JOURNAL

OF

MATERIALS

SCIENCE

25 ( 1 9 9 0 )

2193-2198

IR spectroscopic study of some oxine transition

metal complexes
A. A. S H A B A K A *
M. F A D L Y ++ , M. A. EL G H A N D O O R * ,
F. M. A B D E L K E R I M *
t

*Spectroscopic Laboratory, National Research Centre, Dokki, Cairo, Egypt

;Physics Department, Faculty of Science, He/wan University, Helwan, Cairo, Egypt
The IR absorption spectra of oxine and their transition metal ( M n Co ++, Ni ++, Cu ++, Zn ++,
Cr ++, Cr + and Fe +++) complexes were recorded in the region 200 to 2 0 0 0 c m 1 and are
discussed. It can be assumed that the transition metal oxine complexes are of higher symmetry
and hence only t w o metal-ligand ( M L ) bands appear. The intensity of the M L bands was
calculated by computer. It was found that the intensity of these bands forms the sequence:
Mn ++ < Co ++ < Ni < Cu + > Zn + w h i c h is the same as that for a tetrahedral high spin
CFSE.

1. I n t r o d u c t i o n
In previous work considerable attention has been paid
to the interpretation of the IR absorption spectra of
complex organic compounds [1-7]. Interest has centred principally on attempts to associate absorption
bands at a specific frequency with the presence of
certain groups in the molecule. Some workers have
reported the IR spectra of the metal chelated compounds. Cardwell and Magee [8, 9] have studied the
IR spectra of metal oxine complexes prepared by
different methods. The metal-ligand vibrations have
become a subject of some controversy. Gorden and
Magee [10] have assigned the band appearing at
732cm-~ to M - O stretching vibration. Larsson and
Backillson [11] have shown that the band at 490cm l
is due to M - N stretching vibration in trisoxinato
aluminium, iron and cobalt . Clark et al. [12] and
Goldestein et al. [l 3] have shown that the M - N vibration in pyridine and quinoline complexes of some
divalent metal ions lie in the region of 260 cm ~. In
previous work [14] the M - O stretching vibration was
assigned at 485 + 5cm -~. Hullet et al. [15] also
assigned the M - O stretching vibration at 460 to
560cm ' and the M - N vibration appeared in the
300cm ~ region. Hassan et al. [16] assigned the M - O
stretching vibration at 325cm ~ and M - N vibration
at 290cm ~.
This work aims to investigate the IR spectra of
some transition metal oxine complexes in the range
200 to 2000 cm 1. The metal-ligand stretching vibration frequency will be assigned and discussed. The
intensity of the M L band has been calculated which
will throw light upon the structure of these complexes.

2. E x p e r i m e n t a l t e c h n i q u e
The different metal chelates were prepared according
to the procedure given by Charles et al. [17]. The
IR spectra were carried out using a Beckman 4250
spectrophotometer. The spectrum obtained is automatically recorded on a paper whose scale is in
0022-2461/90 $03.00 + .12 9 1990 Chapman and Hall Ltd.

percentage transmittance against wavenumber in

cm ~. The IR spectra of these complexes are obtained
in a potassium bromide (KBr) disc used as a reference.
The measurements were made at room temperature
(20 ~ C). The frequencies of the bands are reproducible
to _ 1 cm-~.

3. Results and discussion

The infrared absorption spectra of oxine and their
transition metal complexes are shown in Figs la and
lb. Assignments of the absorption bands are shown in
Table I. If the spectra of the metal-ligand complexes
are compared with those of the ligand, it is interesting
to notice that the new bands at 405 __ 12 and 504 _+
17 cm- 1 appearing in the case of all the chelated compounds are not found in the spectra of the ligand
(oxine). The position of these bands are found to be
metal sensitive and to be strongly dependent on the
metal ion. These two bands show a high dependence
on the number of 3d electrons, Fig. 2a. In this respect,
the order of change in the band position form the
sequence Mn < Co < Ni < Cu > Zn. In other
words, it assumes the Irving-Williams sequence of
stability constants which also reflects the CFSE in a
tetrahedral environment [18]. Fig. 2b shows the relation between the absorption frequency and the ionic
radius of the metal ion. From this figure, it can be seen
that, as the ionic radius decreases the frequency
increases. This means that these bands at 405 _
12cm ~ and 504 4- 17cm J are due t o M - N a n d / o r
M - O stretching vibrations. The frequencies of these
two bands increase linearly with increasing atomic
weight as shown in Fig. 2c. The contradiction observed
in this case can be explained on the basis of the other
factors which must be taken into account, the band
length in particular. Further, it could be suggested
that the electrostatic interaction between the metal ion
and the ligand is the factor determining the variation
in the force constant rather that the atomic weight of
each metal. Thus it can be concluded that these two
21 93

