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Apatite-Like Complex Oxides in the Ca-Cr-Cu-O System: Synthesis, Crystal

Structure, XPS and Magnetic Study

Article  in  Berichte der deutschen chemischen Gesellschaft · September 2016

DOI: 10.1002/ejic.201600882

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 DOI: 10.1002/ejic.201600882
Metal Oxides
Apatite-Like Complex Oxides in the Ca–Cr–Cu–O System:
Synthesis, Crystal Structure, XPS and Magnetic Study
Gennady V. Bazuev*[a] Alexander P. Tyutyunnik,[a] Michail V. Kuznetsov,[a] and
Rina P. Samigullina[a]
Abstract: Calcium chromates Ca5(CrO4)3Cux(OH)1–x with apatite
structure and different content of copper and OH– groups have
been synthesized by solid-phase reactions under usual condi-
tions in air. The composition, structure, degree of oxidation of
the elements, and the properties of the produced chromates
have been characterized by X-ray diffraction, X-ray photoelec-
tron spectroscopy (XPS), differential thermal analysis (DTA),
Introduction
The attention of researchers to the phase chemistry of the sys-
tem Ca(Sr)–Cr–O is explained by the application of compounds
constituting this system in high-temperature electrochemical
devices,[1–3] as well as by the complicated behavior of Cr in the
production of cement clinker.[4] In all these cases, it is important
to know composition and properties of the produced complex
oxides, which depend on the temperature and the presence or
absence of an oxidizing medium.
The above-mentioned reasons also account for some contra-
dictions in establishing the oxidation states of chromium and
the phase composition of this system in a wide temperature
range in air. According to previous investigations,[5] under usual
conditions in air, the system Ca–Cr–O contains chromates
CaCr23+O4, Ca3(Cr5+O4)2, CaCr6+O4, and Ca5Cr3O12. Except for
CaCr2O4, all presented chromates are formed only under oxidiz-
ing conditions. This list includes also Ca2Cr2O5 chromate, which
can be synthesized from CaCO3 and Cr2O3 at 1000–1400 °C.[6]
Ca2Cr2O5 has been obtained also with use of a topochemical
reaction, namely by low-temperature reduction of the high-
pressure chromate CaCrO3.[7] In the course of restoration, the
series of phases CaCrO3–α was formed (α = 0.33, 0.4) along with
Ca2Cr2O5 (α = 0.5). Phases with α = 0.4 and 0.33 contain chro-
mium in the mixed valence (Cr3+/Cr4+) state. When heating the
phases in air, Ca2Cr2O5 is reconstituted.
Ca3(CrO4)2 chromate is formed in the temperature range of
959–1143 °C. In accordance with measurements of the mag-
[a] Institute of Solid State Chemistry, Ural Branch of the Russian Academy of
Sciences,
Pervomayskaya str. 91, 620990 Ekaterinburg, Russia
E-mail: bazuev@ihim.uran.ru
www.ihim.uran.ru
Supporting information make SI/orcid here
Eur. J. Inorg. Chem. 2016, 5340–5346
Full Paper
thermogravimetric analysis (TGA), and magnetochemical meth-
ods. It was concluded that the reason for the apatite stabiliza-
tion is the introduction of Cu+ and Cu2+ cations into the hexag-
onal O(4) sites in the tunnels of the Ca5(CrO4)3OH apatite struc-
ture. This is caused by the substitution of OH– according to the
scheme OH– → (Cu+O)– or 2 OH– → (Cu2+O2)2– which gives rise
to infinite chains along the c-axis.
netic susceptibility and X-ray absorption near-edge structure
(XANES) spectroscopy, it contains a mixture of two chromium
valence states (+5 and +6).[8] However, these results are con-
trary to the conclusion, which suggests that crystal structures
of Ca3(CrO4)2 and β-Ca3(PO4)2 are similar and that phosphorus
is present as P5+.[9]
CaCrO4 is an important cathode material in electrochemical
cells. As an intermediate compound formed in the system of
Ca–Cr–O it was studied to better understand the nature of the
chemical reactions that occur in the Ca/CaCrO4 thermal bat-
tery.[10] The melting temperature of CaCrO4 with zircon struc-
ture is 1073 °C.[11]
The last-mentioned compound (Ca5Cr3O12) is formed above
1143 °C and has an orthorhombic structure (space group
Pnma). The X-ray diffraction[12] and XANES spectroscopic[8] data
show that chromium in Ca5Cr3O12 is present in two valence
states, namely Ca5(Cr4+O4)2(Cr6+O4). The crystal structure of
Ca5Cr3O12 consists of isolated CrO4 tetrahedrons connected
with two Ca2+ cations that are related to the structure of
hydroxyapatite Ca5(CrO4)3OH.[13] Below 1143 °C, the compound
decomposes to Ca3(CrO4)2 and CaO. The composition of a sec-
ond calcium chromate compound with the ratio Ca/Cr = 5:3,
formed under usual conditions at T = 930 °C, is Ca10Cr6O25.[8]
The unit-cell parameters and the space group for Ca10Cr6O25[8]
and Ca5(CrO4)3OH[13] are the same.
Recently,[14] Ca10(Cr5+O4)6(Cr6+O4) was confirmed to be a new
type of mixed-valence Cr5+/Cr6+ compound. This chromate, ini-
tially described with the formula 9CaO·4CrO3·Cr2O3,[15] was pre-
pared from a Ca5(CrO4)3OH and CaCrO4 melt as dark green crys-
tals. Its formation reduces the refractoriness of calcium-rich
compositions of the system Ca–Cr–O in an oxidizing atmos-
phere. At present, this compound with formula Ca10Cr7O28 is
considered as a two-dimensional frustrated antiferromagnet
5340 © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

