Bpectrccklmlcr,

Acti.1967,

Vol. 0, pp. 51 to 58.

Pergmon

PIWE Ltd., London

Infra+ed absorption spectra of inorganic co-ordination complexes*-IX

I&wed spectraof oxalato complexes
M. JUDITH Scmumz,j TATSUO MIYAZAWA,SAN-ICHIROMI~USHIIU$
T. J. LANE, and J. V. QUAQLIANO
Ab&ract-The in&wed qmotra of simple met& oxsletes have been measured end the essignment of bends hes been besed on the normal vibration oalculetion for the free oxalate ion. The
i&m-red speotre of ox&to complexes of Fe(III), Co(III), Cr(III), Al(III), Pd(II), end Cu(II)
hsve been measured in the NeCl and CsBr regions. Assignment of bends hes been made by the
oomparieon of the spectra with those of elkeli mti
ox&&s and dimethyl oxslste.

SIMPLE oxalate salts consist of a metal cation and the oxalate anion. Therefore,
the infrared spectra of these compounds in the NaCl and CsBr regions are considered to arise from the oxalate ion and from water of crystallization present in
the compound. In most metal oxalato complexes the ligand is co-ordinated to the
central metal ion through two oxygen atoms, whose oxygen-to-metal bonds have
at least some covalent character. DOUVILLI$ DUVAL, and LECOMPTE[l] have
carried out a number of absorption studies of simple and complex metal oxalates.
Oxalato complex salts can be explained approximately by considering the vibrations
of the structure, whiah in some respects is similar to dimethyl oxalate. However,

in a complex ion such as thetrioxalato metal complex, coupling of similar vibrations

of the same structure must also be considered.
The results of this research, based on the normal vibration calculation of the
free oxalate ion, explain the nature of the vibrations of simple oxalate salts. The
infrared bands of the oxalato metal complexes are assigned by comparison with
those of simple oxalate salts and of dimethyl oxalate.

Experimental
Prepamtion and purQ2caGm of mwpoud.
Calcium, lithium, end berium oxalates were
Fisher-certi5ed reagents; potassium oxelete was 8 Baker8 C.P. product; and sodium oxelete
w8s obtained from the Nntion8l Buresu of Stendards. &mples were dried et 110. Iron(III),
oobslt(III), chromium(III), end&mini um(III) triox&ato complexeswerepreparedend &31l8lysed
by Dr. D. N. SEN [2]. Tran+W.sssium dioxaletodiaquochromte(II1) trihydrate and tranesodium diox&todisquoohrom&e(III) pentahydrste wereprepsred by themethod of Wxnmrx[2].
l PaperVIII in scrics,J. Amer. Clmtn. Sm. 1956 78 889. Prcscntcd
in part beforethe Physics1and
InorgenioDivisionof the AmericanChemicalS&&y, KansscCity, Misscuri,March 1954; contribution
from the Departmentof Chemistry,Universityof Notre Dsme.
t Sr. M. Junrr~. R.S.M.
$ VisitingProfcsscrfrom Faculty of Science,Tokyo University.
4 Rev. T. J. Lm, C.S.C.

51

M. JUDITH

SCAHELZ

ti al.

Anal. c&d. for K[Cr(CI0,),(H,0)813HIO:

Cr 14.56. Found: Cr 14.87. Calcd. for
Se[Cr(C,O,),(H,O),]*sH,O:
Cr 13.79. Found: Cr 13.75.
Sodium dioxaletodiiuocuprste(I1) wee prepared ee described by RILEY [4].
Anal. calcd. for Na&u(C,O,),(H,O),]:
Cu 19.75. Found: Cu 19.50.
Potassium dioxalatopalledate(I1) [5] was prepared by adding a concentrated solution of
K&&O, to a concentrated aqueous solution of qPdCl,].
[Pd(NH.J,(C,O,)] was prepared by
dissolving cie-~d(N&)&ls]
in a concentrated aqueous solution of K&,0, [6]. The complexes
DreciDitated
in the cold.
_
A&. celcd. for KJPd(C,O,),]*ZH,O:
C,O, 44.36. Found: 44.10. C&d. for [Pd(NH&C,OJ:
C&O,
- _ 38.47. Found: 37.98.
Deuteration was effected by recrystellizetion of the metal ox&tea from 99.6% D,O.
Table 1. Observed frequencies of simDle
. ox&tee in cm-l*
Li,C,O,