(a)

20

1[ (e)

60

100

2 0 (b)
to
kn
kn

/1

,,,

It

~,~

'

(f)

60

E
c

(g)
c
u
@
n

100

(d)

(h)

2"0

60

100
200

600

1000

'

'

1400

1800

200

600

Wavenumber (cmq)

1000

1400

1800

Wavenumber (cmq)

Figure 1 IR absorption spectra of oxine and their transition metal complexes. (a) Ni(OX)3, (b) Co(OX)3, (c) Mn(OX)3, (d) (OX),
(e) Cu(OX)3, (f) Zn(OX)3, (g)Cr(OX)3, (h) Fe(OX)3.

bands are due to M - N and M - O vibration. These two

bands (ML) are found to exhibit a frequency variation
with the variation of CFSE of a tetrahedral high spin,
Fig. 2d. Thus, the spectra of these complexes exhibit
a similar order of sensitivity to the CFSE and therefore similarly assigned.
The carbon-oxygen (C-O) vibration bands at
1108 -I- 4 c m ~ show a frequency change because of
the change of electronic distribution in the environment of the C - O band in chelation. This band is
largely affected with the physical properties of the
cation as shown in Figs 3a, 3b, 3c and 3d. This indicates that the electronic distribution of the molecule
specially in the neighbourhood of the C - O bond is
greatly affected by chelation.
The absorption bands in the region of 1630 to
t 400 c m - ~of C = N and C = C stretching vibration are
21 9 4

mostly shifted to lower frequencies in the spectra of

the metal complexes than the respective bands in oxme
(Table I). This shift could be explained on the assumption that, on chelation, the electron distribution of the
quinoline ring is slightly disturbed and partially contributes to chelation.
As a confirmation, the integrated intensity of the
M L bands was calculated according to the Dwcius
and Thomson equation [19]
A

n a [,.2 D(v) dv

~YvJ,,,

where A is the integrated intensity, W the weight

of the solute in the disc, a its surface area, D(v)
the optical density and v the wavenumber. The calculations in each case were taken as an average of
five different measurements. The intensities of these

/ k

50O

500

U*

5-

E
"-'490

Ni

M +*

.9 460

.+

Zn

9+
C
0

Co++
480

Mn.+

EL

Ul
0
13.

Cu *

4Z0
C

O
cn

400

Mn~..J

C U*

C
0
133

co

~ O

O#.

~00

Z-n** %\ I

zn"
(a)
380

(b)
1

0.06

0.07

0.08

0.05

10

Ionic

Number of 3d electrons

radii (nm)

~,10
247

Cu

C U +
O

~'~ 500

"7

ZOO

N i*

h 490

M "n
- ~" ~ """/~176O*

Mn**

C
O

-~ul

.~4BO
t,q

4BO

O
G.

cI
m

O
rn
z,00

M%/-

(c)
50

420

Ni*"

4O0

Mn""

J
I .....

Cu**

'ID

U+ *

7:3
C

54

56

62

66

Atomic weight

0.5

1.0

1.5

CFSE

Figure 2 (a) Relation between band position and number of 3d electrons. (b) Relation between the ML band position and ionic radii.
(c) Relation between the ML band position and atomic weight. (d) Relation between the ML band position and CFSE.

bands form the sequence M n ++ < Ni ++ < C o ++ <

Cu ++ > Z n + + ; Fe +++ < Cr +++. It was found that
the intensities o f the M L bands depend on the metal
ion. F r o m Fig. 4a it can be seen that the intensity

increases with decreasing ionic radius o f the metal ion.

