Chemistry—A European Journal

Supporting information

Co-precipitation of Fe-Cu bimetal oxalates in an aqueous solution and their

thermally induced decomposition
Josef Kopp,[a] Petr Novák,*[a] Soňa Lisníková,[a] Vlastimil Vrba,[a] and Vít Procházka[a]

This supporting information contains the Fe-Cu oxalates XRD patterns and further details of their Rietveld analysis.

The transition metal oxalates crystalize in different structures, where one compound usually exhibits more polymorphs.
Moreover, the situation is complicated by incorporation of water to the crystalline structure, which may influence the
overall crystal lattice. Therefore, the analysis of X-ray diffraction experiments for oxalates samples is rather challenging.
Frequently, the X-ray diffraction patterns of oxalate compounds are analysed only qualitatively by identification of
diffraction pattern maxima and by comparing them with their positions in database cards. [1–3] The complete Rietveld
analyses of oxalates patterns are rather rare.[4,5] This situation is presumably caused by rather complicated structures of
oxalate compounds and, therefore, complicated diffraction patterns.

X-ray powder diffraction experiments in this paper were analysed by Rietveld refinement using MAUD software.[6,7] The
ferrous oxalate can crystalize in two different structures, namely α- (monoclinic C2/c) and β- (orthorhombic Cccm). The
sample Fe100 exhibited β-FeC2O4∙2H2O structure. The atomic positions and corresponding fit are shown in Table S1
and Figure S1, respectively. The copper oxalate (Cu100) was described by monoclinic P21/c structure. The individual
atomic positions are listed in Table S2 and the diffraction pattern with corresponding Rietveld fit is presented in
Figure S2. The shown uncertainties of the listed values are given as obtained from MAUD. The Rietveld analysis of
Fe-Cu samples was carried out by a sequential fitting procedure, where the fitted parameter values from the previous
fitting are used as input parameter values for the fitting of the following diffraction pattern. A model containing CuC2O4,
α-FeC2O4∙2H2O, β-FeC2O4 phases was used for the fitting. The fits and whole diffraction patterns of Fe-Cu oxalates are
given in Figure S3a‒l. The atomic positions used for the fitting model are listed in Table S3.

Some additional supporting figures (Figure S4 and Figure S5) are included as well.

REFERENCES

[1] A. Angermann, J. Töpfer, J. Mater. Sci. 2008, 5123–5130.

[2] I. Pasquet, H. Le Trong, V. Baco-carles, L. Presmanes, C. Bonningue, V. Baylac, J. Eur. Ceram. Soc. 2017, 37, 5315–
5320.

[3] Y. Li, N. Luo, G. Sun, B. Zhang, G. Ma, H. Jin, Y. Wang, J. Cao, Z. Zhang, J. Alloys Compd. 2018, 737, 255–262.

[4] A. N. Christensen, B. Lebech, N. H. Andersen, J. Grivel, Dalt. Trans. 2014, 16754–16768.

[5] L. Zwiener, F. Girgsdies, R. Schlögl, E. Frei, Chem. - A Eur. J. 2018, 56, 15080–15088.

[6] L. Lutterotti, Nucl. Instruments Methods Phys. Res. Sect. B Beam Interact. with Mater. Atoms 2010, 268, 334–340.

[7] “MAUD: Materials Analysis Using Diffraction,” can be found under http://maud.radiographema.eu/, 2021.
Table S1. Atomic positions of β-FeC2O4
Name Ion Occupancy x y z B factor
2+ 2+
Fe1_Fe Fe 1 0.25 0.25 0 11.0(1)
Fe2_Fe2+ Fe2+ 1 0 0 0.25 7.7(8)
C1_C C 1 0.25 0.75 0.9715222 -7.1(5)
C2_C C 1 0 0.5 0.25887603 2.0(1)
O1_O2- O2- 1 0.24997598 0.035597 0.08970008 0.5(6)
2- 2-
O2_O O 1 0.027801031 0.69319737 0.333855 11.0(1)
O3_O2- O2- 1 0.42600614 0.29267234 0 12.0(1)
O4_O2- O2- 1 0.17041609 0 0.25 0.4(3)
Lattice parameters: a = 12.546(1) Å, b = 5.5552(5) Å, c = 15.439(2) Å
Space group number: 66
Space group: Cccm

Figure S1. XRD patterns of Fe100 fitted with MAUD software.

