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Rietveld Refinement of the Crystal Structure of Potassium Iron Oxalate

Trihydrate from Laboratory X-Ray Powder Diffraction Data

Article  in  Materials Science Forum · January 2001

DOI: 10.4028/www.scientific.net/MSF.378-381.655

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Materials Science Forum Vols. 378-381 (2001) pp. 655-658
© 2001 Trans Tech Publications, Switzerland

Rietveld Refinement of the Crystal Structure of Potassium Iron Oxalate

Trihydrate from Laboratory X-ray Powder Diffraction Data

G. Delgado and A.J. Mora

Laboratorio de Cristalografía, Departamento de Química, Facultad de Ciencias,
Universidad de Los Andes, Mérida 5101, Venezuela.

Keywords: Powder Diffraction, Rietveld refinement, Metal complexes.

Abstract Potassium iron oxalate trihydrate [K3Fe(C2O4)3·3H2O] has been synthesized and its
crystal structure was refined by the Rietveld method using X-ray powder diffraction data collected
with a conventional diffractometer. The crystal structure consists of discrete Fe(C2O4)33- anions, K+
cations and water molecules, held together by electrostatic interactions.

Introduction

Metallic oxalates are materials which have technological applications as precursors to

nanocrystalline metallic oxides obtained by pyrolisis at low temperature [1-2]. Rare earth metallic
oxalates have also shown interesting properties and thermal behaviour and have been the subject of
recent investigations [3-5].
In particular, the structures of trioxalate metallate complexes of general formula MI3 MIII
(C2O4)3·3H2O, with MI = K, Rb, NH4 and K0.9Na0.1 and MIII = Al, Cr, Ga, Fe, and Mn [6-12], have
been investigated by X-ray diffraction techniques and they either crystallise in a monoclinic cell,
space group P21/c, or in a triclinic cell approximately half the volume of the monoclinic one, space
group P 1 , (see Table 1). Both structures have in common the distorted octahedral coordination of
the MIII atom, in which six O atoms from the three oxalate groups are linked to the MIII atom at
distances MIII-O between 1.89-2.00 Å, depending on the trivalent metal. On the other hand, the
structures differ in the degree of disorder of the water molecules.
Of these compounds, the one with formula K3Fe(C2O4)3·3H2O can be found as a natural mineral
named minguzitte, and can be synthesised in the laboratory by standard methods. This material was
prepared in our laboratory in order to investigate an interesting solid state reaction observed when
K3Fe(C2O4)3·3H2O its heated, changing colour from green to white at about 400K. Only twinned
crystals were obtained from the synthesis. Considering that this problem can be overcome when the
sample is pulverised, this material was therefore investigated using X-ray powder diffraction.

Experimental

A solution of 25 mL H2C2O4 1.0M was added slowly at room temperature to a solution of 5.0 g
Fe(NH4)2(SO)4·6H2O in 15 mL water. Yellow crystals of FeC2O4·2H2O precipitate were washed
and added to a solution of 10 mL K2C2O4 in 20 mL water at 333K. Then, to this solution 20 mL
H2O2 (3%) were added slowly with continued agitation at the same temperature. Green crystals of
K3Fe(C2O4)3·3H2O precipitated and were separated by filtration and air-dried at room temperature.
The crystals were investigated under the polarised light microscope, which revealed that they were
twinned.
A small quantity of the green precipitate, K3Fe(C2O4)3·3H2O, was ground with an agate pestle and
mortar, and then loaded into a flat sample holder, 25 mm in diameter and 2 mm deep. A powder
diffraction pattern was measured with Ni-filtered CuKα radiation at room temperature in θ/θ
reflection mode using a Bruker D5005 diffractometer working in step-scanning mode and equipped
656 Seventh European Powder Diffraction Conference EPDIC 7

with a scintillation counter. The sample was scanned from 7–80° 2θ, with a step size of 0.02° and
counting time of 40 s.
A thermogravimetry study was performed to examine the dehydration of the complex. This
analysis was carried out using a Perkin-Elmer TGA-7 instrument, with a sample mass of 4.739 g.