and a new candidate for a spin-liquid ground state built on spin
1
/2 Cr5+ ions.[16]
Hydroxyapatite Ca5(CrO4)3OH is formed in air in the presence
of water vapor at T < 959 °C[17] and has a hexagonal structure
(space group P63/m) with parameters a = 9.67 Å and c = 7.01 Å.
This chromate forms spontaneously during production of
materials based on the Ca–Cr–O system, for example at the
introduction of chromium into hydrated cement[2] or doping of
lanthanum chromites with Ca.[3] In a previous report,[17] it is
asserted that chromium is present in the pentavalent state in
Ca5(CrO4)3OH and also in the apatites with Ba and Sr that have
analogous composition. A similar conclusion is made based on
XANES spectroscopic analysis for Ca5(Cr5+O4)3O0.5.[8] It is signifi-
cant that apatites Ca5(CrO4)3Cl and Ca5(CrO4)3F are obtained
by the introduction of negative singly charged ions Cl– and
F–.[18]
A compound with apatite structure, Sr5(CrO4)3OH, is also
formed in the SrO–chromium oxide system in air and in an
oxygen atmosphere.[19] Its presence affects the composition of
the system in the temperature interval 502–792 °C. Above
792 °C, the apatite phase decomposes to Sr3Cr2O8, SrO, and
H2O. A stabilizing effect of fluorine on the apatite phase giving
rise to Sr5(CrO4)3F is shown.[19] F– ions occupy the O(H) sites in
the hexagonal channels in the apatite lattice, thereby forming
linear chains.
As shown previously,[20–22] besides F–, Cl–, OH–, and O2– ions,
more complex groups such as MO– (M = Cu, Ni, Co) and BO2–
can occupy the 2a anion sites in the hexagonal tunnels of
apatite. For example, in Sr5(PO4)3(CuO2)1/3,[20] A10(PO4)6Cux-
(Oy)(H)z (A = Ca, Sr, Ba),[21] and Sr5(VO4)3(CuO),[22] the Cu atoms
occupying the (0,0,0) positions are coordinated by two O(4)
anions and form indefinite linear chains [CuO]1– along the c-
axis. In these compounds, copper can be in the form of Cu+,
Cu2+, or Cu3+ cations depending on the synthesis conditions.
The presence of single paramagnetic copper cations (Cu2+ or
Cu3+) in the linear chains can lead to extremely anisotropic
paramagnetism [found for Sr5(PO4)3CuxOH1–x–y[23]] and to slow
spin relaxation. The materials possessing such characteristics
meet the requirements imposed on monomolecular magnets.
Examining the interaction in the systems of Sr, Cr, and 3d
transition-metal (Cu, Ni, Co) oxides, the authors[24] suggested
that these elements also have a stabilizing effect on the forma-
tion of chromates with apatite structure in air. The compound
Sr5(CrO4)3(Cu0.586O) with apatite structure and parameters a =
10.0292(1) Å, c = 7.4623(1) Å, Z = 2, and space group P63/m has
been isolated and characterized while studying the Sr–Cr–Cu–
O system.[24] This compound is stable up to 1200 °C and, ac-
cording to magnetic susceptibility data, it contains chromium
mainly as Cr5+ and copper as Cu+ cations. The underestimated
value of the magnetic moment as compared with the theoreti-
cal value of the Cr5+ cations indicates that some part of
chromium is present in the form of Cr6+ cations.
In connection with these results, in the present work we ana-
lyze the stabilizing effect of Cu oxides on the formation of
apatite phase in the Ca–Cr–O system using X-ray diffraction,
thermal analysis, photoelectron spectroscopy, and magneto-
chemistry methods.
Eur. J. Inorg. Chem. 2016, 5340–5346 www.eurjic.org
Full Paper
Results and Discussion
In order to verify the suppositions about possible stabilization
of the apatite phase in this system, we synthesized samples of
Ca5(CrO4)3, Ca5(CrO4)3(CuO)0.75, and Ca5(CrO4)3(CuO) at different
temperatures in air. Syntheses at 800 °C (18 h) and 900 °C (18 h)
gave rise to a phase with apatite structure in all cases. Along
with the main phase, the samples contained an impurity of
calcium chromate CaCrO4.[25] Then, the obtained products were
successively annealed: in air at 1100 °C with cooling with the
furnace or by quenching, as well as at 900 °C in an argon flow.
The sample containing no CuO, which was annealed at 1100 °C
[that is above the decomposition temperature of apatite
Ca5(CrO4)3OH] and cooled to room temperature with the fur-
nace, contained Ca3(CrO4)2 and CaO along with the apatite-like
phase. By subsequent quenching from 1100 °C the amount of
impurity phases in the sample increased. This sample was addi-
tionally annealed in an argon atmosphere at 900 °C. As a result,
apatite phase in the pure form was obtained, which has the
hexagonal cell parameters [a = 9.676(2) Å, c = 7.028(3) Å, V =
