Crystal and molecular structures of alkali oxalates: First proof of a staggered oxalate anion in the solid state

Article abstract of DOI:10.1021/ic0205536

The molecular and crystal structures of solvent-free potassium, rubidium, and cesium oxalates have been determined ab initio from high-resolution synchrotron and X-ray laboratory powder patterns. In the case of potassium oxalate K₂C₂O₄ (a = 10.91176(7) A, b = 6.11592(4) A, c = 3.44003(2) A, orthorhombic, Pbam, Z = 2), the oxalate anion is planar, whereas in cesium oxalate Cs₂C₂O₄ (a = 6.62146(5) A, b = 11.00379(9) A, c = 8.61253(7) A, β = 97.1388(4)°, monoclinic, P2₁/c, Z = 4) it exhibits a staggered conformation. For rubidium oxalate at room temperature, two polymorphs exist, one (β-Rb₂C₂O₄) isotypic to potassium oxalate (a = 11.28797(7) A, b = 6.29475(4) A, c = 3.62210(2) A, orthorhombic, Pbam, Z = 2) and the other (α-Rb₂C₂O₄) isotypic to cesium oxalate (a = 6.3276(1) A, b = 10.4548(2) A, c = 8.2174(2) A, β = 98.016(1)°, monoclinic, P2₁/c, Z = 4). The potassium oxalate structure can be deduced from the AIB2 type, and the cesium oxalate structure from the Hg₉₉As type, respectively. The relation between the two types of crystal structures and the reason for the different conformations of the oxalate anion are discussed.

Full text of DOI:10.1021/ic0205536

Inorg. Chem. 2003, 42, 1499−1507
Crystal and Molecular Structures of Alkali Oxalates: First Proof of a
Staggered Oxalate Anion in the Solid State
Robert E. Dinnebier,* Sascha Vensky, Martin Panth o1 fer, and Martin Jansen*
Max Planck Institute for Solid State Research, Heisenbergstrasse 1, D-70569 Stuttgart, Germany
Received September 12, 2002
The molecular and crystal structures of solvent-free potassium, rubidium, and cesium oxalates have been determined
ab initio from high-resolution synchrotron and X-ray laboratory powder patterns. In the case of potassium oxalate
K
2
C
2
O
4
(a ) 10.91176(7) Å, b ) 6.11592(4) Å, c ) 3.44003(2) Å, orthorhombic, Pbam, Z ) 2), the oxalate anion
is planar, whereas in cesium oxalate Cs (a ) 6.62146(5) Å, b ) 11.00379(9) Å, c ) 8.61253(7) Å, â )
7.1388(4)°, monoclinic, P2 /c, Z ) 4) it exhibits a staggered conformation. For rubidium oxalate at room temperature,
two polymorphs exist, one (â-Rb ) isotypic to potassium oxalate (a ) 11.28797(7) Å, b ) 6.29475(4) Å, c )
.62210(2) Å, orthorhombic, Pbam, Z ) 2) and the other (R-Rb ) isotypic to cesium oxalate (a ) 6.3276(1)
Å, b ) 10.4548(2) Å, c ) 8.2174(2) Å, â ) 98.016(1)°, monoclinic, P2 /c, Z ) 4). The potassium oxalate structure
can be deduced from the AlB type, and the cesium oxalate structure from the Hg99As type, respectively. The
2 2 4
C O
9
1
2 2 4
C O
3
2 2 4
C O
1
2
relation between the two types of crystal structures and the reason for the different conformations of the oxalate
anion are discussed.
Introduction
well-established experimental fact is indicative of a bond
order of 1 or even less. Thus, one would expect a staggered
conformation (point symmetry D2d) of the oxalate anions to
be preferred. This view is strongly supported by quantum
Alkali oxalates play an important role in nature and
chemistry. The sodium and potassium salts of oxalic acid
are found in many plants (clover, sorrel, salicornia, spinach,
rhubarb, bamboo shoots, cacao, roots, and tree barks).
Oxalates find some technical and medical applications such
as stain removal in photography, metal coatings for stainless
steel, nickel, chromium, titanium, and their alloys, cleaning
and bleaching of natural fibers, textile dyeing, anticoagulants
in medical tests, and dental seals. Furthermore potassium
and sodium oxalate complexes are able to pass the gastric
mucous membrane, and therefore they are the main com-
ponents of kidney stones.
Nevertheless, the long-standing efforts aimed at under-
standing the characteristic structural features of the oxalate
anion using conventional concepts of chemical bonding still
remain without closure. In the first place, the C-C bond
lengths of oxalate anions (1.567(2) Å) are about 0.04 Å
too large for two sp -hybridized C atoms (1.515 Å). This
5
mechanical calculations. However, experimentally the
opposite is found: only few exceptions from planarity (D2h
)
have been reported so far. If crystal structures with R values
>
14% are disregarded, only NaHC
2
O
‚H
4
‚H
2
O (twist angle of
6
7-9
10-12
13°), KHC
2
O
4
(13°), (NH
4
)
2
C
2
O
‚0.5H
4
2
O (27°),
4 2
(NH ) -
1
3
14
C
2
O ‚H O
4 2 2
(28°), and BaC
2
O
4
2
O (30°) remain to
be considered. Evidently, in each of these instances the
oxalate is involved in significant bonding interactions, i.e.,
(
5) Colby College, Chemistry Department, Paul J. Schupf Computational
Chemistry Lab, Waterville, USA; http://www.colby.edu/chemistry/
webmo/mointro.html.
(
(
(
6) Tellgren, R.; Olovsson, I. J. Chem. Phys. 1971, 54, 127-134.
7) Pedersen, B. F. Acta Chem. Scand. 1968, 22, 2953-2964.