This means that the integrated band intensity is
inversely proportional to the b o n d distance. F r o m
Fig. 4b it can be concluded that the intensity increases

2195

1114

1114--

Fe

F e*
!

1112

E
qJ

Cr"*

...1112
"T
E

247

C F ++
0

c<H

IJ

o,/Cu "~

1110
c
o

o
r
o

13.
C
CI
rn

1108

,,I-

Mn*

~1108
9

z2

1106

~ 1106
M

if3

5~

62

66

weight

\o

1112

e+.l.4t,

.e 4,~

q-

111

C r *247

,F 247247

o C J

1110

-/

c
o

Cu

1110

o 1108
~q

U3

~
'o
c
0
cn

1114

~D

Atomic

111/4

54

50

10

Number of 3d electrons

n+;/[N i+
I

1104
4

(b)

(a)

1104

Zn
d

Cd

Zn *247

"tD
C

1106

1106

N~247
~!n* 1
(c)

1104
0.05

110/.

0.06

0.07

0.08

Ionic radii (nm)

(d)
.5

Zn+*

N i +
o

1.6

1.7

1.6

Etectronegot iv ity

Figure 3 (a) Relation between the CdD band position and number of 3d electrons. (b) Relation between the Cd~) band position and atomic
weight. (c) Relation between the C4) band position and ionic radii. (d) Relation between the C4) band position and electronegativity.

as the frequency or the force constant increases. This

means that the intensity increase is due to the increase
in covalency. The M L bands show intensity variation
with CFSEs of a tetrahedral high spin configuration
(Fig. 4c) which is qualitatively parallel to the variation
in the 3d orbital population of the metal ion.
From the previous discussion it can be concluded
that these complexes are of tetrahedral structure.
2196

Nakamoto et al. [20] suggested that metal chelates 1 : 2

compounds show for IR(ML) bands in the case of
tetrahedral structure. In the present work, only two IR
bands appeared in the region from 250 to 550cm
and were assigned as metal-ligand vibration bands as
previously mentioned and confirmed. T h i s can be
explained assuming that the transition'metal oxine
complexes under investigation probably possess

TABLE

I IR spectra of some transition metal oxinate in the 2000 to 200cm ~ region

Oxine

Mn ++

Co ++

Ni ++

Cu ++

Zn ++

Cr +++

Fe +++

RI

Assignment

1627
1595
1582
1504
1473
1435
1412
1382
1283
1225
1208
1168
1140

1602

1625

1603

1610

1605

1610

1572
1495
1464

1582
1493
1470

1587
1503
1470

1585
1505
1473

I425
1380
1330
1268
1222
1207
1178
1142
1107

1422
1376
1325
1283
1224
1208
1175
1136
I105

1095
1060
1030

1060
1030

1068
1023

1066

1404
1380
1316
1276
1240
1208
1178
1137
1116
1094
1066
1035

1572
1498
1465
1422
1375
1322
1280
1235
1222
1170

1580
1495
1462
1426
1384
1375
1268
1242
1184
1140
1112
1060
1035

W
W
S
V.S
V.S

1418
1382
1313
1265
1230
1202
1168
1132
I105

1605
1583
1480
1452
1380
1270
1240
1206
1176
1138
1107
1067
1022

C = N Stret.
C = C Stret.
C = C Stret.
C = C Stret.
C = C Stret.
C = C Stret.
C = C Stret.
ring C-H bending
C-N
C = C Stret.
C-N
C~2 ring Sket.
O-H bending
C-H bending
C~) Stret.
O-H bending.
O-H bending.
O-H bending.
C4)
C-H deform.
C-H deform9
C ~ deform.
C ~ deform.
C-H out of plane
deformation.
C-H out of plane
deformation.
C-H out of plane
deformation.
C-H out of plane
deformation 9
C-H out of plane
deformation.

895
829
810
787

905
824
802
782

972
913
815
807
795

870
828
802
785

871
822
802
783

918
835
810
783

M
S
S
S
Sh
W
M
M.Sh
V.S
Sh
W
M
V.S
M
W
S
M
S

738

755

750

763

754

743

733

V.S

7ll

724

727

728

738

738, 728

745

670

665

668

668

671

665

Sh

635

635

628

630

623

625

610

613

575
465
270

574
487

545
488

544
490
.
410
260

598, 552
502
.
417
280

543
487

522

533
509

398

415
305

S
S
M
M

1 0 1 5

975
898
820
808
784

902
818
800
782

743

392
270

400
275

1111
1087
1050
1030

.
396
270

(M~O) Stret.
(M-N) Stret.