569.4 Å3] close to those reported in previous work[13] [a =
9.671 Å, c = 7.010 Å for Ca5(CrO4)3OH]. Upon annealing at
1100 °C, the samples, whose initial composition included CuO
[Ca5(CrO4)3(CuO) and Ca5(CrO4)3(CuO)0.75], contained a com-
pound with apatite structure and a small amount of CuO (if the
sample was cooled with the furnace) or Cu2O (in the case of
quenching). In the powder-like state, these samples, like
Sr5(CrO4)3(Cu0.586O),[24] had a dark green color. Additional an-
nealing confirmed the thermal stability of these compounds at
1250 °C. Structural analysis (the results are given below) was
used to establish the general composition and amount of cop-
per in the compounds: Ca5(CrO4)3(Cu0.752O) in the first sample
and Ca5(CrO4)3(Cu0.541O) in the second sample. An increased
content of Cu in the synthesized product was obtained by an-
nealing of the initial sample Ca5(CrO4)3(CuO) in Ar at 1000 °C.
The composition of the formed apatite, according to the struc-
tural analysis, corresponded to the formula Ca5(CrO4)3(Cu0.840O).
In order to establish the effect of Cu on the apatite stabiliza-
tion, we synthesized Ca5(CrO4)3(CuO)x compounds with x =
0.15, 0.25, 0.45, and 0.55 under analogous conditions at 1100 °C
with cooling in the furnace. According to the X-ray phase analy-
sis of the samples, with increasing quantity of CuO the content
of an apatite-like phase increased, and the number of impurity
compounds decreased. Among them, CaCrO4, CaCu2O3, and
CuO have been found. As follows from Figure 1, the unit-cell
parameters a, c and the volume V of the produced phases in-
crease with the copper content, which proves the formation of
a continuous solid solution (SS). The absence of a linear de-
pendence between the parameters and the copper content is
likely due to the structural peculiarities of the stabilized
apatites[20] and the presence of impurities in samples with low
values of x.
The chemical stability of Ca5(CrO4)3(Cu0.752O) was studied by
the TG/DTA method in air in the temperature interval 20–
1100 °C during heating and cooling of a powder-like sample.
The results of the analysis (Figure 2) were compared with analo-
gous investigations on hydroxyapatite Ca5(CrO4)3OH.[3] Accord-
ing to that data,[3] during heating of Ca5(CrO4)3OH from room
5341 © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 1. Dependence of unit-cell parameters and cell volume on the content
of copper in Ca5(CrO4)3Cux(OH)1–x.
temperature up to 1100 °C, the DTA and TG curves exhibit a
cascade of exothermic and endothermic effects accompanied
both by a decrease and an increase in the sample's mass. When
heating to 400° C, the mass of the Ca5(CrO4)3OH sample de-
creases by more than 3 % with exothermic effects at 220 and
350 °C. It was established that at 400 °C the chromate CaCr6+O4
is formed (the mass being increased), which decomposes at
higher temperatures. In the temperature range of 800–900 °C,
Figure 3. Observed (crosses), calculated (solid line), and difference (bottom line) X-ray powder diffraction pattern of Ca5(CrO4)3(Cu0.840O). First and second
vertical lines indicate the reflections of impurity phases CuO and Cu2O, respectively.
Eur. J. Inorg. Chem. 2016, 5340–5346 www.eurjic.org
Full Paper
the apatite phase Ca5(CrO4)3OH is stable, and at higher temper-
atures it decomposes to Ca3(CrO4)2, CaO, and H2O. Overall, the
sample's mass decreases by more than 6 % during heating in
the interval 20–1100 °C.
Figure 2. DTA and TG curves for the apatite-type chromate
Ca5(CrO4)3(Cu0.752O).
The results of the DTA and TG studies of the synthesized
sample Ca5(CrO4)3(Cu0.752O) (Figure 2) clearly demonstrate a dif-
ferent behavior. The DTA curve does not show any thermal ef-
fects in the interval 240–900 °C, which can be due to the proc-
esses of oxidation, formation, or decomposition of compounds.
The wave-like increase in the mass of the initial sample by
0.28 % during heating up to 800 °C and subsequent decrease
by 0.38 % can be caused by oxidation of chromium to Cr6+ with
formation of CaCrO4 in the surface layer and by subsequent
decomposition of this chromate. The low-intensity endothermic
effects at 1006 and 1040 °C in the heating curve and the exo-
thermic effect at 965 °C in the cooling curve (not given) are
induced by melting of the oxide impurity CuO (0.3 wt.-%) giving
rise to Cu2O and Cu2O (0.3 mass-%) and by oxidation of Cu2O
to CuO.[26]
5342 © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
 Full Paper

