Formation of triacetylthiocarbamide chromium perchlorate

A C T A

U N I V E R S I T A T I S

L O D Z I E N S I S

FOLIA CHIMICA

1, 1982

J o a n n a M aslow ska, E l i b i e t a t o d y g a - C h r u s c i r i s k a

FORMATION OF TRIACETYLTHIOCARBAMIDE CHROMIUM PERCHLORATE *

The

method

w ere

e l a b o r a t e d

f o r

t h e

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

[Cr(CHs C0NHCSNHt) 4 l \ C 1 0 j , .

I n t h i s

p a p e r we

¿-ive

c o n d i ­

t i o n s f o r t h e

s y n t h e s i s , c o m p o s i t i o n ,

p r o p e r t i e s a n d

p r o ­

p o s e t h e s t r u c t u r e

o f t h e o b t a i n e d compound.

C e r v o n e ,

C a n c e l l i e r » i

a n d

F u r 1 a n 1

[ 1 ] p r e p a r e d a s o l i d compound

o f Chromium ( I I I )

w i t h

t h i o c a r b a -

m ide (TM)

o f f o r m u l a [ C r ( T M ) j ] C l j .

K h a n

[ 2 ] u s e d

t h i s

co m p lex t o p r e p a r e o t h e r

s i x - c o o r d i n a t e d m ixed

c o m p le x e s o f

t h e

t y p e :

[ Cr(TM X^LgCljjCl

w here

L - p i r i d i n e :

[ C H T M ^ L ^ j c i j

w here

L* - O « p h e n a n t r o l i n e an d [ C r C T M ^ L ^ J c i

w here

L" - p h e n y l a r s e n i c

a c i d .

I n l i t e r a t u r e t h e r e

i s a l a c k o f

d a t a on

C r ( I I I )

com­

p l e x e s c o n t a i n i n g

t h i o c a r b a m i d e

d e r i v a t i v e s

i n

t h e

i n t e r n a l

s p h e r e . D u rin g

t h e i n v e s t i g a t i o n s

o f t h e c o m p l e x i n g r e a c t i o n

i n

t h e s y s t e m :

C r(C 10A) 3-AcTM-H20 ,

w here

A c T M - N - a c e t y l t h i o c a r b a m i ­

de

CH3CO.NH.CS.NH2

we d e t e r m i n e d t h e f o r m a t i o n

o f a v e r y

c h a ­

r a c t e r i s t i c c r y s t a l l i n e d e p o s i t

o f a new com pound.

I n t h i s p a p e r

we g i v e c o n d i t i o n s

f o r t h e s y n t h e s i s ,

c o m p & s itio n p r o p e r t i e s and

p r o p o s e t h e s t r u c t u r e o f t h e

o b t a i n e d compound.

/

E x p e rim e n t a l

P r e p a r a t i o n o f (~Cr(CHj CO.NH.CS.NHp ^ ^ C ^ O y^ *

To 50 ccm o f 0 , 2 5 M

a q u e o u s s o l u t i o n

o f C r ( C 1 0 ^ ) j

k e p t

a t

room t e m p e r a t u r e

we a d d e d

150 ccm o f 0 , 2 5 M

( s a t u r a t e d

s o l u

-*

The work h a s b e e n c a r r i e d o u t w i t h i n t h e

r e s e a r c h

P ro b le m

M R -I-1 1 .

t l o n ) a q u e o u 3 s o l u t i o n o f

N - a c e t y l t h l o c a r b a m i d e

( S ch u ch a rd t-M U n -

c h o n ) .

A f t e r h a v i n g t h o r o u g h l y

m ixed t h e r e a g e n t s

t h e

s o l u t i o n

was h e a t e d

on a w a t e r b a t h u n t i l t h e

moment o f s h a r p

c o l o u r

c h a n g e fro m g r e e n

t o d a r k v i o l e t .

A f t e r

c o o l i n g

t h e

s o l u t i o n

y i e l d e d a m i c r o c r y s t a l l i n e

d a r k v i o l e t d e p o s i t . The e d u c e d

c r y ­

s t a l s w e re

w ashed a few t i m e s

w i t h c o l d w a t e r

a n d d r i e d

I n t h e

a t m o s p h e r e o f a i r

a t room t e m p e r a t u r e

t o c o n s t a n t w e i g h t .