NB*C*O,

1650vs
1420m
1330V8
782 ah
771 vs
607 s
434 8
3708

K&,O,*H1O
33708
-

1640vs
1418m
1338v8
1320VB
i80 ah
774 vs
514 s
360 m

1600vs
1408m
1310v8
772 s
716 m
613 6
623 s
349 m

cac*04*~o
34008
33008
3020E
1620vs
1366m
I316 VB
943 m
881 m
780 VB
6608
511 s
416 w
306s

Ek3C*04*~0
3600m
3400m
1620VB
1600~1
1470m
1326vs
1310VB
896w
866 m
771 VB
662 m
620 s
406 w
343 m

lvs = very strong,8 -_ strong,m = medium,w = weak, ah = shoulder.

Table 2. Observed frequencies of trioxalato complexes in cm-l
I%MC,O,),l.3H,O
3440w
1726VB
1696vs
1400va
1290a
1268a
906 m
820 m
800m
677 s
478 8
434 m

3460w
1710vs
1680vs
1400vs
1300w
1265m
903 w
823m
804 m
540 8
480 m
409 B

3466w
1710VB
1680vs
1390vs
1266m
1248m
890 m
802 8
785 m
674 sh
628 B
493 a
L

52

3460w
1710VB
1680va
1397vs
1300w
1266m
QOOW
823m
806 m
661 B
470 B
445s

Infra-redapeotmof oraleta oomplexea

A&umydon +twatum.
Spectra were obtained by merm~ of a Per&n-Elmer mode1 21
i&a-red ~~~~r
u&g N&l and CkBr priamt~ The region from 2 to 3B microns wae
examined and the kgectra obtained by the KBr d&k method were checked u&g Nujol mu&.
The abeorption bands obeerved we Ii
in Tables 1.2, and 3.
Table 3. Observed frequenciesof mono- and dioxalato complexes in cm-1

wwIoI)*
WWC,ol),
@J$%iP@%Q @%%13W
3430 8
3350 sh
2980 B
17111vs
1090 v8
1660 vs
13911VB
1255 8
967 m
88313
812 VB
663m
64(lm
$43 e
424 B
398 a
316 m

35Ooa
3400s
1728 m
1680 vs
1412 vl!
1275 s
898 m
800s
6&Hs
4Q78
387 m
346 s
-

3460 m
3400 lab

32PX@
3X0(
liws Ys
1665 vs
1630 ah{
1400 ve
1318 e(a)
12bOE
895 w
823 e
779 m(O)
649 B
467 8
374 m
363 m
299 m

1708 ve
1680 vs
13SovfJ

1240 e
890 m
813 e
6Ooe
570 6
434m
374 a
367 m

3430 0
3360 ah
2960 a
I715 VE
1690 WJ
I66Ove
1396 vs
I257 a
967 m
886 e
815 vs
658 m
-

5408
422 6
399 B
3111m
-

(*I Thesefrequencies
are attributedto NH, stmtohing and deformation vibrationa [7).