Table 1. Unit cell parameters for compounds with formula MI3 MIII (C2O4)3·3H2O
(MI= K, Rb, NH4, K0.9Na0.1 and MIII= Al, Cr, Ga, Fe, Mn)

MI3 MIII Ref S. G. a(Å) b(Å) c(Å) β(°) V(Å3) PDF[11] F30[17]

K3Al [6] P21/c 7.712(1) 19.518(3) 10.286(2) 108.21(3) 1495.8 - -

K3Cr [6] P21/c 7.714(1) 19.687(4) 10.361(2) 108.06(3) 1502.2 38-1446 28 (0.015,69)
(NH4)3Fe [7] P21/c 7.817(4) 20.173(9) 10.529(5) 107.20(5) 1586.1 38-1994 13 (0.023,102)
Rb3Cr [8] P21/c 7.916(2) 19.864(9) 10.594(4) 108.38(1) 1580.9 38-1448 19 (0.023,67)
K3Mn [9] P21/c 7.72(1) 19.88(3) 10.41(1) 108.22(3) 1517.4 - -
K3Fe0.9Na0.1 [10] P21/c 7.746(1) 19.914(3) 10.344(1) 107.70(1) 1520.1 - -
K3Fe (minguzitte) [11] - - - - - - 14-720 -
-
K3Fe This work P21/c 7.762(1) 19.937(3) 10.353(1) 107.75(1) 1526.0 - 62.1 (0.008,62)

MI3 MIII Ref S. G. a(Å) b(Å) c(Å) PDF[11] F30[17]

α (°) β(°) γ(°)

(NH4)3Ga [12] 7.901(1) 10.674(2) 10.710(2) 798.0 - -

P1
83.14(1) 70.18(1) 69.88(1)
(NH4)3Al [12] 7.888(4) 10.667(4) 10.643(2) 788.3 - 33 (0.018,51)
P1
83.33(2) 70.44(2) 69.10(4)

Results

The Bruker analytical software EVA [13] was used to establish the positions of the peaks from the
α1 component and to strip mathematically the α2 component from each reflection. The first 20 peak
positions were measured from the pattern and input to the auto-indexing program DICVOL91 [14].
A unique solution was readily obtained in a monoclinic system, a = 7.757(3) Å, b = 19.944(4) Å, c
= 10.353(2) Å, β= 107.76(2)° and M20 = 25.2, F20 = 58.9 (0.0064, 53).
An analysis of the systematically absent reflections showed the space group to be P21/c (C52h,
Nº14). From the review of the whole diffraction pattern using the program NBS*AIDS83 [15],
better cell parameters were obtained: a = 7.762(1) Å, b = 19.937(3) Å, c = 10.353(1) Å, β
= 107.75(1)°, with figures of merit M20 = 30.3 [16] and F30 = 62.1 (0.0078, 62) [17].
The Rietveld refinement [18] was carried out using the program WinRIETVELD [19]. The initial
model of K3Fe(C2O4)3·3H2O was obtained from the isostructural compound K3Cr(C2O4)3·3H2O [6].
The final refinement involved 95 parameters, including scale factor, zero shift, asymmetry, the U,
V, W, and mixing parameters of the pseudo-Voigt peakshape function, four coefficients for the
polynomial of the background, four unit cell parameters, 75 positional parameters and 5 isotropic
temperature factors. The final figures of merit were: RP = 11.61%, Rwp = 4.50%, Rp = 3.44%, Rexp =
3.06% and χ2 = 1.47. The final Rietveld plot is shown in Figure 1. Figure 2 shows a view of the
metal complex plotted using the program DIAMOND [20].
 Materials Science Forum Vols. 378-381 657

Figure 1. Observed (·), calculated (-), and difference plot of the final Rietveld refinement of
K3Fe(C2O4)3·3H2O.