8) Einspahr, H.; Marsh, R. E.; Donohue, J. Acta Crystallogr., Sect. B:
Struct. Sci. 1972, 28, 2194-2198.
1
(9) Kholodkovskaya, L. N.; Trunov, V. K.; Tskhelashvili, N. B. J. Struct.
2
2-4
Chem. 1990, 31, 509-511.
(
10) Robertson, J. H. Acta Crystallogr. 1965, 18, 410-417.
*
Authors to whom correspondence should be addressed. E-mail:
r.dinnebier@fkf.mpg.de (R.E.D.); m.jansen@fkf.mpg.de (M.J.). Fax: (+49)
11-689-1502.
(11) Padmanabhan, V. M.; Srikantha, S.; Medhi Ali, S. Acta Crystallogr.
1965, 18, 567-568.
(12) Taylor, J. C.; Sabine, T. M. Acta Crystallogr., Sect. B: Struct. Sci.
7
(
1) K u¨ ppers, H. Acta Crystallogr., Sect. B: Struct. Sci. 1973, 29, 318-
1972, 28, 3340-3351.
327.
(13) Pedersen, B. F. Acta Crystallogr., Sect. B: Struct. Sci. 1972, 28, 746-
(2) Bastiansen, O.; Trætteberg, M. Tetrahedron 1962, 17, 147-154.
(3) Beagley, B.; Small, R. W. H. Proc. R. Soc. A 1963, 276, 469-491.
(4) Coulson, C. A.; Skancke, P. N. J. Chem. Soc. 1962, 2775-2782.
754.
(14) Mutin, J. C.; Dusausoy, Y.; Protas, J. J. Solid State Chem. 1981, 36,
356-364.
1
0.1021/ic0205536 CCC: $25.00 © 2003 American Chemical Society
Inorganic Chemistry, Vol. 42, No. 5, 2003 1499
Published on Web 02/06/2003

Dinnebier et al.
Figure 1. Scattered X-ray intensities for A2C2O4 [A ) K (top left), â-Rb (bottom left), R-Rb (top right), and Cs (bottom right)] at ambient conditions as
a function of diffraction angle 2Θ. Shown are the observed patterns (diamonds), the best Rietveld-fit profiles (line) and the enlarged difference curves
between observed and calculated profiles (below in an additional window). The high-angle parts are enlarged by a factor of 5, starting at 2Θ values of 27°
(
K2C2O4), 30° (â-Rb2C2O4), 44° (R-Rb2C2O4), and 21° (Cs2C2O4). The wavelengths were λ ) 0.7 Å for K2C2O4 and Cs2C2O4, 0.83 Å for â-Rb2C2O4, and
.54 Å for R-Rb2C2O4. In case of â-Rb2C2O4, several excluded regions in the powder pattern have been defined, in order to account for small amounts of
Rb2C2O4‚H2O present in the sample, and in the case of R-Rb2C2O4, â-Rb2C2O4 was included as a second phase.
1
H-bonds. This raises the question, whether the strong
prevalence of the planar configuration is related to intermo-
lecular interactions rather than to the intramolecular electron
density distribution. In order to empirically clarify this issue,
we have undertaken a systematic structural investigation of
ionic oxalates that exhibit the lowest possible covalent
bonding to the cations, i.e., the anhydrous oxalates of
potassium, rubidium, and cesium.
of K
Cs
2
C
2
O
4
(I), R-Rb
2
C
2
O
4
2 2 4
(II-R), â-Rb C O (II-â), and
2
C
2
O
4
(III) at ambient conditions.
Experimental Section
Potassium, rubidium, and cesium oxalate were prepared by
dehydration of the corresponding monohydrates for 18 h at 373 K
in a vacuum. Potassium oxalate monohydrate was used as purchased
(
K
2
C
2
O
4
‚H
monohydrate were synthesized by reaction of the corresponding
carbonates (Rb CO , Alfa Aesar, p.a.; Cs CO , Chempur, p.a.) and
oxalic acid dihydrate (H ‚2H O, Fluka, puriss. p.a.) in an
2
O, Fluka, puriss. p.a.). Rubidium and cesium oxalate
Due to the hygroscopic nature of the oxalates, only few
instances of successful single-crystal syntheses of solvent-
free oxalates in sufficient size and quality for single-crystal
2
3
2
3
2
C
2
O
4
2
aqueous solution. The solution was stirred for 12 h at 353 K, and
the water was subsequently removed by distillation. The precipitates
were washed with diethyl ether and acetone. The dehydrated
oxalates were handled under argon as an inert atmosphere to prevent
a possible contamination by water.
X-ray powder diffraction data of the room temperature phases
of I, II-â, and III were collected at T ) 295 K on beamline X3B1
of the Brookhaven National Synchrotron Light Source in transmis-
sion geometry with the samples sealed in 0.7 mm (I), 0.5 mm (II-
â), and 0.3 mm (III) lithiumborate glass (Hilgenberg glass No. 50)
capillaries (Figure 1). X-rays of wavelength 0.7 Å (I and III) and
1
5
analysis have been reported so far: by diffusion (Ag
2
C
2
O
4
),
,16
2 2 4 2 2 4 2
C O , K Be(C O ) ), or hydrothermal crystallization
slow evaporation from an aqueous solution (Li
2
2 4
C O
1
7
18
Na
SrC
Therefore we performed high-resolution X-ray powder
diffraction experiments to determine the crystal structures
19
(
2 4
O ).
(
15) Naumov, D. Y.; Virovets, A. V.; Podberezskaya, N. V.; Boldyreva,
E. V. Acta Crystallogr., Sect C: Cryst. Struct. Commun. 1995, 51,
6
0-62.
(
(
16) Beagley, B.; Small, R. W. H. Acta Crystallogr. 1964, 17, 783-788.