Figure 4. Observed (crosses), calculated (solid line), and difference (bottom line) X-ray powder diffraction pattern of Ca5(CrO4)3(Cu0.541O). The first vertical lines
indicate the reflections of the impurity phase CuO.

Figures 3 and 4 show the experimental and calculated diffrac- Table 1. Structural data for Ca5(CrO4)3(Cu0.840O) (1), Ca5(CrO4)3(Cu0.752O) (2)
tion patterns of Ca5(CrO4)3(Cu0.840O) and Ca5(CrO4)3(Cu0.541O), and Ca5(CrO4)3(Cu0.541O) (3).
respectively, upon refinement in the space group P63/m. Struc- 1 2 3
tural data for Ca5(CrO4)3(Cu0.840O) (1), Ca5(CrO4)3(Cu0.752O) (2), Space group, no. P63/m, 176 P63/m, 176 P63/m, 176
and Ca5(CrO4)3(Cu0.541O) (3) are given in Table 1. The atomic Z 2 2 2
coordinates and isotropic thermal parameters of the atoms in a = b [Å] 9.72821(5) 9.7264(1) 9.7067(1)
compounds 1 and 3 are listed in Table 2, and their interatomic c [Å] 7.10731(4) 7.10178(9) 7.0639(1)
V [Å3] 582.508(6) 581.84(1) 576.39(1)
distances are given in Table 3. The studied chromates are iso-
DX [g/cm3] 3.522 3.494 3.450
structural with Sr5(VO4)3(CuO)[22] and Sr5(PO4)3(CuO2)1/3,[20] Mass of CuO [wt.-%] 0.3 0.8 2.4
whose crystal structure is a derivative of the structure of apatite Mass of Cu2O [wt.-%] 0.3
Ca5(PO4)3OH.[27,28] This structure contains isolated tetrahedrons Number of variables 69 69 69
with [CrO4]3– anions and infinite O–Cu–O chains (Figure 5). The wRp [%] 1.44 1.61 1.38
Rp [%] 1.11 1.23 1.06
oxygen atoms O(4) are in the F-positions of classic apatite R(F2) [%] 4.27 5.24 4.00
Ca5(CrO4)3F,[17] and the Cu atoms occupy the H+ positions of χ2 1.706 1.622 1.443
hydroxyapatite. As the content of Cu increases, the occupancy
of the chains grows but does not reach 100 %. Thus, it is not
excluded that a certain amount of OH– groups is present in the Table 2. Atomic coordinates and isotropic thermal parameters (Uiso × 100 [Å2])
tunnels. The Cu atoms are bound to two O(4) atoms, the Cu–O for Ca5(CrO4)3(Cu0.840O) and Ca5(CrO4)3(Cu0.541O) (given in italics).
distances being 1.77544(2) Å. The Cr atoms are in the center Atom x/a y/b z/c Fraction Uiso × 100
of slightly distorted oxygen tetrahedra with an average Cr–O Ca(1) 4f 1/3 2/3 0.5016(4) 1.0 3.7(1)
distance of 1.698 Å. A small distortion of the polyhedron is due 1/3 2/3 0.4999(4) 1.0 2.9(2)
to the Jahn–Teller nature of Cr5+ cations (d1 configuration). By Ca(2) 6h 0.0020(2) 0.2527(2) 1/4 1.0 3.3(1)
taking into consideration the fact that copper cations replacing 0.0002(2) 0.2444(2) 1/4 1.0 2.7(2)
Cr 6h 0.6296(1) 0.0295(2) 1/4 1.0 3.3(1)
a part of the protons in the OH– groups are present in the
0.6271(2) 0.0280(2) 1/4 1.0 2.6(2)
tunnels, as well as the obtained data on the crystal structure, Cu 2b 0 0 0 0.840(4) 3.3(1)
the composition of the compounds can be expressed by the 0 0 0 0.541(5) 2.4(2)
chemical formula Ca5(CrO4)3Cux(OH)1–x. However, the presence O(1) 6h 0.5109(6) 0.8285(5) 1/4 1.0 4.4(2)
of vacancies in the Cu positions in the chains cannot be ruled 0.5115(5) 0.8291(5) 1/4 1/0 2.7(1)[a]
O(2) 6h 0.5308(5) 0.1328(5) 1/4 1.0 2.4(2)
out. 0.5251(5) 0.1297(6) 1/4 1.0 2.7(1)[a]
Photoelectron spectroscopy is widely used for studying the O(3) 12i 0.3425(4) 0.2512(3) 0.0583(4) 1.0 3.4(1)
electronic structure, chemical composition, and degrees of 0.3437(4) 0.2487(4) 0.0612(4) 1.0 2.7(1)[a]
oxidation of elements in the examined materials. This method O(4) 2a 0 0 1/4 1.0 2.7(2)
0 0 1/4 1.0 2.7(1)[a]
provides information about the thin surface layer on samples
and, consequently, allows to make a conclusion about the cor- [a] Thermal parameters of oxygen atoms were constrained as a single varia-
ble.
respondence between the surface composition and the compo-
sition of the bulk.[29] In this work, photoelectron spectroscopy
was used to confirm the composition of apatites Figure 6 presents the XPS spectra of these two compounds.
Ca5(CrO4)3(Cu0.752O) and Sr5(CrO4)3(Cu0.586O)[24] and to estimate The spectra contain the lines of photoelectron energy levels of
the degree of oxidation of Cr and Cu. Cr and Cu. Considering previous results,[24] according to which

