

as an e l e c t r o n

of the

maximum

of

that

in both C H 3 N O 2

maxima

239,

of I, II,

The e x i s t e n c e

molecule,

to the p r e s e n c e

to the t r a n s i t i o n

has been

at 222,

complexes

286 nm in the

of the a n i l i n e

anions

larger

suggests

obtained

solvent

to ~ ÷ ~* and n ÷ ~* e l e c t r o n i c

from the r e a c t i o n

of the c o m p l e x obviously,

(16).

the

of II and V the a b s o r p t i o n

absorption

This

is low or

the d i s s o l u t i o n

between

of A n and c o o r d i n a t i o n

nm is a t t r i b u t e d

complexes

the A M v a l u e s

spectra

is also v e r i f i e d

at 233 and

transitions

in the

transfer

to solvent)

For

and A M

in C H 3 N O 2 , a r e

(15).

show a b s o r p t i o n

complexes

220 nm in the

of c h a r g e

264 nm are a t t r i b u t e d

here

that t h e s e b e h a v e

after

complexes

362 nm,

of II and V

(13).

10 -5 - 10 -4 M and the r e g i o n

of the p y r i d i n e

transfer

slight

is a t t r i b u -

(uncorrected)

electrolytes

of the UV spectra

those

solutions

1:1

of the ether

360 nm,

charge

to In(III) ;the

sup-

(15).

half

at about

points

a strong

compounds,

in ethanol

considered

it is c o n c l u d e d

of the e t h e r a t e

the t r a n s i t i o n

nic

dissociated complexes

C 2 H 5 0 H , the c o n c e n t r a t i o n s

The m a x i m u m to

has t a k e n

V and VI,

electrolytes

spectra

ions

yields,melting

velocity

For the r e c o r d i n g

recording The

for the ether

formation

II,

for the p y r i d i n e

lends

I.

than tho s e the

compounds

ions are c o o r d i n a t e d

of the c o m p l e x

colors,

in T A B L E

and a n i l i n e

a short time

slight d i s s o c i a t i o n

The a n a l y t i c a l values

acids.

for the p y r i d i n e

p o r t ot the a s s u m p t i o n cloudiness,

mineral

379

IV and V 02I

(19),

ionization the latter, This

absor-

the o x y g e n (19).

The

acvery

is due to traces In the

spectrum

220 nm is m u c h m o r e

three m a x i m a

appear

clear-

380

Etherate, Pyridine and Aniline Compounds

0 0

vI •

o~

t

c,,I O~

C~I

0

C',l

v-

ITM O~

',.0 I.t3

Cq O0

O~ I~

0

In 0 •

o ~

C.

I~

~-

~ o

° 0

~ 121

O -,-4 4~ -,..4

•

O

~ >

O O

v-

0 •

0

I~ 0%

Z

0

o c~

"~

v-

0 O

0

0

0

~ I~

C~I ~

I~ 0%

vO0

I~ Ce~

~

-~

-,4

o

~

0

O

'D

~-

0 I:::I

o 0

0

0

0 tD

•

~

O~ , - 4 .,.-I

~

,.--I

0 ,--I ,,-,I

~ ,--4 -,-I

0

0

,.-I

,,--I

II

Z

m

d= In

4-~

O

II

-,-'t

O

O ,--4

t~

•

~

•

.~

.

..

.,-4 O

-,-.I 4~ ,---I O

..

ee

g

m

"O ,--4 O -,-.I

~

t.3

¢N Z O

v

v

d

O UI •

-,...I

O ,--t O O

~

-,.-I

~

O m

0 0 t~ -,-I 0 m

,° O 0

--° 0 0

°, O 0

v

0

,° O 0 ~

°, O 0 v

Ul

°° O 0 v

m O

O

f~l

cN

,--4 ,---I O

O

0 o -,.4 0 t.D

ro

0

rO

~

~ O ©

,<

d

H

H H

H H H

> H

O '44

>

H >

O tn

Etherate, Pyridine and Aniline Compounds

ly r ein f o r c e d , the

when

solution.

(these b e g i n and VI

IR Spectra:

medium

to a p p e a r

The

approximately

spectra

6h)

of I and IV are a l m o s t

probably

shows the

after

from the shows

the p r e p a r a t i o n

spectra

of III and

the g r e a t e r

to an In-Cl

indicates

a tetrahedral

characteristic

lid p y r i d i n e

3220-3095

existence hydrogen

(21).

of a weak, bond,

negatively

stability

of VI

of III

and V is c l e a r l y cm -I

indicated

ether

are g i v e n

band

ion

the c e n t r a l

of these

The p r e s e n c e

by the b a n d s

metal

at 1630,

its

,

fre-

(I).