Table S2. Atomic positions of CuC2O4
Name Ion Occupancy x y z B factor
Cu1_Cu Cu 1 0 0 0 0.0(2)
O1_O O 1 0.14919814 0.1615315 0.8008034 -2.6(3)
O2_O O 1 0.23911804 0.26933348 0.3303986 15.0(1)
C1_C C 1 0.062802315 0.077875406 0.56923646 -6.6(4)
Cu2_Cu Cu 1 0 0 0.5 4.6(6)
O3_O O 1 0.18292536 0.12668635 0.3780338 0.0(4)
O4_O O 1 0.32320175 0.22848219 0.85887235 18.0(1)
C2_C C 1 0.11129376 0.07327189 0.0408527 -4.0(3)
Lattice parameters: a = 6.018(1) Å, b = 5.5846(7) Å, c = 5.1133(6) Å, β = 115.51(1) °
Space group number: 14
Space group: P21/c

Figure S2. XRD patterns of Cu100 fitted with MAUD software.

Table S3. Atomic positions and structural information used for Rietveld analysis of Fe-Cu samples

CuC2O4
Space group number: 14
Space group: P21/c
Name Ion Occupancy x y z B factor
Cu1_Cu Cu 1 0 0 0 0
O1_O O 1 0.14633214 0.17214723 0.806287 2.6
O2_O O 1 0.25800827 0.18194117 0.403627 15
C1_C C 1 0.090401135 0.09055487 0.5525062 6.6
Cu2_Cu Cu 1 0 0 0.5 4.6
O3_O O 1 0.16230182 0.12751372 0.3591197 0
O4_O O 1 0.2872252 0.25127742 0.8786109 18
C2_C C 1 0.09155351 0.06374135 0.0416814 4

α-oxalate (α-FeC2O4∙2H2O)
Space group number: 15
Space group: C2/c
Name Ion Occupancy x y z B factor
2+ 2+
Fe1_Fe Fe 1 0 0.17341395 0.25 2.6
C1_C C 1 0.025773257 0.68810093 0.2576945 3.9
O1_O2- O2- 1 0.0962692 0.4590646 0.4168024 4.3
O2_O2- O2- 1 0.11201711 0.89285827 0.43495727 4.6
O3_O2- O2- 1 0.2077176 0.16876233 0.2698881 6.7
H1_H H 1 0.22872706 0.21871634 0.47611374 6.679984
H2_H H 1 0.28415227 0.21992634 0.124223985 8

β-oxalate (β-FeC2O4)
Lattice parameters: a = 12.527 Å, b = 5.5337 Å, c = 15.449 Å
Space group number: 66
Space group: Cccm
Name Ion Occupancy x y z B factor
2+ 2+
Fe1_Fe Fe 1 0.25 0.25 0 11
Fe2_Fe2+ Fe2+ 1 0 0 0.25 7
C1_C C 1 0.25 0.75 0.9975521 7
C2_C C 1 0 0.5 0.26200074 2
2- 2-
O1_O O 1 0.260813 0.08208233 0.10189298 0.5
O2_O2- O2- 1 0.046247978 0.70345604 0.34452778 11
O3_O2- O2- 1 0.36843535 0.297375 0 12
O4_O2- O2- 1 0.14179371 0 0.25 0.4
Figure S3a. XRD pattern of Fe90Cu10 fitted with MAUD program.

Figure S3b. XRD pattern of Fe80Cu20 fitted with MAUD program.

Figure S3c. XRD pattern of Fe75Cu25 fitted with MAUD program.

Figure S3d. XRD pattern of Fe70Cu30 fitted with MAUD program.

Figure S3e. XRD pattern of Fe65Cu35 fitted with MAUD program.

Figure S3f. XRD pattern of Fe60Cu40 fitted with MAUD program.

Figure S3g. XRD pattern of Fe55Cu45 fitted with MAUD program.

Figure S3h. XRD pattern of Fe50Cu50 fitted with MAUD program.

Figure S3i. XRD pattern of Fe45Cu55 fitted with MAUD program.

Figure S3j. XRD pattern of Fe40Cu60 fitted with MAUD program.

Figure S3k. XRD pattern of Fe30Cu70 fitted with MAUD program.

Figure S3l. XRD pattern of Fe20Cu80 fitted with MAUD program.

Figure S4. Phase composition of Fe-Cu oxalates as a function of
the nominal amount of Fe. Data on the y-axis are expressed as
volume percentages.

Figure S5. Evolution of the sample colour with increasing amount

of copper in the sample.