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 Full Paper

Table 3. Selected interatomic distances d [Å] and angles [°] for chromium is present in Sr5(CrO4)3(Cu0.586O) mainly as Cr5+
Ca5(CrO4)3(Cu0.840O) and Ca5(CrO4)3(Cu0.541O) (given in italics). cations and copper as Cu1+ cations, we will analyze the XPS
Interatomic Interatomic spectrum of this apatite at first. The XPS analysis of Cr2p and
distances distances Cu2p spectra of Sr5(CrO4)3(Cu0.586O) (Figure 6, lower panel) con-
Ca(1)–O(1) 3× 2.437(3) Ca(2)–O(2) 2.361(4) firms the previous conclusions.[24] The spectrum of Cr2p con-
2.422(3) 2.364(4) sists of two doublets, 2p3/2 and 2p1/2. The positions of the peak
Ca(1)–O(2) 3× 2.469(3) Ca(2)–O(3) 2× 2.358(3) centers of the first doublet are at 578 and 587 eV, and for the
2.490(3) 2× 2.392(3)
second doublet at 580 and 589 eV. According to literature
Ca(1)–O(3) 3× 2.866(3) Ca(2)–O(4) 2.448(1)
2.849(3) 2.371(1) data,[30,31] the values of the binding energy Eb of Cr2p increase
Average 2.591 Ca(2)–O(3) 2× 2.554(3) with the oxidation state of this element, and the reported val-
2.587 2× 2.493(3) ues correspond to pentavalent (578 eV for 2p3/2 and 587 eV for
Expected* 2.56 Ca(2)–O(1) 2.766(5) 2p1/2) and hexavalent (580 eV for 2p3/2 and 589 eV for 2p1/2)
2.793(5)
Cr–O(1) 1.702(4) Average 2.486
chromium. The identification of a large amount of Cr6+ cations
1.680(5) 2.471 is explained by the formation of strontium chromate SrCr6+O4
Cr–O(2) 1.703(4) Expected[a] 2.44 in the surface layer of the sample. Possibly, surface oxidation
1.712(4) took place as a result of “compaction”, a kind of preparation of
Cr–O(3) 2× 1.693(3) Cu–O(4) 2× 1.77683(1)
samples for investigations. According to the structural analysis
2× 1.695(3) 2× 1.76598(2)
Average 1.698 Expected[a] 1.85 data, this compound was not found in the sample.
1.696 Cu–O(3) 6× 3.017(3)
Expected* 1.718 6× 3.015(4)
angles angles
O(1)–Cr–O(2) 114.8(2) O(1)–Cr–O(3) 2× 111.0(2)
114.6(2) 112.3(2)
O(3)–Cr–O(3) 107.2(2) O(2)–Cr–O(3) 2× 106.2(1)
103.8(2) 106.5(4)
[a] The sum of the crystal radii were calculated according to ref.[36] and the
general formulae Ca + 25(Cr + 50.947Cr + 60.053O – 24) × 3(Cu + 10.840O
– 2) and Ca + 25(Cr + 50.917Cr + 60.083O – 24) × 3(Cu + 10.752O – 2),
respectively.