1. Ncan?&

~b~~~

~~~~

of OX&i?0 ion

and

the a&Ggwne&

of obS$f-#~

freque9uGecr.The calculation of normal vibrations of the free oxdate ion hadibeen

made on the basis of the Urey-Bradley type potential:
Table 4. ?dokcular oonstnn~ and force constants
(106 dyne/cm) of the ox&&e ion
Mohouler

Force con&at&

COImtante
I

ef--a
w--Q
(O-C-O)
(c--G-o

1~6

1.27 A
124
IlfY

K(c-a)
WC-01
Rfo-C-0)
R(c-c-0)
P(O *. .O)
P(C . . . 0)

2.60
7.20
0.15
0.15
3.00

040

M. JUDITH SCHMELZet

d.

V = Xd&(ArJZ + E*H.,,T~~Y,~
( Aaij)a + EQP,, ( AqJe + linear terms, where ri and
r, are bond lengths with equilibrium values rio and r,O; ai, bond angles and qu
distances between nonbonded atoms. In addition, K, H, and Prepresent stretching-,
bending-, and repulsive-force constants respectively.
The atomic distances, bond angles, and force constants used in this calculation
are shown in Table 4. The molecular constants have been taken from data obtained
for ammonium oxalate monohydrate [8], and the stretching-force constant K,
bending-force constant H, and repulsive-force constant P have been taken from
the corresponding constants of ethane [9], formats ion [lo], and acetate ion [Ill
respectively. The frequencies calculated for the VI, model are shown in Table 6.
Table 6. Calculated and observed frequencies of the ox&&e
Symmetry

of vibration

B,,(R)

calcul8ted

Type

PP
S

VI (O--c--Q
v (C-C)
6 (O-C-O)

C-C

"6

va P--c--o)

VI
A,(R)

torsion

Obaervedt

1407
973
412

1489
902
460
inactive

I
1696
432

CO, rocking

VI3

ion with point group V,*

1647
317

CO, We&X43

CO, W%&%

B,,(I)

1S
lo

v, (O-C-O)
CO, rocking

1644
222

1600
-

B,,(I)

Vll
VlS

v, (O--c-o)
6 (O-C-O)

1336
777

1310
772

B,,(I)

V?

B,,(R)

* R = Raman active; I = infra-red active; v = stretching; v, = symmetric stretching; v,, = antistretching; b = in-plane deformation vibrations.
t Observed values are those for K,C,O,.H,O.

symmetric

In Na,C,O, three absorption bands have been observed at 1640, 1329, and 774
cm-l. These three bands can undoubtedly be assigned to Y*, yll, and wX1,respectively. In the case of K,C&O,*H,O, LiaCaOr, CaC,O,*H,O, and BaCpO,*H,O the
corresponding three bands occur at about 1010, 1314, and 775 cm-l. The band
arising from the deformation frequency of water in the monohydrates overlaps the
y0 band. Furthermore, the spectra of the monohydrates show a broad absorption
band at about 680 cm-l which in some way may be related to the water molecule,
since this band disappeared upon deuteration.
Raman lines of K&,0, in aqueous solution were reported by EDSALL [12] at
1647 (ib), 1489 (7), 902 (6), 456 (3) cm-l, and they can be assigned to Y&,yl, vz, and
64

I&a-red epeatraof oxslat complexes

respectively. Since the latter three lines are strong Raman lines, they can be
assigned quite reasonably to the A, class.
The vli (B,,) and Y@ (B,,) bands are forbidden in the Raman effect by the
selection rule for the Vh symmetry. Since they were observed in the aqueous
solution, however, the VIhsymmetry may be changed to V in this state. That is to
say, the oxalate ion is no longer planar, and consequently yll and vp have been
observed in aqueous solution. In this connection, Table 6 shows the corresponding
vibrations for the planar V* model and the nonplanar V model. It is to be noted
that for all the B, vibrations, frequencies become independent of the azimuthal
angle 8 of the internal rotation about the central C-C axis, since the G and F
matrices for B, do not include 8. Consequently, the B, frequencies of ?a become
Raman-active for V without a change of frequency.
Ye,

