~0&4F?

&alof ilfolecz&r Structure iTheochem), 209 (1990) 157-162 157

Eieevier Science Publishers B.V., Amsterdam

STRUCTURE OF THE OXALATE ION

MICH~L J.S. DEWAR* and YA-JUN ZHENG

Department of Chemistry, Uni~ersi~ of Texas at Au&&z, Austin, TX 78712 (U.S.A.)
(Received 2 March 1990)

ABSTRACT

While the oxalate ion is planar in some crystalline oxalates, it is twisted in others, with variable
twist angles between the carboxylate groups. Calculations by AM1 and ab initio procedures have
now shown free oxalate ion to have an orthogonal fiZh structure. Intr~uction of disembodied
charges (“sparkles”) as models of metal cations reduces the twist angle and zinc oxalate is calcu-
lated to be planar, like oxalic acid. The hydrogen oxalate anion exists in two isomeric forms with
similar energies, a planar form with cis hydroxyl and an orthogonal form with trans hydroxyl.

INTRODUCTION

The crystal structures of a number of metal oxalates show interesting vari-

ations in the geometry of the oxalate ion [l-9]. Thus, while the ion is planar
in lithium, sodium, and silver oxalates ( 1 ), as it is in oxalic acid (2; both CY
and /? forms), it is nonplanar in potassium hydrogen oxalate ( 3 ) , ammo~um
oxalate monohydrate (4) and in copper ammonium (5) and copper potassium
(6) oxalate dihydrates. Whether this structural difference is caused by inter-
molecular forces in the crystal or simply reflects inherent nonplanarity in the
oxalate ion itself is not known,
This question cannot easily be answered by experiment because it would be
extremely difficult to study the structure of free oxalate ion. No problems
should, however, arise in a theoretical study. Here we report a detailed theo-
retical investigation of the oxalate ion and of the effects of adjacent cations on
its structure.

PROCEDURE

The calculations were carried out using both the AM1 [lo] and ab initio
models as implemented in the AMPAC2.1 [ 111 and GAUSSIAN 86 [ 12 ] pro-
grams. Geometries were located by minimizing the total energy with respect to

*Author to whom correspondence should be addressed.

0166-1280/90/$03.50 0 1990 - Elsevier Science Publishers B.V.

158

all geometrical parameters. Stationary points on the potential-energy surface

were characterized by calculating force constants [ 131. A population analysis
was carried out in both calculations.

RESULTS

AM1

AM1 calculations were first carried out for the planar (Dzh; 7) and orthog-
onal (Dzd; 8) structures of oxalate ion. Both corresponded to stationary points
on the potential surface. The calculated heats of formation, geometries, and
formal charges are shown in Table 1. In contrast to a previous claim [ 141, the
stable form of oxalate ion is predicted to be the orthogonal form (8)) 7 being
a saddle point on the potential-energy hypersurface, higher in energy than 8
by 5.1 kcal mol-‘. Since the C-C bond is very long and the K bond order ex-
tremely small, the two CO, groups are essentially singly bonded in both types
of structure, in agreement with experiment.
Since AM1 parameters are not available for the relevant metals, their effect
was simulated by introducing disembodied charged spheres (“sparkles”). Pro-
vision for this is incorporated in both AMPAC and AMPAC2.1. The radius of
the sparkle was chosen to make the corresponding M+-O- distance the same
as that in ammonium oxalate (2.83 A).
As Table 2 shows, the presence of sparkles tends to reduce the twist angle.
In the presence of one sparkle, the twist angle becomes 66.8”. Addition of a
second sparkle reduces it to 30’) which is in excellent agreement with experi-
ment for ammonium oxalate (28’ ) .
Calculations were next carried out for zinc oxalate (9 ) , oxalic acid (2 ) , and
hydrogen oxalate ion ( 10).The results are shown in Table 2. In 9, the oxalate
ion is virtually planar, due to chelation with the metal, and AM1 also predicts
a planar structure for 2. In the case of 10,both the cis (10a) and truns (lob)
isomers were predicted to be stable species with similar energies. However,
while 10a is predicted to be planar, due to hydrogen bonding between the
hydroxyl and carboxylate groups, lob has an orthogonal structure, like 8. The

TABLE 1
The calculated geometries, heats of formation, and formal charges for oxalate ion

c-c c-o Heat of formation Formal charge

(kcal mol- ’ )
0 C

&h 1.5406 1.2751 - 124.614 -0.6390 0.2781

&d 1.5361 1.2752 - 129.725 - 0.6506 0.3011
 159

TABLE 2
AM1 results for the oxalate ion and its derivatives

Compound Bond length (A) oco Twist angle

(“) (“)
c-c c-o

czo.y 1.5361 1.2752 120.1 90

C204M- 1.5382 1.2886 120.4 66.8
1.2594
C,C,M, 1.5418 1.2715 120.9 30
CzOIZn 1.5467 1.2304 117.0 0
1.3457
C,C,H, 1.5074 1.2291 116.7 0
1.3516
Cz04H- 1.5426 1.2645 126.6 0 (cis)
1.2504 112.5
1.2338
1.3744
1.5503 1.2528 128.0 90 (truns)
1.2387 114.3
1.3676
CzOIHM 1.5404 1.2645 126.7 0 (cis)
1.2502 113.9
1.2394
1.3588
1.5162 1.2639 122.0 90 (trans)
1.2346 116.1
1.3629

same situation holds when a sparkle is placed near 10a or lob.The only
difference is that lob becomes more stable than 10a by 1.6 kcal mol-‘.