• The

r e a c t i o n y i e l d

c a l c u l a t e d

i n r e l a t i o n t o

t h e i n i t i a l

am ount o f

C r ( I I I )

i s a l m o s t 100%.

I t . w a s e s t a b i l i s h e d t h a t

t h e

s o l u t i o n

w h ic h

u n d e r g o e s c r y s t a l l i z a t i o n

s h o u l d hav e

a n a c i d i c

r e a c t i o n

s i n c e a t h i g h e r

pH

v a l u e s t h e r e

t a k e s p l a c e

t h e d e s u l p h u r a t i o n

o f a c e t y l t h l o c a r b a m i d e

c o m p l e x e s o f C r ( I I I )

w i t h t h e

i s o l a t i o n

o f

H2S .

The p r e s e n c e o f chrom ium ,

a c e t y l t h l o c a r b a m i d e an d

p e r ­

c h l o r a t e i o n s

was

d e t e r m i n e d

i n t h e o b t a i n e d p r e c i p i t a t e .

The c o n t e n t o f

C, N, H, S

a n d

C l

was d e t e r m i n e d by e le m e n ­

t a r y a n a l y s i s

m e th o d s an d t h e

c o n t e n t o f

C r ( I I I )

by

c o m p le x o -

m e t r i c m e th o d .

The a n a l y s i s

r e s u l t s

f o r t h e assu m e d

f o r m u l a

[C r(CH jC 0.N H .C S .N H g)j](C 104 >3

a r e a s f o l l o w s :

c a l c u l a t e d : 10.27% C r ,

21.37% C,

1 6 . 61% N,

3.59% H, 19.01% S

an d 21.02% C l:

f o u n d :

10.17% C r , 20.40% C,

16.7196 N,

3.57% H, 19.01% S an d

2 0 . C2% C l j

R e s u l t s

P r o p e r t i e s a n d t h e r m a l r e s i s t i v i t y o f [ C r ( A c T M ) j ] ( C 1 0 ^ j

The o b t a i n e d compound

i s ap a n a q u e o u s d a r k - v i o l e t

s u b s t a n c e ,

h a r d l y s o l u b l e

i n a c e t o n e an d

i n w a t e r . . I t s m .p . t e m p e r a t u r e i s

191°C .

D u rin g h e a t i n g w i t h

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

i t

c o m p l e t e l y

d e c o m p o s e s .

I t i s s i m i l a r l y

decom posed

by s t r o n g

a l k a l i s

( d e -

s u l p h u r a t i o n o f c o m p o u n d ).

I n v e s t i g a t i o n s

made by

d e r i v a t o g r a -

phl. s m e th o d s

i n t n e

a t m o s p h e r e

o f a i r showed

t h a t t h e o b t a i n e d

c.--''.pound i s a l s o h a r d l y

r e s i s t i v e

t o t h e a c t i o n

o f h i g h

te m p e -

r i . jf-o s.

Tne d e r i v a t o g r a m

o f t h e i n v e s t i g a t e d

compound i s shown

i n F i g . 1.

200 TIME (MIN)

P i g . 1 . T h erm a l a n a l y s i s

c u r v e s co m p le x [Cr(CH3CO • NH • CS • N i f e ^ ]

(C IO^H .

D e r i v a t o g r a p h made i n H ungary,

h e a t i n g r a t e

5 C /m in ;

sa m p le mass 59 mg;

s e n s i t i v i t y :

DTA - 1 /1 5 ,

DTG - 1 / 1 5 :

TG

-- 2 0 0 , R e f e r e n c e s u b s t a n c e

a -A120 3

The d e r i v a t o g r a m

o f a c e t y l t h i o c a r b a m i d e

i s shown i n p a p e r 3 .

I t f o l l o w s

fro m

d e r i v a t o g r a p h i c d a t a

t h a t t h e t h e r m a l

decompo-

s i t i d r t - o f t h e

o b t a i n e d

compound

i s o f

a

com p lex n a t u r e .

The

r u n 0 f

phenomena c o n n e c t e d

w i t h e f f e c t s

shown on

DTG, DTA

and

TG c u r v e s c a n be d e s c r i b e d by t h e f o l l o w i n g schem e:

[C r(A cT M )](C ł04 ) 3 - f s W * ' C r iC lO ^ j

C r0( 1 , 5 « ) 4 C102 ♦ C12 * 2

5 * x ) 0 2

The d e c o m p o sitio n

end p ro d u c t i s Cr^Oy

S ta g e s

o f th e t h e r ­

mal d e c o m p o sitio n

p rop osed by

u s In T a b le 1

w sre co n firm ed

by

a d d i t i o n a l

a n a l y t i c s t u d ie s

o f o b ta in e d t h e r m o ly s is p r o d u c ts

o f

th e i n v e s t i g a t e d compound.