Figure 6. XPS Cr2p and Cu2p core-level spectra of Ca5(CrO4)3(Cu0.541O) (upper

panel) and Sr5(CrO4)3(Cu0.586O) (lower panel).

The Cu2p XPS spectrum of Sr5(CrO4)3(Cu0.586O) (Figure 6,

Figure 5. Structure of Ca5(CrO4)3(Cu0.840O): (a) projection along the c-axis,
(b) side view showing the infinite [CuO]1– chains and the coordination poly-
hedra of the Cr and Ca atoms.
lower panel) is also split into two sublevels, 2p3/2 and 2p1/2,
located at 932.7 and 952.7 eV, respectively. Such values of the
binding energy Eb, according to previous observations,[32,33] are
typical for the Cu2p XPS spectrum of univalent copper oxide
Cu2O.
Analogous analyses of the Cr2p and Cu2p XPS spectra of
apatite of the composition Ca5(CrO4)3(Cu0.541O) (Figure 6, upper
panel) allowed us to conclude about the mixed oxidation states
of these elements. Considering the positions of the Cr2p3/2 and
Cr2p1/2 peaks on the energy scale, the sample contains a small
amount of a phase with low-valence chromium (Cr3+ or Cr4+)
on the background of the basic Cr5+-containing apatite and
chromate CaCr6+O4 in the surface layer. Besides, the Cu2p XPS
spectrum of Ca5(CrO4)3(Cu0.541O), as compared with that of
Sr5(CrO4)3(Cu0.586O), is complicated because of additional satel-
lite peaks in the region of 940–943 eV. This indicates that along
with Cu+ cations, some Cu2+ cations are present in this com-