I MZC204 M= Li, No, Ag IO

-1%” _;wo_ H
2 H2C2°4 HP
0 b

3 KHC204

4 (NH4)2 C204 H20 ,..O.\\

5 CdNH4)2(C20412.2H20 O$ i;
ll

6 CuK2(C204)2.2H20 *\.,

ZnC2O4
160

TABLE 3

Calculated geometrical parameters, total energies, and charge distributions for the oxalate ion

6-31G*
Etic f a.u.) -375.070~63 - 375.0782~
&a (kcaI_moI-’ ) 4.88 0
rWJ) (A) 1.2427 1.2474
r(CC) (A) 1.6030 1.5489
LOCO (0) 125.9 126.3
LOCC (0) 117.0 116.8
0 - 0.7946 - 0.8273
C 0.5892 0.6546
6-31(l-)G
Em*(a.=) -374.955829 - 374.9658874
&‘_, f kcaI_moI-‘) 6.31 0
r(CO) (A) 1.2663 1.2708
r(CC) (A) 1.5876 1.5368
LOCO f”) 124.9 125.8
LOCC (0) 117.5 117.1
0 - 0.7532 - 0.7464
C 0.5068 0.4928

Ab initio results

We also carried out ab initio c~culations for 7 and 8, usingthe 6-31G* and
6-31+ G basis sets. The calculatedbond lengths, energies,and charge distri-
butions are given in Table 3. As comparison of Tables 1 and 3 shows, the ab
initio resultsagreereasonablywell with the AM1 ones. Thus 7 is predictedto
be higher in energy than 8 by 5.1 (AMl), 4.9 (6-31G*), and 6.3 (6-31G+)
kcal mol-l and the corresponding differences in bond lengths and atomic
chargesare similarin all three methods.The biggestdiscrepanciesconcern the
CC bond length and the OCO bond angle. While all three procedurespredict
the CC bond to be longer in 7 than in 8, the ab initio calculations lead to a
largerdifference (0.05 vs. 0.005 A), and the ab initio valuesfor the OCO bond
angleare greaterthan the AM1 valuesby ca. 6 *.

DISCUSSION

Our results seem to show unambiguouslythat the carboxyl groups in free

oxalate ion are orthogonal to one another, the ion having a twisted structure
with a twist angle of 90”. The ion is less twisted in correspondingsalts, due to
electrostaticinteractionsbetween the carboxylateoxygens and the metal cat-
ions; see 11.If the cation is small enough to fit between the oxygen atoms in
 161

TABLE 4

Some early experimental M-O distances

M M--O in crystal
(A)

Li+ 2.076,2.033
1.999,1.935
Na+ 2.29, 2.54
2.45, 2.35
K+ 2.704,2.964
NH: 2.67, 2.81
2.85
Sparkle 2.83

8, the oxalate moiety will be planar. Otherwiseit will be twisted, and the twist
anglewill be greater,the largerthe cation. Table 4 comparesthe metal-oxygen
distances in some crystallineoxalates. The planar oxalates are the ones with
the smallest metal-oxygen distances. The diametersof the sparkleswere de-
liberatelychosen to mimic ammoniumion. As noted above,both lead to similar
twist angles.
Ions that are good chelating agents will tend to form oxalates in which the
oxalate ion is planarbecausethe metal-oxygenbonds are then largelycovalent
and hence shorterthan ones whichare essentiallyelectrostatic.As noted above,
our calculationspredict the oxalate moiety in zinc oxalate to be planar.
The results for the hydrogen oxalate ion ( 10) are in~resting. The predic-
tion that it can exist in either of two equally stable isomeric forms was quite
unexpected. The orthogonal isomer might well be the preferred form in salts
containing bulky cations. No experimentalstudies of this kind seem to have
been reported.

ACKNOWLEDGEMENT

This work was supported by the Air Force Office of Scientific Research
(Contract AF 89-0179)) The Robert A. Welch Foun~tion (Grant F-126)) the
National ScienceFoun~tion (CHE 87-12022). The ab initio copulations were
carried out on the Cray Computer at the Universityof Texas System Center
for High PerformanceComputing (UTCHPC ).

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