Table 6. CYkaificetionof vibration typea for the plansr V,

and nonplanar V mod& with selection rulea
Nonplaner (V)

pl@ner ( VA)

3A,W)

14

4A(R)

2%,(R)
l%(Z)

3B,(R, 4

lB,,(R)
2&u(Z)
04,(R)
2%(Z)

3B,(R, I)

2B,(R, I)

The G and F matrices of the B,- and B,-type vibrations contain 8 and therefore
change considerably with a change of internal rotation. This change is most marked
for the O-C-O
rocking and wagging frequencies. It would be interesting to
compare the Raman effect of K,C,O,*H,O in the solid state with that in aqueous
solution.
Probably in aqueous solution the energy of conjugation between the two
O-C-O
groups is reduced and thus steric repulsion between them becomes
more important, resulting in an out-of-plane twisting about the C-C bond. It is
easily seen that the steric repulsion potential is a minimum when one O-C-O
group is at right angles to the other.
2. Aesignmem? of IR band.8 of oxalato compleaw.
To assign the bands observed
in the oxalato complexes, the spectrum of dimethyl oxalate in the CWform together
with that of the oxalate ion must be considered. Dimethyl oxalate in the liquid
state was shown by one of us (B~IYAZAWA)
to exist in both the trana and cis forms.
Of these, the c&3form may be considered similar in vibrational spectrum to chelated
oxalato metal complexes. The assignment of the spectrum of the tie ester was
made as shown in Table 7 [ 131, listing only the frequencies necessary for comparison.
55

M. JUDITH SCENELZ e4 al.

From these data the assignment of infrared bands for the chelated trioxalato
metal complexes can be made as follows:
(1) An intense doublet band observed at about 800 cm-l .ie considered to
correspond to the 772~am-l (B,,) band of the oxalate ion of the potassium salt,
and the 851~cm-l (B,) band of the tie ester and can be assigned to the (O-C-O)
deformation vibration (B,) . The doublet structure arises from coupling of vibrations
of the three oxalato groups, as will be explained later.
(2) The band at about 900 cm-l corresponds to the band at 902 (A,) of the
oxalate ion and that of the cti eater at 862 cm-1 (A,). Therefore, this can be
assigned to the C-C stretching vibration (A,).
(3) A doublet baud observed between 1260 and 1300 om-1 is considered to
correspond to the 1310~cm-1 (B,) band of the oxalate ion of the potassium salt
and to the 1166-cm-1 (B,) band of the cis ester. This is the C-C-O
stretohing
vibration in the oxalate ion. In the c&3ester the C-O bond order is less than the
C=O bond order and therefore this vibration arises mainly from the C-0 vibration.
However, there is a contribution of the C=O stretching vibration in the same
phase as the C-O vibration, and therefore we shall denote this vibration of the
oxalato complex as Y, (C-C-O).
Table 7. Adgnment of Borneobserved frequenaieaof
dimethyl oxdate in the cis form

observed

fiwqutmcy

Tspe of vibr8tion

404
861
882
958
987
1166
1326
1770
1778

(4) A strong absorption observed at about 1400 cm-l corresponds to the

1489~om-l band (a,) of the oxalate ion and to the 1326-cm-1 band (A,) of the tie
ester. Therefore, this band can be assigned to the C-C-O
symmetrio stretching
vibration (A,). This band does not show a doublet splitting.
(6) Strong doublet bands were observed in the 1700~cm-l region. Here we may
expect A, and B, type C-C-O
stretching vibrations. As shown below, the B,type vibrations appear as double bands, of which the higher frequenoy band is
considered to overlap the A,-type band.
(6) The band observed at about 3460 cm-l can undoubtedly be assigned to the
stretching vibrations of the water of crystallization.