RI: Relative Intensity; W: Weak; M: Medium; S: Strong;

VS: Very Strong, Sh: Shoulder.

4.4

4.4

mo 4.o

m4.0

e L ] ++

x
<

,++Co+* ~ / F e

3.6

247

cr

zn

E
0)

c 3.2

M n'"
I

O1
eo
G

3.2

~247247247 Cu+.

(b

o
1.7

1"'50.065

Ni

o/M~
I

400

410

420
CUo++/

t (.

C~+
Ni

....

(a)

-,*+ . /

i,,n
c
(1,,

oFe*247

1.9

3.6

Zn 247

/..o J * *
Zn
oMrf*

"---...~n

0.070

0.075

0.080

Ionic radli

1.7

(nm)

1'~86

(b)

490
495
500
Band position ~ (cm -1)

Figure 4 (a) Relation between the integrated intensity and ionic radii. (b) Relation between the integrated intensity and band position.
(c) Relation between the integrated intensity and CFSE.

2197

2.

4.4

4.0

Cu**
Co* ~

"~ 3.6 Cr
/ME +
Zrl**

"u 3.2~ ;Fe...+

..,-,
o
,-o'1

C r.,.,.+

C~

Faraday Society Symposium, Trans. Faraday Soc., 41 (1945)

171.
3. H. W. THOMSON, J. Chem. Soc. 1 (1948) 328.
4. V. Z. W I L L I A M S , Rev. SoL Instrum. 19 (1948) 143.
5. J. LECOMTE "Le Rayonnement lnfrarouge", Tome 2,
(Gauthier Villars, Paris, 1949).
6. N. B. C LO TH U P , J. Opti. Soc. Am., 40 (1950) 397.
7. D. A. RAMSY, J. Amer. Chem. Soc. 74 (1952) 72.
8. T. J. C A R D W E L L and R. J. MAGEE, Anal. Chem.
Acla, 43 (1968) 321.
9. Idem, ibid. 36 (1966) 180.
10. R. J. MAGEE and L. G O R D E N . Talanta 12 (1962) 441.
11. R. LARSSON and O. B A C K ILLS O N , Acta. Chem. Scan.
22 (1968) 1067.
12. R. J. C LA R K and C. S. W I L L I A M S , Chem. Ind. London
4 (1969) 1317.
13. M. G O L D E S T E I N , E. F. MOONEY, A. A N D E R S O N
and H. A. GABBI. Spectrochim. Acta, 21 (1964) I05.
14. H. F. ALI, F. M. A B D EL-K ER 1M and A. T. J A N D I L ,
J. h~org. Nucl. Chem. 33 (1971) 4340.
15. L. G. H U L L E T and O. A. T H O R N T O N , Spectrochim.
Acta, 29A (1973) 757.
16. M. K. HASSAN a n d A . M. ELDIB, ibid. 36A(1980) 903.
17. R. G. C H A R LES ,
H. F R E I S E R ,
R. F R I E D E L ,
L. E. H I L L A R D and W. D. JOHNSON, Spectrochim.

Acta. 8 (1956) 1.
18.
19.

0.5

1.0

1.5

CFSE

20,

D. H. W H I F F E N , J. Chem. Soc. 2(1956) 1350.

J. C. DWCIUS, O. G. MOLEN and H. W. THOMSON,
Proc. Soc. A275 (1963) 295.
K. N A K A M O T O ,
P . J . Mc C A R TH ,
A. RUDY
and
A. E. M A R T E L L , J. Amer. Chem. Soc. 83 (1961) 1273.

higher symmetry and only two metal-ligand (ML)

bands appear.
References
I.

R. B. BARNES, U. L1DDLE and V. Z. W I L L I A M , Ind.

Eng. Chem. Anal. 15 (1943) 659.

2198

Received 3 January
and accepted 17 August 1989