(cm -I)

bands

and

of the

bands

in the

indicate

so-

and

region

the p r e s e n c e

the s i m u l t a n e o u s

show the e x i s t e n c e

the PyH + ion and one h a l o g e n (21).

bonding -I

at 325 cm

2.

absorption

2850 cm -I

band

~(In-Cl);

IR f r e q u e n c i e s

vibrations

intensity at about

in h y d r o g e n

intensity

in T A B L E

bands

are a b r o a d band of -I cm . The first of

1095

vibration

around

value

stretching

between

complex

a medium

the three m e d i u m

The m e d i u m broad

The o n l y a b s o r p t i o n

at 2910 and

stretching

environment

to N + - H

probably

charged

terminal

complexes

com2!e~

cm -I are due

of the PyH + ion

of I shows

and of d i a g n o s t i c

and a n i l i n e

For the ~ y ~ i d i n e

similar.

of d i e t h y l

that the E t 2 O H + ion is i n v o l v e d

spectrum

is a s s i g n e d

Some

of a w e a k

atom or the w h o l e

of PyH + in the m o l e c u l e s 1600,

1530,

1480,

1330,

of II

1240

and

(22).

The two a b s o r p t i o n 1215,

after

many hours

three m a x i m a

c o u n t e r p a r t s in the s p e c t r u m -I i n t e n s i t y at 3350 cm and two o t h e r s

bands

quency

1195

is r e c o r d e d

of these

obvious

(20). A d d i t i o n a l l y , which

spectrum

in ethanol.

without

t hese

the

The a b s e n c e

381

1070,

1040,

bands

1015,

-I and 1443 cm as well -I 690 cm are due to m o d e s

at 1570

750 and

as the

strong

ones

of c o o r d i n a t e d

Py(22).

Of p a r t i c u l a r i n t e r e s t in the IR s p e c t r u m is the l o w - f r e q u e n c y r e g i o n from -I to 250 cm . In the spectra of II and V the two low e n e r g y ring v i b r a t i o n s free p y r i d i n e tion of Py

at 604 and 405 cm -I

(23);

consistent

shift

to h i g h e r

frequencies,

w i t h the c o o r d i n a t i o n

of Py

is,

at

650 of

due to c o o r d i n a -

also,

the

splitting

of the band at 430 cm -I in the s p e c t r u m of II (23). The w e a k band at about 390 -I cm indicates that PyH + is a c o n s t i t u e n t of the p y r i d i n e c o m p l e x e s (23).The In-N

stretching

limit

of the

Careful

modes

spectrophotometer

examination

characteristic

bands

of c r y s t a l l i s a t i o n The these

spectrum

In-I

(24),

a frequency

which

is the lowest

employed. spectra

of II and V c l e a r l y

since

these

complexes

shows

contain

the a b s e n c e no lattice

of

base

(25).

indicate

vibrations

stretching

250 cm -I

of free Py;

it is p o s s i b l e

chlorine

of the

of II shows

frequencies

event,

lie b e l o w

(26)

two bands

that we have that

but a r i s e

modes

also

at 271

and

from

-I

a six-coordinate

the o b s e r v e d

occur,

255 cm

~(In-Cl)

bands coupled

in general,

below

assigned complex

to

(26).

are not due to pure with

~(In-N).

250 cm -I

The

9(In-Cl) ; In

any

indiumIn-Br and

(26).

For the a n i l i n e c o m p ! ~ the s p e c t r u m of III shows two m e d i u m and b r o a d bands -I at 2880 and 2570 cm ; in the s p e c t r u m of VI these b a n d s a p p e a r at 2840 and 2560 -I cm . T h e y are i n d i c a t i v e of the AnH + ion i n v o l v e d in h y d r o g e n b o n d i n g (12). The

382

Etherate, Pyridine and Aniline Compounds

TABLE

IR S p e c t r a l Pyridine

Assignments

and A n i l i n e

Complex

~(~-H)

II

V

2

of Some A b s o r p t i o n

B a n d s of D i a g n o s t i c

Value

for

the

Complexes.

~asym(N-H)

~ym(N_H)

V i b r a t i o n s of the p y r i d i n e ring a

3220m 3160m

637s 435sh

3095w

427s

2870w,b

385w

3215m

637vs

3160m

426vs

31 00w

390w

~(In-N)

~(In-X)

271sh <250

255s

<250

<250

2850w,b III

3325m

3262m

352m 260s

287sh

<250

VI

ain-and dium;

fact, the

that

same

that

for the c o m p o u n d

frequency

-NH 3

In the

(TABLE

In the

m = me-

frequency (12),

occurs

probably

almost

in

indicates

in III is of the a n i o n - c a t i o n type. The p r e c i s e a s s i g n -I cm are difficult, since b a n d s in this region

of III,

spectrum

530 cm -I show also

o n l y one

three

bands

ly a s s i g n e d

mation

one of AnHI

s = strong;

1620-1500

2) have

same

pears

these

the band of h i g h e r

strong; Br.