The following explanation is proposed for the observed doublet structure of the
66

B,-type vibrations. In the preceding discussion we have been dealing with the
vibrations of oxalato complexes as a seven-body problem, taking into account one
oxalato group and the central metal atom. Strictly speaking, however, the vibrations should be treated as a nineteen-body problem. In other words, in addition to
the frequencies just considered, we have to take into account the coupling of three
such systems.
The trioxalato metal complex ions have a symmetry of D,. Consequently, the
B,-type vibrations of a single oxalato group are classed as symmetric to the trigonal
axis (A,) or degenerate (B), both of which are ix&a-red-active. On the other hand,
of the AI-type vibrations of a single oxalato group those symmetric to the trigonal
axis (A,) are inactive and those degenerate are active. Thus it is understandable
that the BI vibrations of the oxalato group are observed as double bands, whereas
the A, vibrations of the group are single .
The carboxylate frequencies in the spectra of the oxalato metal complexes am
intermediate between those of the oxalates of the alkali metals (in which the
metal-to-oxygen bonds are essentially ionic) and those of dimethyl oxalate,
Table 8. Fraoticnal shiftaof oerboxylofeetretohing
fbqllenoiefJ in trioxlbl8to ccxnplex~
!Cype~
of vibration

Fe

Cr

Co

Al

suggesting a partial covalent character for the oxygen-to-metal bonds in these

complexes. Using the carboxylate frequencies of sodium oxalate as the standard
of reference, the ratio of the shift in these frequencies in a complex to that in the
ester, which we shall term the fractional shift, may be taken as a measure of the
covalent character of the M-O bonds. The relative positions of the absorption
bands in K,C,O,*H,O and KJAl(C,04)&3H,O
are shown in Pig. 1.
For this comparison of frequencies we have chosen the O-C-O
antisymmetric
stretching vibration (B,) and the O-C-O
symmetric vibration (A,), thereby
avoiding the difficulty arising from coupling with the M-O stretching vibration,
the CHgO
stretching vibration, and the CH, rocking vibration. The result is
shown in Table 8, where simple oxalate salts are assigned a value of zero and dimethyl ester a value of unity. The mean value of the fractional shift is about O-6,
which indicates that the M-O bonds in these complexes have about half the covalent character present in the C-O bond of the dimethyl ester.
Acknowledgement--This
investigation was supported in part by a research grant
H-2218 (C) from the Department of Health, Education and Welfare, Public Health
Service.
57

M. J~DITE i!hxwsz

St at.: Infkw0d spehxb of oxal& complexes

Wave

em-*

numbers

Wove

10

11

12

13

length

14
15
micron

Fig. 1.
Potsssiumoxalete monohydrmti,
K&,O,*H,O.
- - - - - - Potiium trioxalatoal
uminak trihydrsti,K&u(C,O,),~3H,O.

[l]
[2]
[3]
[4]
[6]
[6]
[7]
[S]
[9]
[lo)
[I l]
[12]
[13]

DO~IIJ& F., DWAL C., snd LECOMPXE

J. BUU. So& CM?& Fvavace 1942 9 548.
SEN D. N. Ph.D. thesk,.Utivereity of Notre Dame, 1964.
WYBBXER
A. Ann. 1914 408 261.
R-Y
I% L.
J. Okem,Sot. 1929 1307.
LAXD~EN G. 2. Anmg. Clbcna.1926 154432.
MANX F. G,, CisoWroo%D., GA-B
D. C., and WOOB~
N. J. Cliern.Sot. 1936 184%
MIZUS~
S., NAKAGAWAI., snd QOA~LXAS~O
3. V. J. Chess. Z%y8. 1966RB;1867.
JEEFItBY C. A. and PARRYG. S. J. Cbra. Sot. 1962 4864.
Priveti communicationof Dr. T. Stiouchi.
&ffYAZAWA
T. J. ChRnr.Sot. Jcqxxn1986 77 381.
OUUIXIT., and NAIIAB~UF~A
K. p&a& oommunioetion.
MrznS~
s., s=
EDSAX&J. T. J. Churn.P&p. 1937 & 608.
Sot. Japan 1954 745540.
MntazhWA T. J. C?te~%.