A

C r ( I I I )

c a t io n a t t r i b u t e d p rob a b ly

t o

Ct

2

°j,

was i d e n t i f i e d in an

a g g lo m er a te

p rep ared a t

800°C .

C o n c lu s io n s drawn

from our s t u d i e s a r e

i n a cco rd a n c e w ith Buzas*

d a ta [ 4 ] ,

T a b l e

1

S ta g e s o f th erm al d e c o m p o sitio n o f

[Cr(AcTM)3 ](C 104 ) 3

( S t a g e

r...

iTempera-

i t u r e

“V---

1---Loss o f mass

( * )

Maximum o f

e n d o e f f e c t

on DTA

c u r v e

Maximum o f

e x o e f f e c t

on DTA

c u r v e

P r o c e s s

! r a n g e

_{c a l c u ­}

l a t e d

i

fo u n d

_c

I

.

.

d e m o i s t u r i z a t i o n

-

-

m e l t i n g o f

sam ple

j

e l i m i n a t i o n o f

t h e f i r s t m ole­

c u l e AcTM

!

e l i m i n a t i o n o f

t h e s e c o n d m o le­

c u l e AcTM

5

J 370-440 7 0 . 5

7 0 . 0

420

e l i m i n a t i o n o f

t h e t h i r d mole­

c u l e AcTM

6

I 4 4 0 -4 6 0

i

-■

d e c o m p o s i t i o n

o f C r l C l O ^

IR s p e c t r u m o f [C r(C H 3C0NHC3NH2 ) 3 ](C 1 0 /f) ?

T a b l e 2 g i v e s

c h a r a c t e r i s t i c b a n d s

o b s e r v e d i n

IR

s p e c t r a

f o r a c e t y l t h i o c a r b a m i d e

a n d f o r

t h e o b t a i n e d

com pound. A n a l y s i s

o f t h e s e d a t a

made on t h e b a s i s

o f p a p e r s [ 2 , 3 ,

shows t h a t

t h e

C r ( I I I )

i o n c o o r d i n a t e s w i t h

N - a c e t y l t h i o c a r b a m i d e

t h r o u g h

T a b 1 e

2

C h a r a c t e r i s t i c a b s o r p t i o n b a n d s i n IR s p e c t r a

r e c o r d e d w i t h i n t h e r a n g e 4 6 0 0 -7 0 0 cm1.

S p e c o r d 71 I R , KBr p e l l e t s

E n t r y

C h a r a c t e r i s t i c b a n d s , cm“ 1

_{T y p e s o f}

v i b r a t i o n

CHjCO.NH.CS.NHg [C r(C H 3C0.NH.CS.NH2 >3 ]( C 1 0 4 ) 3

1

3420 vw

.3420

2

3260 vw •

3250

3

3220 m

3200

4

3170 m

3170

J

5

1590 s

1600 v s

6NH2 (B.,)

6

1400 s

1420 a

vNCN (A1)

6NH2 (A t )

VCS (An)

7

1360 m

1370

6

ch3

8

1035 v s

1040 vw

.

f i r NH2 (At )

v(NCM) ( A^)

6 r NH2 ( B1)

vCS (A.,)

9

715 s

700 s

vCS (A1 ) uCH

t h e s u l p h u r a to m

( C r - ^ ---- S ) .

I t i s i n d i c a t e d b y

a s m a l l

c h a n g e

o f t h e b a n d s ( v N-H,

6 NH )

i n t h e c o m p l e x .

A b a n d a t 715 cm" ,

c h a r a c t e r i s t i c f o r AcTM

i s s h i f t e d

i n

t h e

com plex

to l o w e r

f r e q u e n c i e s s u g g e s t i n g

t h e

f o r m a t i o n

o f a

m e t a l - s u l p h u r

band

1 5 ] .