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pound. Figure 6 shows the spectrum of the decomposition of
Cu2p recorded based on the known[32,33] XPS values of Eb for
Cu2O and CuO. From these data it can be concluded that cop-
per in the composition of Ca5(CrO4)3(Cu0.541O) is present in
mixed valence state (as Cu+ and Cu2+).
The magnetic susceptibility measurements revealed consid-
erable differences in the magnetic behavior of the samples with
the composition Ca5(CrO4)3(Cu0.752O) and Ca5(CrO4)3(Cu0.541O)
(Figure 7). The complex oxide Ca5(CrO4)3(Cu0.752O) is paramag-
netic in the temperature interval 5–300 K with magnetic sus-
ceptibility following the Curie law χ = C/T, where χ is the molar
susceptibility, C the Curie constant (1.015 cm3/mol), and T the
temperature. The value of the effective magnetic moment (μeff )
corresponds to 1.644 μB per Cr atom, which is close to μtheor for
the Cr5+ cation (1.732 μB). These results coincide almost com-
pletely with the data obtained earlier for Sr5(CrO4)3(Cu0.586O)[24]
and demonstrate that copper is in the form of Cu+ cations, and
chromium is partially present as Cr6+ cations. The dependence
χ = f(T) for Ca5(CrO4)3(Cu0.541O) deviates from the Curie law
and follows the equation χ = χ0 + C/(T – Θ), where χ0 is the
temperature-independent component equal to 2.4 × 10–6 cm3/
mol, C = 0.73 cm3/mol, and Θ is the Weiss constant (2 K). Based
on these values we find that the effective magnetic moment
referring to one Cr atom is 1.39 μB. The differences in the mag-
netic behavior of the examined samples are in good agreement
with the results of the XPS spectra showing that a considerable
amount of Cu2+ cations is present in the sample with a smaller
copper content.
Figure 7. Temperature dependence of inverse magnetic susceptibility 1/χ for
(1) Ca5(CrO4)3(Cu0.752O) and (2) Ca5(CrO4)3(Cu0.541O).
Taking into consideration the XPS and magnetic measure-
ments, an idealized conclusion can be made on the composi-
tion of anion groups stabilizing the SS Ca5(CrO4)3Cux(OH)1–x. It
can be proposed that the (Cu+O)– anion is responsible mainly
for the formation of the phase with high Cu content
[Ca5(CrO4)3(Cu0.840O)], while the formation of phases with a
lower copper content takes place with participation of OH–
groups according to the scheme of substitution 2 OH– →
(Cu2+O2)2–. Depending on the amount of introduced copper
cations and heat-treatment conditions, variants with a mixed
substitution of OH– anions, described by the simplified formula
Ca5(CrO4)3Cux(OH)1–x, is possible. To specify the presented re-
sults it is planned to define the composition of the formed
apatites Ca5(CrO4)3Cux(OH)1–x by analyzing the 1H magic-angle
spinning (MAS) NMR spectra.
Eur. J. Inorg. Chem. 2016, 5340–5346 www.eurjic.org
Full Paper
Conclusion
The solid solution Ca5(CrO4)3Cux(OH)1–x (0 ≤ x ≤ 0.84) with
apatite structure, stable in air up to 1250 °C, was synthesized
by the solid-state reaction method under usual conditions. The
crystal structure of the SS was determined by X-ray diffraction
studies. Cu atoms in the SS occupy the O(H) sites in the hexago-
nal channels in the apatite Ca5(CrO4)3OH. They are coordinated
by two O(4) anions and form infinite linear chains along the c-
axis. Unit-cell parameters and volume constantly increase with
increasing copper content. According to XPS and magnetic
measurements, the valence state of Cr is +5 and that of Cu
presumably +2 and +1.
Experimental Section
Ca5(CrO4)3(CuO)x complexes with apatite structure were synthesized
by the solid-phase reactions from oxides Cr2O3 (99.9 %), CuO
(99.9 %), and CaCO3 (99.95 %). The initial reagents were carefully
mixed, ground, and pressed under a pressure of 3000 kg/cm2 at
800–1250 °C in air in corundum crucibles. The samples were re-
ground after 18 h of annealing. The total time of treatment was
36 h. The crystal structure and presence of impurities was deter-
mined by X-ray diffraction studies using Cu-Kα1 radiation with a
STADI-P(STOE) diffractometer equipped with a mini-PSD in trans-
mission geometry with a scanning step δ2θ = 0.02° in the 2θ angle
interval from 5° to 120°. Polycrystalline silicon [a = 5.43075(5) Å]
was used as an external standard. To identify possible impurity pha-
ses, the powder standard database PDF2 (ICDD, USA, Release 2009)
was used. The crystal structure refinement of the samples was per-
formed with the GSAS program suite by using XRD data.[34]
The peak profiles were fitted with a pseudo-Voigt function, I(2Θ) =
x × L(2Θ) + (1 – x) × G(2Θ) (where L and G are the Lorentzian and
Gaussian part, respectively). The angular dependence of the peak
width is described by the relation (FWHM)2 = Utg2Θ + VtgΘ + W,
where FWHM is the full line width at half maximum. The back-
ground level was described by a combination of thirty-six-order
Chebyshev polynomials. The absorption correction function for a
flat plate sample in transmission geometry was applied.[34]
The XPS spectra of the samples were recorded with a VG ESCALAB
MK II electron spectrometer. The powder samples were applied on
a double-faced conducting sticky tape. The Mg-Kα line (1253.6 eV)
without monochromator was used as exciting X-radiation. The en-
ergy scanning pitch was 0.1 eV, and the energy resolution of the
spectrometer was calculated from the Ag3d5/2 line at the analyzer
transmission energy of 10 eV. The width of this line at half height
was 0.82 eV. The spectrometer was calibrated against the Au4f7/2
line (84.0 eV), and charging of the sample was estimated by using
the C1s carbon spectra (284.5 eV) from natural hydrocarbon surface
contaminations. The composition of the complex oxides was deter-
mined from the Cr2p, Cu2p, Ca2p, and O1s lines with use of the
calculated values of photoionization cross sections for these states.
TGA was performed with a Setaram SETSYS Evolution DSC calorime-
ter. The sample heating rate in the DTA and DTG mode was 10 K/
min in air.
The magnetic measurements were performed with an MPMS-5-XL
SQUID magnetometer (QUANTUM DESIGN). The temperature was
varied in the interval from 5 to 300 K. The applied magnetic field
was 1 kOe. Magnetization M and static magnetic susceptibility χ =
M/H were determined from the measurements of the static mag-
5345 © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