17) Reed, D. A.; Olmstead, M. M. Acta Crystallogr., Sect. B: Struct. Sci.
0.83 Å (II-â) were selected by a double Si(111) monochromator.
1
981, 37, 938-939.
Wavelengths and the zero point were determined from eight well-
defined reflections of the NBS1976 flat plate alumina standard.
The diffracted beam was analyzed with a Ge(111) crystal and
detected with a Na(Tl)I scintillation counter employing a pulse
(
18) Jaber, P. M.; Faure, R.; Loiseleur, H. Acta Crystallogr., Sect. B: Struct.
Sci. 1978, 34, 429-431.
(
19) Price, D. J.; Powell, A. K.; Wood, P. T. Polyhedron 1999, 18, 2499-
2503.
1500 Inorganic Chemistry, Vol. 42, No. 5, 2003

Crystal and Molecular Structures of Alkali Oxalates
Figure 2. Three-dimensional semitransparent representation of the microstrain distribution of K2C2O4 (left), and â-Rb2C2O4 (right) at ambient conditions.
-
6
The scale is in ∆d/d × 10 strain.
Table 1. Crystallographic Data for A2C2O4 [A ) K, Rb, Cs]
orthorhombic unit cells for I and II-â and to primitive monoclinic
unit cells for II-R and III with lattice parameters given in Table 1.
The number of formula units per unit cell could be determined to
be Z ) 2 for I and II-â and Z ) 4 for II-R and III, respectively,
from packing considerations and density measurements. The
extinctions found in the powder patterns indicated either Pbam or
K
2
C
2
O
4
â-Rb
Rb
2
C
2
O
4
R-Rb
Rb
2
C
2
O
4
Cs
2
C
2
O
4
formula
temp (K)
fw (g/mol)
space group
Z
K
295
166.216
Pbam
2
2
C
2
O
4
2
C
2
O
4
2
C
2
O
4
Cs
295
353.830
P2 /c
1
4
2
C
2
O
4
295
260
258.955
258.955
Pbam
2
P2
1
/c
4
Pba2 for I and II-â and P2
most probable space groups. Pbam and P2
confirmed by Rietveld refinements23 to be the appropiate groups.
1
/c for II-R and III, respectively, as the
/c could later be
a (Å)
10.91176(7) 11.28797(7) 6.3276(1)
6.62146(5)
b (Å)
c (Å)
6.11592(4)
3.44003(2)
90
90
90
229.572(3)
2.404
2.409(1)
0.70003(5)
6.29475(4)
3.62210(2)
90
90
90
10.4548(2) 11.00379(9)
1
8.2174(2)
90
8.61253(7)
90
R (deg)
â (deg)
γ (deg)
The peak profiles and precise lattice parameters were determined
98.016(1)
90
97.1388(4)
90
2
4
25
by LeBail-type fits using the programs GSAS and FULL-
PROF.
3
26,27
V (Å )
257.369(3)
3.341
538.30(2)
3.195
3.172(2)
1.54060
0.2
622.654(9)
3.774
3.792(4)
0.70003(5)
0.3
The background was modeled manually using GUFI.
3
F
calc (g/cm )
The peak profile was described by a pseudo-Voigt function in
combination with a special function that accounts for the asymmetry
due to axial divergence.2 The powder pattern of I and II-â exhibit
severe anisotropic peak broadening caused by lattice strain, with
the sharpest peaks along the [001] direction having a 2Θ full width
at half-maximum (fwhm) of 0.014° for I and 0.021° for II-â,
3
Fobsd (g/cm )
wavelength (Å)
0.82978(4)
8,29
capillary diam (mm) 0.7
0.5
5.1
6.1
8.7
R-p (%)a
4.9
5.9
6.4
4.4
7.1
a
R-wp (%)
5.8
8.3
2
a
R-F (%)
8.9
8.2
a
R-p, R-wp, and R-F2 as defined in GSAS:25 R-p ) ∑i|yi(obsd) -
30
respectively. The phenomenological strain model of Stephens as
2
2
1/2
yi(calcd)|/[∑iyi(obsd)]. R-wp ) {∑iwi(yi(obsd) - yi(calcd)) /[∑iwi(yi(obsd)) ]}
.
implemented in GSAS was used to model the anisotropy of the
fwhm. Four parameters were refined for the orthorhombic phases.
A three-dimensional representation of the isosurface of the micro-
strain is shown in Figure 2.
2
2
2
2
R-F ) ∑i|Fi(obsd) - Fi(calcd) |/[∑i|Fi(obsd) |].
height discriminator in the counting chain. The incoming beam was
monitored by an ion chamber for normalization purposes in order
to take the decay of the primary beam into account. In this parallel
beam configuration, the resolution is determined by the analyzer
crystal instead of slits.20 Data were taken in 2Θ steps of 0.005°
from 5° to 46.34° for 7.2 h (I), from 5° to 59.06° for 9.3 h (II-â),
and from 3° to 45.14° for 9.4 h (III) (see Table 1). Although
Θ-scans did not show serious crystallite size effects, the samples
were spun during measurement for better particle statistics. The
powder patterns of (I) and (III) exhibit several peaks of very small
amounts (<0.5%) of the corresponding monohydrate phases.
X-ray powder diffraction data of the R-phase of rubidium oxalate
The crystal structures of I and III were solved in the following
3
1
way with use of the DASH structure solution package for the
NSLS synchrotron and laboratory data sets: The measured powder
patterns were subjected to a Pawley refinement32 in space groups
Pbam for I and P2 /c for III in order to extract correlated integrated
1
intensities from the pattern. Good fits to the data were obtained.
(21) Dinnebier, R. E.; Finger, L. Z. Kristallogr. 1998, Suppl. Issue 15, 148.
(
(
(
22) Visser, J. W. J. Appl. Crystallogr. 1969, 2, 89-95.
23) Rietveld, H. M. J. Appl. Crystallogr. 1969, 2, 65-71.
24) Le Bail, A.; Duroy, H.; Fourquet, J. L. Mater. Res. Bull. 1988, 23,
447-452.
(
II-R) were collected at room temperature with a Stoe Stadi-P
transmission diffractometer (primary beam Johann-type Ge mono-
chromator for Cu KR radiation, linear PSD) in 2Θ steps of 0.01°
(
25) Larson, A. C.; von Dreele, R. B. GSAS, version 2002; Los Alamos
National Laboratory Report LAUR 86-748; Los Alamos National
Laboratory: Los Alamos, NM, 1994.
1
from 10° to 90° at a temperature of T ) 260 K for 67 h with the
sample sealed in a glass capillary of 0.2 mm diameter (Hilgenberg,
glass No. 50) (Figure 1). Weak reflections corresponding to small
traces of the â-phase as an additional phase were observed in the
scan. Further experimental details are given in Table 1.
(26) Rodriguez-Carvajal, J. Abstracts of the Satellite Meeting on Powder
Diffraction of the XV Congress of the IUCr; p 127; Toulouse, France,
1
990.
(
27) Rodriguez-Carvajal, J. Fullproof.2k, version 1.9c; Laboratoire Leon
Brillouin: Gif-sur-Yvette, France, 2001.
(28) Thompson, P.; Cox, D. E.; Hastings, J. B. J. Appl. Crystallogr. 1987,
2
0, 79-83.
29) Finger, L. W.; Cox, D. E.; Jephcoat, A. P. J. Appl. Crystallogr. 1994,
7, 892-900.
Data reduction on all four data sets was performed using the
GUFI program.21 Indexing with ITO led to similar primitive
(
(
22
2
30) Stephens, P. W. J. Appl. Crystallogr. 1999, 32, 281-289.
(
20) Cox, D. E. Handbook of Synchrotron Radiation, Vol. 3, Chapter 5
Powder Diffraction; Brown, G., Moncton, D. E., Eds.; Elsevier:
Amsterdam, 1991.
(31) David, W. I. F.; Shankland, K.; Shankland, N. Chem. Commun. 1998,
931-932.
(32) Pawley, G. S. J. Appl. Crystallogr. 1981, 14, 357-361.
Inorganic Chemistry, Vol. 42, No. 5, 2003 1501

Dinnebier et al.
Table 2. Positional Parameters and Temperature Factors for A2C2O4
[A ) K, Rb, Cs] at Ambient Conditions
atom
x
y
z
Ui/Ue (Å2)
K2C2O4
0.59497(9)
1.0699(4)
1.2729(3)
0.9639(2)
K(1)
C(1)
O(1)
O(2)
0.34860(6)
0.4383(2)
0.4505(1)
0.3408(2)
1/2
0
0.0214(2)
0.0195(7)
0.0268(6)
0.0190(5)
0
0
â-Rb2C2O4
0.59308(8)
1.0632(6)
1.2584(4)
0.9706(3)
Rb(1)
C(1)
O(1)
O(2)
0.34720(5)
0.4402(3)
0.4517(2)
0.3486(2)
1/2
0
0.0283(2)
a
0.00(1)
0
0.0006(8)
a
0
0.00(1)
Figure 3. Sketch of the oxalate anion as found in Cs2C2O4.
R-Rb2C2O4
0.2938(1)
0.5851(1)
0.0459(5)
0.1035(3)
0.1255(6)
-0.0583(5)
0.1047(5)
0.1570(5)
Rb(1)
Rb(2)
C(1)
C(2)
O(1)
O(2)
O(3)
O(4)
0.2827(2)
0.2306(2)
0.6904(6)
0.8215(6)
0.5518(9)
0.7124(2)
0.7949(7)
0.9909(8)
0.9790(2)
0.3350(2)
0.7802(7)
0.6544(7)
0.8050(8)
0.8369(8)
0.5090(8)
0.7155(8)
0.0533(5)
0.0484(5)
0.056(1)
0.056(1)
0.056(1)
0.056(1)
0.056(1)
0.056(1)
An internal coordinate description of the oxalate moiety (Figure
3
) was constructed using bond lengths, angles, and torsion angles
33-36
from corresponding hydrated phases K
2H O. The torsion angles between the two carboxyl groups could
2
C
2
O
4
‚H
2
O,
2 2 4
and Cs C O ‚
37
2
not be assigned precise values in advance, and thus they were treated
as variables for refinement in the simulated annealing procedure.
The positions of the crystallographically independent alkali cations
Cs2C2O4
0.2948(1)
0.5886(1)
0.0560(6)
0.1115(4)
0.1256(9)
-0.0511(6)
0.1108(6)
0.1541(7)
Cs(1)
Cs(2)
C(1)
C(2)
O(1)
O(2)
O(3)
O(4)
0.2840(2)
0.2294(2)
0.691(1)
0.833(1)
0.547(1)
0.724(2)
0.778(1)
1.001(1)
0.9827(2)
0.3316(2)
0.7777(7)
0.6652(9)
0.8075(8)
0.8309(8)
0.5180(9)
0.733(1)
0.0307(5)
0.0322(5)
0.034(2)
0.034(2)
0.034(2)
0.034(2)
0.034(2)
0.034(2)
(one in the case of I and II-â; two in the case of II-R and III) as
well as the position, orientation, and conformation of the oxalate
anions in the unit cell were postulated, and the level of agreement
between the trial structure and the experimental diffraction data
was quantified by
2
2
- 1
2
ø )
[(I - c|F | )(V ) (I - c|F | )]
a
∑
∑k
h
h
hk
k
k
Absorption correction was only applied to the data set measured at λ
h
) 1.54 Å, but not for data sets measured at higher energies, explaining the
low-temperature factor for oxygen in the case of the refinement of
â-Rb2C2O4.
h k
Here I and I are Lorentz-polarization corrected, extracted
integrated intensities from the Pawley refinement of the diffraction
data, Vhk is the covariance matrix from the Pawley refinement, c is
Table 3. Selected Bond Lengths (Å) and Angles (deg) for A2C2O4 [A
)
K, Rb, Cs] at Ambient Conditionsa
a scale factor, and |F
h
| and |F | are the structure factor magnitudes
k
calculated from the trial structure. The trial structure was subjected
to a global optimization31 where the torsion angle between the
carboxyl groups and the bond length between the carbon atoms
were the only internal degrees of freedom. The external degrees of
freedom consisted of the fractional coordinates describing the
positions of the alkali cations and the oxalate anions, and four
quaternions38 describing the orientation of the molecule. The
structure giving the best fit to the data was validated by Rietveld
refinement of the fractional coordinates obtained at the end of the
simulated annealing run.
K2C2O4
â-Rb2C2O4
R-Rb2C2O4
Cs2C2O4
distances (Å)
C-C
C-O
1.595(3)
1.246(3)
1.567(5)
1.187(4)
1.236(5)
2.960(2)-
3.051(2)
1.536(7)
1.19(1)-
1.25(1)
1.56(1)
1.27(1)-
1
.249(3)
2.806(2)-
.901(1)
1.28(1)
A(1)-O
A(2)-O
2.888(6)-
3.386(5)
2.816(7)-
3.069(9)-
3.557(9)
3.015(8)-
3.737(9)
2
3.580(7)
angles (deg)
O-C-O
127.5(2)
125.4(3)
0.0(4)
113.2(5)
26.6(5)
125.7(8)
125.8(8)
1
torsion angles (deg)
O-C-C-O 0.0(3)
Rietveld refinements were performed on all powder patterns of
I, II-â, II-R, and III using the program package GSAS (Figure 1).
The background was modeled manually using GUFI. No additional
phases were included in the refinement of I, II-â, and III, but in
the case of II-â, several excluded regions containing reflections of
rubidium oxalate hydrate were defined. In the refinement of II-R,
the polymorph II-â was included as an additional phase (about 18
wt %). The peak profile was described by a pseudo-Voigt function,
in combination with a special function that accounted for the
94(3)
99(1)
a
The given esd’s are Rietveld statistical estimates and should be
multiplied by a factor of up to 6 according to ref 52.
stabilize the refinements. Agreement factors (R values) are listed
in Table 1, the coordinates are given in Table 2, and a selection of
intra- and intermolecular distances and angles is given in Table 3.
1
Guinier-Simon measurements (Enraf-Nonius FR 553, Cu KR ,
Johansson monochromator) were conducted from room temperature
up to 373 K. Densities of the alkali oxalates were determined by
use of a He pycnometer (Micromeritics AccuPyc 1330 GB). IR
data were recorded using the KBr disk method (1 mg of oxalates
at 500 mg of KBr, prepared in a glovebox in an argon atmosphere)
using a Bruker IFS 113v (Karlsruhe) FTIR spectrometer. Raman
spectra were recorded of samples in sealed quartz capillaries
28,29
asymmetry due to axial divergence.
Due to the excellent
reflection-to-parameter ratio, no soft constraints were necessary to
(
33) Pedersen, B. F. Acta Chem. Scand. 1964, 18, 1635-1641.
(34) Hodgson, D. J.; Ibers, J. A. Acta Crystallogr., Sect. B: Struct. Sci.
1
969, 25, 469-477.
(
(
(
(
35) Sequeira, A.; Srikanta S.; Chidambaram, R. Acta Crystallogr., Sect.
B: Struct. Sci. 1970, 26, 77-80.
(diameter 1 mm) using a Jobin Yvon (Horiba) Raman spectrometer.
36) Jovanovski, G.; Thomas, J. O.; Olovsson, I. Acta Crystallogr., Sect.
B: Struct. Sci. 1987, 43, 85-92.
Results and Discussion
37) Kholodkovskaya, L. N.; Trunov, V. K.; Tskhelashvili, N. B. J. Struct.
Chem. 1990, 31, 667-670.
Freshly prepared anhydrous rubidium oxalate consists of
a mixture of both phases of rubidium oxalate with the
38) Leach, A. R. Molecular Modelling Principles and Applications;
Addison-Wesley Longman Ltd.: Reading, MA, 1996; pp 2-4.
1502 Inorganic Chemistry, Vol. 42, No. 5, 2003

Crystal and Molecular Structures of Alkali Oxalates
spacer. Each oxygen atom of the oxalate anions is coordi-
nated to four alkali cations. Pairs of potassium cations
(distance 3.502(1) Å; rubidium cations 3.643(1) Å; Table
3), which are interconnected by parallel (C-C bond) oxalates
in a zigzag manner, form infinite parallel double chains along
the c-axis. In the a-direction, the double chains are alternately
inclined by approximately (20° against the a-axis, leading
to a herringbone arrangement (Figure 6). Each alkali cation
is surrounded by eight oxygen atoms in the form of a
distorted cube (Figure 7). Two cubes form a pair via a
common face, and these pairs are stacked to infinite chains
along the c-axis via common faces. Therefore, each cube
shares three faces with neighboring cubes. Four of the side
edges of a double cube are shared with four neighboring
double cubes. Each oxalate chain is connected to four double
chains of alkali cations and vice versa.
In contrast to the crystal structures of I and II-â, the
isotypic crystal structures of II-R and III are not layer but
framework structures (Figure 6). Each of the two crystallo-
graphically different alkali cations is surrounded by a
different number of oxygen atoms forming irregular poly-
hedra (Figure 7). The alkali atoms Cs(1) and Rb(1),
respectively, are coordinated to nine oxygen atoms (distances
Figure 4. Guinier-Simon image plate recordings of Rb2C2O4 as a function
of temperature in the range 300.5-370.5 K. Whereas at room temperature
the R-and â-phases coexist, the R-phase disappears completely at 333(2)
K.
3
.069(9)-3.557(9) Å for cesium; 2.888(6)-3.386(5) Å for
rubidium; Table 3) which belong to six different oxalate
anions in the form of a distorted tetragonal antiprism capped
at one of its trigonal planes. Consequently, two of the oxalate
anions are side-on coordinated to the alkali cation, while one
is end-on coordinated. Each alkali cation Cs(1)/Rb(1) is
surrounded by eight alkali cations (six Cs(2)/Rb(2) and two
Cs(1)/Rb(1)) in the second neighbor shell. Two alkali cations
are located on top of the tetragonal planes, while each of
the remaining six atoms is located on top of a trigonal face.
The trigonal faces, built by the two side-on coordinated
oxalate anions, are not capped. The alkali cations Cs(2)/Rb-
(2) are coordinated to 10 oxygen atoms (distances 3.015-
(8)-3.737(9) Å for cesium; distances 2.816(7)-3.580(7) Å
for rubidium; Table 3) belonging to only five different
oxalate anions in the form of an irregular polyhedron. This
can best be described as a distorted trigonal prism with
twisted roof and two additional oxygen atoms capping each
of the tetragonal side faces of the prism. The roof is twisted
by approximately 45°. Two end-on coordinated oxalate
anions form the tetragonal base plane of the prism. Two
oxygen atoms of two different oxalate anions form the roof.
One of these oxalates is coordinated with only one oxygen
atom therefore having the shortest alkali oxygen distance of
3.015(8) Å for cesium, and 2.816(7) Å for rubidium,
respectively, while the other anion is coordinated with three
oxygen atoms building one of the two caps. The other cap
is formed by a side-on coordinated oxalate anion. Each alkali
cation Cs(2)/Rb(2) is surrounded by eight alkali cations (six
Cs(1)/Rb(1) and two Cs(2)/Rb(2)) in the second neighbor
shell.
Figure 5. Packing types of K2C2O4 (AlB2-type) (a, c) and Cs2C2O4 (Hg99-
As1-type) (b, d). The relation between the two structure types is visible in
projections c and d. Alkali metal positions are in light gray, and the positions
of the centers of mass of the oxalate anions are in white.
R-phase (II-R) as the predominating phase. Heating the
R-phase above room temperature or storing at room tem-
perature for some time leads to a complete transition into
â-rubidium oxalate (II-â) (Figure 4).
The crystal structures of I and II-â are isotypic. They can
2
be viewed as distorted AlB -type layer structures (3%
distortion from hexagonal metric). The center of gravity of
the oxalate anion is in the origin of a hexagonal unit cell,
1
2 1
and two alkali cations are located close to /
3
/
3
/
2
and
2
1 1
/
3
/
3
/
2
(Figure 5), thus forming alternating layers of oxalate
The positions of the centers of gravity of the oxalate anions
form a hcp-type structure (maximum deviation of 3% and
0.8° from hexagonal metric, respectively) with the (idealized)
anions and alkali cations. The planar oxalate anions are
located on a mirror plane, forming infinite parallel chains
along the c-direction with the length of the c-axis as the
1
2 1
positions of the oxalate anions at 000, /
3 3 2
/ / and the alkali
Inorganic Chemistry, Vol. 42, No. 5, 2003 1503

Dinnebier et al.
Figure 6. Crystal structures of A2C2O4 [A ) Li (top left),16 Na (top right),17 K, â-Rb (bottom left), R-Rb, Cs (bottom right)] in different projections.
Oxygen positions are in white, carbon positions are in dark gray, and alkali metal positions and their corresponding polyhedra are in light gray.
cations at 001/
1
3 3 3 3 4
, / 0, and /
2/ 1/ 1/
2
. This is the type of packing
or, alternatively, corresponds
2
3
9,40
found in Hg99As (P 6h m2)
to a modification of boron nitride with a vacancy at
(Figure 5).
The oxalate anion itself is twisted by 99(1)° for III (94-
3)° for II-R) (Figure 3). This can be attributed to packing
4
1
2
1 1
/
3
/
3
/
4
(
effects in the cesium (rubidium) compound. The influence
of hydrogen bonding as found for other, slightly twisted
oxalates can be excluded. The lengthening of the C-C bond
of the oxalate anion (>1.54 pm) is consistent for all oxalates
4
2,43
and can be explained by MO theory.
The crystallographic relationship between these two dif-
ferent crystal structures (Pbam and P2 /c) can be understood
from the following group-subgroup relationship: Pbam f
1
1
Pbam (doubled c-axis, which is not observed) f P2 /c. The
transformation matrix is given by
0
0 2
T
(a b c )
) 1 0 0 *(a b c )
P2 /c
Pbam
1
(
)
0
1 0
Figure 5 shows the relations of the packings of the two
different crystal structures in two projections. It is clearly
visible that (apart from an internal twist within the oxalate
anion) displacive movements of both the alkali cations and
the center of gravity locations of the oxalate anions occur.
Figure 7. Coordination polyhedra of crystal structures of A2C2O4 [A )
(
39) Puselj, M.; Ban, Z. J. Less-Common Met. 1974, 37, 213-216.
16
17
Li (top left), Na (top right), K, â-Rb (middle left), R-Rb, Cs (A(2) middle
right, and A(1) bottom left)]. Oxygen positions are in white, carbon positions
are in dark gray, and alkali metal positions and their corresponding polyhedra
are in light gray.
(40) Donohue, J. J. Less-Common Met. 1978, 57, 229.
(41) Pease, R. S. Acta Crystallogr. 1952, 5, 356-361.
(42) Brown, R. D.; Harcourt, R. D. Aust. J. Chem. 1963, 16, 737-758.
(43) Zhou, G.; Li, W.-K. J. Chem. Educ. 1989, 66, 572.
1504 Inorganic Chemistry, Vol. 42, No. 5, 2003

Crystal and Molecular Structures of Alkali Oxalates
No major rearrangements within the crystal structures are
necessary.
Table 4. Band Assignment for A2C2O4 (A ) K, Cs)
Cs
K
assignment
It may be speculated that the driving force for the structural
phase transition between II-â and II-R is related to the
increased polarizability and/or size of the rubidium cation
compared to the potassium cation. An unfavorable cation to
anion size ratio for a given packing creates stress in certain
directions in a crystal structure. This is directly related, via
the elastic constants, to the anisotropic microstrain (Figure
(irrep in D2h51)
IR
Raman
743
IR
Raman
1
2δs(CO2)
1
1
663
621
1567
1549
νas(CO2) (b2u)
1
1619
649
1557
1538
νas(CO2) (b3g)
impurity
1
561
325
2). The latter can be derived from high-resolution powder
1
1489
507
1437
1489
νs(CO2) (a1g)
diffraction data. Three-dimensional anisotropic strain distri-
butions of I and II-â on an equal scale immediately reveal
an increase in strain within the alkali and oxalate layers,
respectively, with an increase in the size of the cation. In
both cases, the strain perpendicular to the layers is relatively
low, leaving the packing in the perpendicular direction
essentially unchanged (Figure 5). It should be noted that,
for cesium oxalate, no significant anisotropy of the micro-
strain was found.
1
1301
1298
1
324 (vw)
872
1299
νas(CO2) (b1u)
δ (CO ) (a )
1309
898
s
2
1g
8
817
55
860
822
496
δω(CO2) (b3u)
δas(CO2) (b1u)
774
66
747
745
741
7
519
431
δω(CO2) (b2g) (?)
ν(CC) (a ) (?)
The neutral, solvent-free alkali oxalates clearly show a
strong dependence of the coordination numbers on the size
of the alkali cations, starting with four (tetrahedron, lithium)
and increasing to six (octahedron, sodium), eight (cubic,
potassium and â-rubidium), and nine and ten (cesium and
462
1
g
3
289
00
407
δF(CO2) (b2u/b3g)
angle. The corresponding normal coordinates are represented
by a substantial mix of the symmetry coordinates already
1
4
51
R-rubidium) (Figure 7). The structure of lithium oxalate
consists of planes of corner-shared tetrahedra of LiO
4
present in the highest possible symmetry case of D2h. Due
to this coupling the lowest and second lowest bands of the
totally symmetric modes were reassigned, viz., νCC ) 490
connected by planes of oxalate anions (Figure 6). The
structure of sodium oxalate15 is, except for different coor-
dination numbers, similar to those of potassium and â-ru-
bidium oxalate. All consist of a herringbone arrangement of
infinite double chains of the corresponding alkali cations
interconnected by infinite chains of oxalate anions with a
smaller inclination for sodium oxalate (Figure 6). Edge-
-
1
-1
cm and δCO2 ) 894 cm . This reassignment brings the
2
-
band assignment of C
isostructural N in agreement. Therefore, the band assign-
ments of A (A ) K, Cs), shown in Table 4, are based
2
O
4
and the isoelectronic and
2
O
4
C O
2 4
2
on these new data.
shared slightly distorted octahedra of NaO
6
form the infinite
2 2 4
In the crystal structure of K C O (oP16, Pbam, dihedral
double chains of sodium which are connected to neighboring
double chains via a common corner as in rutile type
structures. The structures of the water-containing alkali
oxalates are completely different from their corresponding
anhydrous compounds.9
The band assignments for the vibrational spectra, and the
conclusions one can draw from these about the geometry of
oxalate anions in solid-state and aqueous solution are still
angle ) 0°), the oxalate anion is placed on the special site
2c of site symmetry C2h. Therefore, 12 and 10 internal modes
of the oxalate anion are expected in the Raman and IR
spectra, respectively (see correlation table, Table 5). In
,33-37,44
contrast, the oxalate anion of Cs
angle ) 99°) is placed on general sites. All modes of
maximum point group symmetry D mix to irreducible
representation A for C point group symmetry. Thus, 24
2 2 4 1
C O (mP32, P2 /c, dihedral
2
1
4
5-50
subject to controversial discussions.
On the basis of the
internal modes are expected in the Raman as well as the IR
spectra of this compound (see Table 5).
12
spectra of isotopically pure samples of K
2
15
C
O
2 4
‚H
as well as
corresponding force field studies, it has been recently
2
O and
13
14
K
2
C
2
O
4
‚H
2
O and the data of N
2
O
4
and N
O
2 4
In particular, the rule of mutual exclusion holds for K C O
4
2
2
but not for Cs C O . As a consequence, the Raman and IR
2
2
4
5
1,46
shown
that the wavenumbers of the oxalate vibrations,
2 2 4
spectra of K C O are complementary, e.g., the Raman
especially the ν(CC) mode, strongly depend on the dihedral
spectra exhibit exclusively bands due to gerade modes, while
the IR spectra exhibit the ungerade modes (Table 4 and
Figure 8). The observed wavenumbers fit quite well to
(
(
(
44) Pedersen, B. F. Acta Chem. Scand. 1965, 19, 1815-1818.
45) Ito, K.; Bernstein, H. J. Can. J. Chem. 1956, 34, 170-178.
46) Begun, G. M.; Fletcher, W. H. Spectrochim. Acta 1963, 19, 1343-
5
1
literature values for the planar oxalate anion of D2h
1349.
-1
symmetry. Except for one band at 1561 cm , which is due
(
(
(
(
47) Pedersen, B. F. Acta Chem. Scand. 1967, 21, 801-811.
48) Shippey, T. A. J. Mol. Struct. 1980, 65, 61-70.
to a small quantity of an impurity, all bands were assigned
49) Shippey, T. A. J. Mol. Struct. 1980, 67, 223-233.
50) Hind, A. R.; Bhargava, S. K.; Van Bronswijk, W.; Grocott, S. C.;
Eyer, S. L. Appl. Spectrosc. 1998, 52, 683-691.
to the given fundamentals. Weak bands in the 4000-2000
-
1
cm region were assigned fully to combination bands and
(51) Clark, R. J. H.; Firth, S. Spectrochim. Acta, Part A 2002, 58, 1731-
overtones, respectively.
1746.
In contrast, the spectra of Cs
2
C
O
2 4
exhibit the ν
s 2
(CO ),
(
52) Hill, R. J.; Cranswick, L. M. D. J. Appl. Crystallogr. 1994, 27, 802-
844.
δ
s
(CO ), and δas(CO ) modes in either case, due to the
2
2
Inorganic Chemistry, Vol. 42, No. 5, 2003 1505

Dinnebier et al.
Table 5. Correlation Table for the Vibrational Modes of K2C2O4 and Cs2C2O4
Figure 8. Vibrational spectra of A2C2O4 (A ) K, Cs; IR, transmission, Raman (R), rel. intensities; all spectra are shifted for clarity, and marked bands
correspond to quartz, used as tube material).
breakdown of the law of mutual exclusion in this particular
case. Nevertheless, bands assigned to gerade modes in
the ν(CC) and δ
wavenumbers in comparison to K
F
(CO
2
) modes are shifted toward lower
(Table 4 and Figure
2
2 4
C O
-1
K
2
C
O
2 4
are more intense in the Raman spectra, while those
8). Additional strong bands at 855 and 817 cm are observed
in the IR spectra, which are also observed as very weak bands
in the corresponding Raman spectra. Taking into account
(i) the high intensities of those bands in the IR spectra, (ii)
the reassignments stated above, and (iii) the strong increase
corresponding to ungerade modes in K exhibit higher
2 2 4
C O
intensities in the IR spectra. Band assignments agreed well
with those found for the twisted oxalate anion in ammonium
5
1
oxalate hydrate. As a consequence of the twist geometry,
1506 Inorganic Chemistry, Vol. 42, No. 5, 2003

Crystal and Molecular Structures of Alkali Oxalates
of the F
and 641 cm for τ ) 0° and 28°, respectively), those bands
very likely arise from the wagging mode F (CO ), which is
observed in the IR spectra of K at 496 cm .
As a result, the vibrational spectra of K and Cs
are in good agreement with the structures of the oxalate
anions derived from the diffraction studies. Due to the phase
behavior, the vibrational spectra of as-prepared samples of
ω
(CO
2
1
) mode on increase of the dihedral angle (526
National Laboratory, which is supported by the US Depart-
ment of Energy, Division of Materials Sciences and Division
of Chemical Sciences. The SUNY X3 beamline at NSLS is
supported by the Division of Basic Energy Sciences of the
US Department of Energy under Grant No. DE-FG02-
-
51
ω
2
-1
2 2 4
C O
C O
2 2 4
2 2 4
C O
8
6ER45231. Special thanks go to Sanela Kevric (MPI-FKF
at Stuttgart) for her support in sample preparation and to
Peter Stephens (SUNY at Stony Brook) for his help during
data collection. Thanks also go to Marie-Luise Schreiber,
Wolfgang K o¨ nig, and Hans Vogt for measuring the IR and
Raman data, and to Klaus Hertel (all MPI-FKF at Stuttgart)
for the Guinier-Simon measurement. Financial support by
the Deutsche Forschungsgemeinschaft (DFG), the Bundesmin-
isterium f u¨ r Bildung und Forschung (BMBF), and the Fonds
der Chemischen Industrie (FCI) is gratefully acknowledged.
2 2 4
Rb C O show the prominent bands of the II-â as well as
the II-R modification. Due to this, vibrational spectra of
spectroscopically pure samples could not be achieved.
The crystal structures of the higher homologues of the
alkali oxalates could be determined from high-resolution
X-ray powder diffraction data. More generally speaking, it
is now possible, on a fairly routine basis, to solve small
molecule structures by high-resolution powder diffraction,
within the accuracy of single-crystal diffraction in the early
1
960s. This allows us to discuss individual bond lengths and
Supporting Information Available: Crystallographic data
(CIF). This material is available free of charge via the Internet at
http://pubs.acs.org. CCDC 192180-192183 also contain the supple-
mentary crystallographic data for this paper. These data can be
obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving-
.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ,
U.K.; fax, +44 1223 336033; e-mail, deposit@ccdc.cam.ac.uk).
angles. As a result, it has become obvious that the conforma-
tion of the oxalate anion, when acting as a weak interacting
ligand, is mainly determined by packing effects: bonded to
nonpolarizing cations K , Rb , and Cs , the planar as well
as the much rarer staggered conformations have been
observed.
+
+
+
Acknowledgment. This work was carried out in part at
the National Synchrotron Light Source at Brookhaven
IC0205536
Inorganic Chemistry, Vol. 42, No. 5, 2003 1507