Such a c o n c l u s i o n

i s a l s o

b a c k e d by a

20 cm

s h i f t o f a

c o m p le x b and

( v NCN,

6r

v ^ g ,

&CH )

t o h i g h e r

f r e q u e n c i e s

i n t h e com plex

(1420 cm"1 )

i n c o m p a r i s o n t o

AcTM

(1400

cm“ 1 ) .

Such a d i r e c t i o n

o f c h a n g e s

was

o b s e r v e d

by

Khan

[ 2 ]

i n IR

s p e c t r e o f r e l a t e d com pounds.

REFERENCES

[ 1 ]

C e r v o n e

E . ,

C a n c e l l i e r i

"P.,

F u r i a

-n i

c . ,

J . I n o r g . N u c i . Chem .,

3 0 , 2431 ( 1 9 6 8 ) . .

[2,3

K h a n

M. M.,

J . I n o r g . N u c i . Chem.,

3 7 , 1621 ( 1 9 7 5 ) .

[ 3 ]

M a s ł 0 w s k a

J . ,

Ł o d y g a - C h r u ś c i n a k a

E . ,

P o l , J . C hem.,

52, 1261 ( 1 9 7 8 ) .

[ 4 ]

B u z ,a".s

I . ,

T herm a l A n a l y s i s ,

B u d a p e s t ( 1 9 7 5 ) .

[ 5 ]

L a n e

T . J . ,

Y a m a g u c h i

A . ,

J . Am. Chem.Soc.,

§ 1 .

3829

( 1 9 5 9 ) .

[ 6 ]

K h a n

M. M.,

J . I n o r g . N u c l . C hem.,

36, 299 (1 9 7 4 ) ; 25»

1395 ( 1 9 7 3 ) .

[ 7 ]

M a s ł o w s k a

J . ,

ZNPŁ, Chem ia, 2 0 , 1 ( 1 9 6 9 ) .

I n s t i t u t e o f G e n e r a l Food C h e m i s tr y

T e c h n i c a l U n i v e r s i t y o f Łódź

J o a n n a M asłow ska, E l ż b i e t a Ł o d y g a - C h r u ś c i ń s k a

PO.','STAWANIE NADCHLORANU TRÓJACETYLOTIOKARBAMIDOCHROMOWEGO

B a d a j ą c r e a k c j e k o m p le k s o w a n ia

w u k ł a d z i e i C r i C l O ^ -AcTM-H^O

s t w i e r d z i l i ś m y p o w s ta w a n ie

b a r d z o c h a r a k t e r y s t y c z n e g o ,

k r y s t a l i ­

c z n e g o o s a d u nowego z w ią z k u , d l a k t ó r e g o . w o p a r c i u o w y n i k i a n a ­

l i z y c h e m i c z n e j

p r o p o n u je m y w z ó r

[Cr(CH^CONHCSNH2)3 ] (C1 0 i ) 3 .

Wykonane widma

w p o d c z e r w i e n i w s k a z u j ą , ż e

j o n C r ( I I I ) k o o r ­

d y n u j e z

N - a c e t y l o t i o k a r b a m i d e m p r z e z ato m S ( C r * — S ) .

O trzym a­

n y z w ią z e k j e s t

mało o d p o rn y

n a d z i a ł a n i e w y s o k i c h

t e m p e r a t u r .

Z d a n y c h d e r y w a t o g r a f i c z n y c h w y n i k a , ż e

b a d a n y z w ią z e k

r o z ę a d a

s i ę w k i l k u e t a p a c h

w z a k r e s i e t e m p e r a t u r y -2 0 0 - 4 6 0 ° C , . a

k o ń c o ­

wym p ro d u k te m s t a ł y m

j e s t Cr20 3.

ÇaHHa MacJiOBcica, 3jiMc<5eTa JIojtura-XpycuMHCKa

0BPA30BAHZE [ C r (CH3CONHCSNH2 ) 3 ] (C 1 0 A) 3

B p e a n u hh KOUiuieKCOBaHHA b c H c re n e : Cr (C10¿ WAcTM-HoO (AcTM ■

CH3CONHCSNH2) nojiy^aetCH HOBoe coejiHHeHHe [C r ( A c lM ) 3] ( 0 1 0 ^ ) 3,. n p o -

BeAeHHhift

HHijpaKpacHbix oneKTpoB yxa3hiBaeT Ha c b h sb Tnna Cr-^S.

3 t o coe^HHeHHe p a 3 J i a r a e i c a np« te w i e p a T y p e 2 0 0 -4 6 0 °C .