(13,14).

spectrum

vibrations

615 and

III,

X = CI,

to s t r e t c h i n g v i b r a t i o n s of the b e n z e n e ring and b e n d i n g v i b r a t i o n s of + -I group. The bands in the r e g i o n 1500-390 cm are c h a r a c t e r i s t i c of

the AnH + ion

(27).

bond

vs = v e r y

sh = shoulder;

as the c o r r e s p o n d i n g

in the r e g i o n

are due

ring d e f o r m a t i o n s ;

b = broad;

the h y d r o g e n

ments

the

out-of-plane

w = weak;

strong

appear to

band

in the

~(In-N);

vibrations. vibration

the ba s i s of the

because lower the

of the c o o r d i n a t i o n

frequencies, shifting

coordinated at ca.385 spectrum

however,

and An

cm -I

of III.

compared splitting

(28). in the These

of An, with

the NH 2 s t r e t c h i n g -I

free An by c a . 1 0 0 c m

of t h e b a n ~ s at ca.750,690,

In the r e g i o n spectra

450-280

of AnHI

additional

bands

cm -I ap-

and V I , w h e r e a s are t e n t a t i v e -

the f r e q u e n c i e s are h i g h e r than e x p e c t e d for -I m a y be a s s o c i a t e d w i t h an a n i l i n e d e f o r -

The band at 352 cm that b e c o m e s foregoing

strongly

study,

IR a c t i v e

it is r e a d i l y

on c o m p l e x concluded

formation

(27).

that the c o m p l e x VI

On

Etherate, Pyridine and Aniline Compounds

does not c o n t a i n c o o r d i n a t e d aniline.

The absence,

383

also, of lattice An is c e r t a i n

for III and VI. The

~(In-Cl)

at 260 cm -I for III i n d i c a t e s an o c t a h e d r a l

the c e n t r a l metal

arrangement

around

(26).

X-ray Powder Patterns:

These are similar for the c o m p l e x e s II and V; c o n s e q u e n t -

ly the p y r i d i n e c o m p l e x e s are isomorphous. ferent. All p a t t e r n s

The p a t t e r n s of III and VI are

suggest, by the m u l t i t u d e of the reflections,

dif-

that the cry-

stals formed are of low symmetry. CONCLUSION The p r o p e r t i e s of the e t h e r a t e c o m p l e x e s are c o n s i s t e n t w i t h the f o r m u l a t i o n E(Et20) 2 H ~ + ~ n X 3 ~ - , for o t h e r In

w h e r e X = CI,Br;

(III) c o m p l e x e s

an a n a l o g o u s f o r m u l a t i o n has b e e n p r o p o s e d

(I).

On the basis of the o v e r a l l

study,

the f o l l o w i n g two general

lae are p r o p o s e d for the new p y r i d i n e and a n i l i n e complexes, II, III, V. VI.

~ n X 3 I B ~ - B H +, ~nBr3~-

structural

formu-

in the solid state:

X = CI,Br and B = Py, An

~An---H---An3+.

The symbol --- r e p r e s e n t s h y d r o g e n b r i d g i n g b e t w e e n the c a t i o n i c h y d r o g e n and the n i t r o g e n atoms of the two a n i l i n e m o l e c u l e s plex; too

in the o u t e r sphere of the com-

such a h y d r o g e n b r i d g e has been e s t a b l i s h e d

(3,7,13,14).

for other a n i l i n e c o m p l e x e s

For the c o m p l e x a n i o n s of II, III and V an o c t a h e d r a l

m e n t is assigned;

for the c o r r e s p o n d i n g of V I a

pseudotetraheCral

arrange-

structure

~s

v e r y probable. The absence of An m o l e c u l e s to steric factors;

r i z a b i l i t y and a d e c r e a s e The

complexes

d i n a t e In

(III)

in the c o o r d i n a t i o n

a m o r e likely e x p l a n a t i o n

sphere of VI is, p r o b a b l y , d u e

(10) is an i n c r e a s e in anion pola-

in e f f e c t i v e a c c e p t o r

s t r e n g t h in the sence CI>Br>I.

II, III and V are b e l i e v e d to be the first e x a m p l e s of six-coorin an InX3IN 2 kernel.

V e r y r e c e n t l y the p r e s e n c e of the m o n o n u c l e a r

~nBr3~-

ion,

te, has been e s t a b l i s h e d by Raman and F a r - I R s p e c t r o s c o p i c

in the solid sta-

studies

(29).

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