Figure 2. Diagram showing a view of K3Fe(C2O4)3·3H2O.

The crystal structure consists of discrete Fe(C2O4)33- anions, K+ cations and water molecules. The
disorder among the water molecules observed in the related compounds was not refined in our
model. The structure of the tri(bidentate) Fe(C2O4)33- complex show a distorted octahedral
coordination with O(1)-Fe-O(2)= 82.74(1)º, O(3)-Fe-O(4)= 81.03(1)º, O(5)-Fe-O(6)= 82.74(1)º,
and an average Fe-O distance of 1.99(1) Å. This distortion is similar to those observed in the
isostructural compounds reported in Table 1. Six oxygen atoms surround each of the K+ atoms
from water molecules and oxalate anions, at distances varying from 2.6(6) to 2.9(9) Å.
The water molecules have 9 short contacts with other water molecules and the oxygens from the
Fe(C2O4)33- moiety, and also show electrostatic interactions with the K+ cations. Although there are
three crystallographically distinct water molecules in the structure, the analysis of contacts and
electrostatic interactions shows that water molecule O2w has weaker interactions than the other
two.
This result is in perfect agreement with the thermogravimetric analysis (TGA) carried out on this
compound. Figure 3 shows the TGA curve for K3Fe(C2O4)3·3H2O. At 113.0 °C the compound loses
3.67% weight corresponding to one water molecule presumably O2w. Then, at 136.5 °C the
compound loses 11.0% in weight corresponding to the other two water molecules.
 658 Seventh European Powder Diffraction Conference EPDIC 7

Figure 3. TGA curve for the decomposition of K3Fe(C2O4)3·3H2O in air

(5º C.min-1 from 70º to 250º C).

A temperature-dependent X-ray diffraction (TDXD) experiment will be performed in the near

future, which will allow us to investigate further the structural changes accompanying the gradual
dehydration of this compound.

References

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[2] Louër, D., Louër, M., Gotor, F.J. and Criado, J.M. J. Solid State Chem. 92, 565 (1991).
[3] Bataille, T. and Louër, D. Acta Cryst. C552, 1760 (1999).
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[5] Bataille, T., Louër, M., Auffredic, J.P. and Louër, D. J. Solid State Chem. 150, 81 (2000).
[6] Taylor, D. Aust. J. Chem. 31, 1455 (1978).
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(1987).
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[10] Wartchow, R. Z. Kristallogr New Cryst Struc. 212, 83 (1997).
[11] Powder Diffraction File (PDF-2, Set 1-49), International Center for Diffraction Data (1999).
[12] Bulc, N., Golic, L. and Siftar, J. Acta Cryst. C40, 1829 (1984).
[13] EVA, Bruker AXS, Sigma-C GmbH. Version 4.0 (1998).
[14] Boultif, A. and Louër, D. J. Appl. Cryst. 24, 987 (1991).
[15] Mighell, A.D, Hubbard, C.R., Stalick, J.K. NBS Tech. Note 1141 (1981).
[16] de Wolff, P.M. J. Appl. Cryst. 1, 108 (1968).
[17] Smith, G.S. and Snyder, R.L. J. Appl. Cryst. 12, 60 (1979).
[18] Rietveld, H.M. J. Appl. Cryst. 2, 65 (1969).
[19] WinRIETVELD, Bruker AXS, Sigma-C GmbH. Version 3.0 (1998).
[20] Branderburg, K. DIAMOND Visual Crystal Structure Information System, v.2.0h, Crystal
Impact GbR. (1998).

e-mail address: gerzon@ciens.ula.ve, asiloe@ciens.ula.ve.

Acknowledgements

This work was supported by CDCHT-ULA and CONICIT, Grant LAB-97000821, for the
establishment of the “Laboratorio Nacional de Difracción de Rayos-X”, and the computer facilities
of CeCalcULA.

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