netic moment of the sample. The molar magnetic susceptibility
value was revised with allowance for diamagnetism of Ca2+, Cr5+,
Cu+, Cu2+, and O2– ions.[35]
Acknowledgments
This work was supported by a grant of the Presidium of the
Ural Branch of the Russian Academy of Sciences, Ekaterinburg.
Keywords: Apatite · Copper · Calcium · Chromates · Solid-
phase synthesis · Magnetic properties
[1] T. Kadowaki, T. Shiomitsu, E. Matsuda, H. Nakagava, H. Tsuenizumi, T.
Maruyama, Solid State Ionics 1993, 67, 65–69.
[2] S. P. S. Badwal, R. Deller, K. Foger, Y. Ramprakash, J. P. Zhang, Solid State
Ionics 1997, 99, 297–310.
[3] I. Yasuda, M. Hishinuma, Solid State Ionics 1995, 78, 109–114.
[4] S. Sinyounga, P. Songsiriritthigul, S. Asavapisitd, P. Kajitvichyanukule, J.
Hazard. Mater. 2011, 191, 296–305.
[5] J. P. R. Villiers, J. Mathias, A. Muan, Trans. Inst. Min. Metall. Sect. C 1987,
96, 55–62.
[6] I. Kontoulis, B. C. H. Steele, J. Eur. Ceram. Soc. 1992, 9, 459.
[7] A. M. Arevalo-Lopez, B. Liang, M. S. Senn, C. Murray, C. Tang, J. P. Attfield,
J. Mater. Chem. C 2014, 2, 9364.
[8] I. Arcon, B. Mirtic, A. Kodre, J. Am. Ceram. Soc. 1998, 81, 222–224.
[9] E. Cuno, Hk. Müller-Buschbaum, Z. Anorg. Allg. Chem. 1989, 572, 95–101.
[10] Y. W. Long, W. W. Zhang, L. X. Yang, Y. Yu, R. C. Yu, S. Ding, Y. L. Liu, C. Q.
Jina, Appl. Phys. Lett. 2005, 87, 181901.
[11] A. Kaiser, B. Sommer, E. Woermann, J. Am. Ceram. Soc. 1992, 75, 1463–
1471.
[12] K. T. Adendorff, J. P. R. Devilliers, G. J. Kruger, J. Am. Ceram. Soc. 1992,
75, 1416–1422.
[13] K. Wilhelmi, O. Jonsson, Acta Chem. Scand. 1965, 19, 117–184.
Eur. J. Inorg. Chem. 2016, 5340–5346 www.eurjic.org 5346
View publication stats
Full Paper
[14] D. Gyepesova, V. Langer, Acta Crystallogr., Sect. C 2013, 69, 111–113.
[15] W. F. Ford, W. J. Rees, Trans. Br. Ceram. Soc. 1948, 47, 207–208.
[16] C. Balz, Investigation of low dimensional and frustrated spin 1/2 magnets,
Doctoral Thesis, Technische Universität Berlin, 2015.
[17] R. Scholder, H. Schwarz, Z. Anorg. Allg. Chem. 1963, 326, 11–24.
[18] E. Banks, K. L. Jaunarajs, Inorg. Chem. 1965, 4, 78–83.
[19] E. Herdtweck, Acta Crystallogr., Sect. C 1991, 47, 1711–1712.
[20] P. E. Kazin, A. S. Karpov, M. Jansen, J. Nussc, Y. D. Tretyakov, Z. Anorg.
Allg. Chem. 2003, 629, 344–352.
[21] T. Baikie, G. M. H. Ng, S. Madhavi, S. S. Pramana, K. Blakt, M. Elcombe,
T. J. White, Dalton Trans. 2009, 6722–6226.
[22] W. Carrillo-Cabrera, H. G. von Schnering, Z. Anorg. Allg. Chem. 1999, 625,
183–185.
[23] P. E. Kazin, M. A. Zykin, W. Schnelle, C. Felser, M. Jansen, Chem. Commun.
2014, 50, 9325–9328.
[24] A. P. Tyutyunnik, G. V. Bazuev, J. Alloys Compd. 2012, 522, 141–143.
[25] G. Weber, K.-J. Range, Z. Naturforsch. B 1996, 51, 751–753.
[26] W. M. Shaheen, I. H. A. Maksod, J. Alloys Compd. 2009, 476, 366–372.
[27] M. I. Kay, R. A. Young, A. S. Posner, Nature 1964, 204, 1050–1052.
[28] M. Hughes, M. Cameron, K. D. Crowley, Amer. Mineral. 1989, 74, 870–876.
[29] G. V. Bazuev, T. I. Chupakhina, A. V. Korolyov, M. V. Kuznetsov, Mater.
Chem. Phys. 2010, 124, 946–951.
[30] M. Aronniemi, J. Sainio, J. Lahtinen, Surf. Sci. 2005, 578, 108–123.
[31] T. Baikie, Z. Ahmad, M. Srinivasan, A. Maignan, S. S. Pramana, T. J. White,
J. Solid State Chem. 2007, 180, 1538–1546.
[32] M. F. Al-Kuhaili, Vacuum 2008, 82, 623–629.
[33] A. Losev, K. Kostov, G. Tyuliev, Surf. Sci. 1989, 213, 564–579.
[34] a) B. H. Toby, J. Appl. Crystallogr. 2001, 34, 210–213; b) A. C. Larson, R. B.
von Dreele, General Structure Analysis System (GSAS), Los Alamos National
Laboratory, Report LAUR, 2004, pp. 86–748.
[35] P. W. Selwood, Magnetochemistry, 2nd ed., Interscience, New York and
London, 1956.
[36] R. D. Shannon, Acta Crystallogr., Sect A 1976, 32, 751.
Received: July 20, 2016
Published Online: October 27, 2016
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim