Phase formation in the Li2MoO4-A2MoO 4-NiMoO4 (A = K, Rb, Cs) systems, the crystal structure of Cs2Ni2(MoO4)3, and color characteristics of alkali-metal nic

Article abstract of DOI:10.1134/S0036023611080298

The subsolidus regions of the Li₂MoO₄-A ₂ ⁺ MoO₄-NiMoO₄ (A⁺ = K, Rb, Cs) systems at 510°C have been triangulated by the intersecting-joins method. The A₂MoO₄

Full text of DOI:10.1134/S0036023611080298

ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2011, Vol. 56, No. 8, pp. 1216–1221. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © E.S. Zolotova, Z.A. Solodovnikova, B.M. Ayupov, S.F. Solodovnikov, 2011, published in Zhurnal Neorganicheskoi Khimii, 2011, Vol. 56, No. 8, pp. 1287–
1292.
SYNTHESIS AND PROPERTIES
OF INORGANIC COMPOUNDS
Phase Formation in the Li2MoO4–A2MoO4–NiMoO4 (A = K, Rb,
Cs) Systems, the Crystal Structure of Cs2Ni2(MoO4)3, and Color
Characteristics of AlkaliꢀMetal Nickel Molybdates
E. S. Zolotovaa, Z. A. Solodovnikovaa, B. M. Ayupova, and S. F. Solodovnikova, b
a Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Akademika Lavrent’eva 3, Novosibirsk, 630090 Russia
b Novosibirsk State University, ul. Pirogova 2, Novosibirsk, 630090 Russia
eꢀmail: solod@niic.nsc.ru
Received November 30, 2009
+
Abstract—The subsolidus regions of the Li MoO –
–NiMoO (A+ = K, Rb, Cs) systems at 510
C
°
A2MoO4
2
4
4
have been triangulated by the intersectingꢀjoins method. The A2MoO4–Li2Ni2(MoO4)3, Li2MoO4–
A2Ni2(MoO4)3, A2Ni2(MoO4)3–Li2Ni2(MoO4)3 (A = K, Rb, Cs), and ALiMoO4–A2Ni2(MoO4)3 (A = K,
Rb) joins have been investigated. The subsolidus phase formation study has also been completed by spontaꢀ
neous flux crystallization. No triple salts have been identified, but only compounds belonging to the boundary
binary systems. The crystal structure of Cs2Ni2(MoO4)3 (a = 10.7538 Å, Z = 4, space group P213, R = 0.0082)
belonging to the langbeinite type has been determined. It is built of a threeꢀdimensional framework of vertexꢀ
sharing MoO4 tetrahedra and NiO6 octahedra and cesium ions occupying large outꢀofꢀframework cavities.
All alkaliꢀmetal nickel molybdates are yellow. These compounds are usable as pigments, as judged from their
reflection spectra and calculated color characteristics, namely, colorfulness (
C
), lightness (
L
), and hue (
H
).
DOI: 10.1134/S0036023611080298
Information concerning double molybdates of nickel molybdate is Li2 – 2xNi2 + x(MoO4)3 (0
≤
x
≤
0.07)
alkali and divalent metals is systematized by Mokhoꢀ [12]. The Na2MoO4–NiMoO4 system contains alluꢀ
soev and Bazarova [1]. Many of these compounds posꢀ auditeꢀtype Na2 + 2xNi1 – x(MoO4)2 (0.20 0.33)
≤
x
≤
sess ferroelectric, piezoelectric, ionꢀconducting, or and the double molybdate Na1.86Ni2.07(MoO4)3 isosꢀ
other functional properties [2–5]. The area of applicaꢀ tructural to Li3Fe(MoO4)3 [13, 14]. On the whole,
tion of these compounds can be further widened by these data were corroborated in a later study [12]. The
employing them as pigments. However, there have A2MoO4–NiMoO4 (A = K, Rb) systems each contain
been only a few examples of use of the molybdates in two nickelꢀcontaining double molybdates, namely,
this field. The most popular molybdate pigments are A2Ni(MoO4)2
those of the yellow–orange–red color range, which A2Ni2(MoO4)3
(
(
K2Ni(MoO4)2 type) [15, 16] and
K2Zn2(MoO4)3 type) [17–20]. The
are based on the lead molybdate chrome Pb(Mo, Cr, cesium analogue of these systems has a single intermeꢀ
S)O4 and the BiVO4–Bi2MoO6 twoꢀphase system [6]. diate compound, Cs2Ni2(MoO4)3 (langbeinite type)
These pigments contain toxic elements, namely, lead, [21–23].
chromium, and vanadium. At the same time, the
bright yellow, nickelꢀcontaining mixed oxides studied
by Rossman et al. [7] include Li2Ni2Mo3O12, which,
like other nickelꢀcontaining molybdates, can serve as
the basic material for new pigments. Besides the douꢀ
ble nickelꢀcontaining molybdates, triple ones might
be usable for this purpose, but there is no information
about the latter.
Here, we report phase relations in Li2MoO4–
A2MoO4–NiMoO4 (A = K, Rb, Cs) ternary systems
and the structure and some properties of alkaliꢀmetal
nickel molybdates.
EXPERIMENTAL
The starting components in the solidꢀphase synꢀ
The alkaliꢀmetal nickel molybdates were characꢀ thesis of molybdates were analyticalꢀgrade MoO3
terized in detail. The Li2MoO4 NiMoO4 system conꢀ pureꢀgrade Li2MoO4, K2MoO4, Cs2MoO4, and
tains a single intermediate compound, which has a NiMoO4 ; and specialꢀpurityꢀgrade Li2CO3, K2CO3,
Li3Fe(MoO4)3 structure. Initially, this compound was Na2MoO4 H2O, and Rb2CO3. Alkaliꢀmetal molybꢀ
;
–
·
viewed as having the stoichiometric composition dates were also obtained by solidꢀphase synthesis from
Li2Ni2(MoO4)3 [1, 8–11], but later it was demonꢀ alkaliꢀmetal carbonates and molybdenum trioxide:
strated that a more correct formula of this lithium Li2MoO4 was synthesized at 500–600 C; sodium,
°
1216

PHASE FORMATION
1217
Table 1. Properties of the starting compounds used in the investigation of joins in the Li2MoO4–A2MoO4–NiMoO4
(A = K, Rb, Cs) systems
Density, g/cm3
Compound
NiMoO4
Tmp
,
°C
Compound
CsLiMoO4
Tmp
,
°C
experimental
theoretical
1310* [24]
700
790
–
–
Li2MoO4
Li2Ni2(MoO4)3
K2Ni(MoO4)2
K2Ni2(MoO4)3
Rb2Ni(MoO4)2
Rb2Ni2(MoO4)3
Cs2Ni2(MoO4)3
1060* [10]
670*
4.36
3.49
3.78
4.00
4.21
4.60
4.38
3.47
3.80
4.00
4.23
4.61
K2MoO4
920
Rb2MoO4
930
755*
Cs2MoO4
940
650*
KLiMoO4
570
700*
RbLiMoO4
* Incongruent melting.
705
700*
potassium, and rubidium molybdates, at 500–550
°
C
.
stoichiometric mixtures of simple molybdates at 500–
550 for 70–120 h. The synthesized double molybꢀ
dates were characterized by Xꢀray powder diffraction and
thermal analysis. The obtained data (Table 1) are in good
agreement with the literature.
°C
The double molybdates LiAMoO4 with A = K, Rb, and
Cs were obtained by 100ꢀh annealing of a mixture of
the corresponding alkaliꢀmetal carbonate (molybꢀ
date), lithium molybdate, and molybdenum trioxide
at 545, 530, and 535 C, respectively. Nickelꢀcontainꢀ
°
The phase equilibria and phase formation in the
ing double molybdates were obtained by annealing subsolidus regions of the Li2MoO4–A2MoO4–NiMoO4
(а)
A2MoO4
(b)
Cs2MoO4
ALiMoO4
A2Ni(MoO4)2
CsLiMoO4
A2Ni2(MoO4)3
Cs2Ni2(MoO4)3
Li2Ni2(MoO4)3
NiMoO4
Li2MoO4
Li2MoO4
Li2Ni2(MoO4)3
NiMoO4
(c)
A2MoO4
(d)
Cs2MoO4
CsLiMoO4
A2Ni2(MoO4)3
ALiMoO4
A2Ni(MoO4)2
Cs2Ni2(MoO4)3
Li2 – 2xNi2 + (MoO )
4 3NiMoO4
Li2MoO4
x
Li2MoO4
Li2 – 2xNi2 + x(MoO4)3
NiMoO4
Fig. 1. Li MoO –A MoO –NiMoO (A = K, Rb, Cs) systems: (a) joins examined in the Li MoO –A MoO –NiMoO (A = K,
2
4
2
4
4
2
4
2
4
4
Rb, Cs) systems; (b) join examined in the Li MoO –Cs MoO –NiMoO system; (c) subsolidus triangulation of the Li MoO –
2
4
2
4
4
2
4
A MoO –NiMoO (A = K, Rb) systems at 510
°
C
(the sector indicates the twoꢀphase region); (d) subsolidus triangulation of the
2
4
4
Li MoO –Cs MoO –NiMoO system at 510°C (the sector indicates the twoꢀphase region).
2
4
2
4
4
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

1218
ZOLOTOVA et al.
Table 2. Xꢀray crystallographic data for Cs2Ni2(MoO4)3
xNi2 + x(MoO4)3, the twoꢀphase region was taken to be
2
twoꢀdimensional, not linear, in accordance with the
rules of triangulation of ternary diagrams with variꢀ
ableꢀcomposition phases [26, 27].
Crystal system
Space group
Cubic
213
P
When choosing a temperature interval for solidꢀ
phase synthesis, we took into account the decomposiꢀ
tion temperatures of the double molybdates (Table 1).
Joins inside triangles were examined in 5–12.5 mol %
steps (Figs. 1a, 1b). The compositions corresponding
to the intersection points of joins connecting the repꢀ
resentative points of a component and a double
molybdate in the ternary systems were prepared in two
ways, namely, from the starting simple molybdates and
from double molybdates belonging to boundary sysꢀ
a
, Å
10.7538(1)
1243.61(2)/4
4.610
Unit cell volume, Å3/
ρtheor, g/cm3
ρexp, g/cm3
Z
4.60
µ
(Mo
K
), mm–1
11.737
α
Crystal dimensions, mm
Scattering angle ( ) range, deg
0.11
×
0.06 × 0.06
θ
2.68–27.40
8471
tems. Samples were annealed at 400–600
200 h with intermittent regrindings one or two times a
day. The annealing temperature was raised by 10–50
°
C for at least
Total number of reflections
Number of reflections involved in strucꢀ
ture determination [
956
°C
I
> 2
σ(I
)]
[
R
(int) = 0.0208]
every 50 h. The equilibration of the samples was
checked by Xꢀray diffraction.
Number of refined parameters
p
59
Search for new phases was also performed with the
flux crystallization method. The loads were the
annealed mixtures corresponding to the intersection
points of joins, and the solvents were alkaliꢀmetal
polymolybdates. The load : solvent ratio was varied
between 1 : 1 and 1 : 3. The molten mixtures were
homogenized at 500–600 С for 20–24 h, and cooled
at a rate of 3–5 K/h.
The samples obtained by solidꢀphase synthesis and
flux crystallization were characterized by Xꢀray difꢀ
Extinction coefficient
0.00406(8)
1.151
Goodness of fit
(calc)2]2 / (
n –
S
p
= [
Σ
w[(F
(exp)2 –
F
)]1/2
R
(F
) for > 2
I
σ
(I
)
0.0082
0.0211
0.0083
0.0212
0.016(11)
wR
(
F2) for
I
> 2σ(I)
°
R
(F
) for all reflections
wR
(
F2) for all reflections
fraction (DRONꢀ3M diffractometer, Cu
K radiation,
Absolute structure parameter
α
scan speed of 1 deg/min) and thermal analysis. An
original thermal analyzer was used, which allowed
heating/cooling and DTA curves to be recorded with a
thermal event temperature determination error of
Δρ extrema, e/Å3
0.299/–0.215
Table 3. Atomic coordinates and the equivalent isotropic
atomic displacement parameters for the Cs2Ni2(MoO4)3 strucꢀ
ture
10
chromel–alumel thermocouple, whose cold junctions
were thermostated at . The sample to be examined
(0.2 g) was placed in a quartz crucible and was heated from
room temperature to 1000 at a rate of 10 deg/min. The
density of substances was measured pycnometrically in
toluene at 20 0.1
with an accuracy of 0.2 g/cm3.
°
C. The temperature was measured with a
0°C
Å2
*
Ueq,
Atom
Cs(1)
x
/
a
y/
b
z/c
°C
0.0707(1) 0.0707(1) 0.0707(1) 0.0167(1)
0.2909(1) 0.2909(1) 0.2909(1) 0.0240(1)
0.6262(1) 0.4472(1) 0.2764(1) 0.0084(1)
0.5874(1) 0.5874(1) 0.5874(1) 0.0092(1)
0.8625(1) 0.8625(1) 0.8625(1) 0.0087(1)
0.6459(2) 0.4958(2) 0.4312(2) 0.0167(4)
0.5114(2) 0.5366(2) 0.2017(2) 0.0179(4)
0.5796(2) 0.2900(2) 0.2649(2) 0.0170(4)
0.7663(2) 0.4741(2) 0.1956(2) 0.0180(4)
°C
Cs(2)
Mo
One of the grown Cs2Ni2(MoO4)3 crystals was taken
for Xꢀray structure analysis. Data collection and unit
cell refinement were carried out at room temperature
on a BrukerꢀNonius X8 Apex automated diffractomeꢀ
Ni(1)
Ni(2)
O(1)
O(2)
O(3)
O(4)
ter (
area detector,
λ
MoK radiation, graphite monochromator, CCD
α
ϕ
ꢀscans with Δϕ
=
0.5 ). Absorption
°
correction was applied by averaging over equivalent
reflections. Structures were determined and refined in
an anisotropic approximation using the SHELXꢀ97
program package [28].
*
U = (U + U + U )/3.
eq 11 22 33
The color parameters of nickelꢀcontaining double
molybdates were calculated according to the CIE Labꢀ
76 standard [29], using the reflection spectra of powꢀ
ders recorded on an SFꢀ18 spectrophotometer with a
barium sulfate–coated photometric sphere. Using the
spectral characteristics of the light source and eye senꢀ
sitivity data [30], we calculated the following three
(A = K, Rb, Cs) systems in air were studied by trianꢀ
gulation of isothermal sections, dividing them into
secondary ternary systems by means of the intersecting
joins method [25, 26]. Because of the existence of a
homogeneity range for the double molybdate Li2 – color parameters: colorfulness (С, %), which characterꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

PHASE FORMATION
1219
Table 4. Selected interatomic distances (Å) in the Cs2Ni2(MoO4)3 structure
Mo tetrahedron
MoꢀO(1)
Ni(1) octahedron
Ni(2) octahedron
1.758(2)
1.758(2)
1.763(2)
1.767(2)
1.762
Ni(1)ꢀO(1)
Ni(1)ꢀO(4)
Ni(1)ꢀO
2.046(2)
2.066(2)
2.056
×
×
3
3
Ni(2)ꢀO(2)
Ni(2)ꢀO(4)
Ni(2)ꢀO
2.045(2)
2.054(2)
2.050
×
×
3
MoꢀO(2)
MoꢀO(4)
MoꢀO(3)
3
〈
〉
〈
〉
〈Mo(1)ꢀO
〉
Cs(1) polyhedron
Cs(2) polyhedron
Cs(1)ꢀO(1)
Cs(1)ꢀO(2)
Cs(1)ꢀO(4)
Cs(1)ꢀO(4')
3.153(2)
3.212(2)
3.235(2)
3.586(2)
3.297
×
×
×
×
3
3
3
3
Cs(2)ꢀO(3)
Cs(2)ꢀO(2)
Cs(2)ꢀO(4)
3.116(2)
3.465(2)
3.465(2)
3.349
×
×
×
3
3
3
〈Cs(2)ꢀO
〉
〈Cs(1)ꢀO
〉
izes the difference between the given color and gray;
lightness ( , %) as the difference between the given color
and white; and hue ( , deg). Pure yellow color is characꢀ
terized by = 90°; pure orange color, by = 48°.
Search experiments using the flux crystallization
technique did not reveal any nickelꢀcontaining triple
molybdates either. In all cases, we obtained only colꢀ
orless crystals of ALiMoO4 (A = K, Rb, Cs) and yellow
(yolk yellow) crystals of alkaliꢀmetal nickel molybꢀ
dates. The crystals of lithium nickel molybdate are
lemon yellow. The crystals were identified by Xꢀray
diffraction, and the obtained data were found to be in
good agreement with the literature. The solidification
of the molten Li2MoO4 + Cs2MoO4 + 2NiMoO4 +
L
H
H
H
RESULTS AND DISCUSSION
The boundary binary systems of the Li2MoO4–
A+2MoO4 (A+ = K, Rb, Cs) concentration triangles
were reported earlier in detail, so they were not revised
in this study. The only compounds forming in the
Li2MoO4–A2MoO4 (A = K, Rb, Cs) systems are the
congruently melting double molybdates ALiMoO4
[31–33]. The phase relations in the A2MoO4–NiMoO4
(A = Li, Na, K, Rb, Cs) systems were described above.
All alkaliꢀmetal nickel molybdates melt incongruently
between 650 and 755°C (Table 1), yielding solid NiO
and molten alkaliꢀmetal polymolybdates [12].
2Cs2Mo2O7 mixture (homogenized at 600 С) and
°
cooled at a rate of 5 K/h yielded Cs2Ni2(MoO4)3 crysꢀ
tals. One of the grown crystals was selected for Xꢀray
structure analysis.
The unit cell parameters of the crystal and the
observed systematic absences (
sistent with the centrosymmetric space group
h
00: h =
2
n
) were conꢀ
P
213
,
which is characteristic of langbeinite, K2Mg2(SO4)3
[34]. The coordinates of the heavy atoms in the langꢀ
beinite structure were used as the initial approximaꢀ
After the equilibrated samples corresponding to the
intersection points of joins were quenched from
510 С, their Xꢀray diffraction patterns did not indicate
°
tion, but their isotropic refinement led to
R = 0.462.
the presence of any phase other than the starting comꢀ
ponents and the double molybdates existing on the
sides of the concentration triangle. This result was
independent of whether the sample was obtained from
the starting components or from the double molybꢀ
dates belonging to the boundary systems. These data
were confirmed by exploring the A2MoO4–
For this reason, the structure was solved by direct
methods of determining the phases of structure ampliꢀ
tudes. The peaks revealed by Еꢀsynthesis were assigned
to Mo, Cs(1), Cs(2), Ni(1), and Ni(2). The refineꢀ
ment of the coordinates and isotropic thermal paramꢀ
eters of these atoms led to
R = 0.014. Next, four indeꢀ
pendent oxygen atoms were located from difference
electron density map. The resulting model was refined
Li2Ni2(MoO4)3,
Li2MoO4–A2Ni2(MoO4)3
,
and
A2Ni2(MoO4)3–Li2Ni2(MoO4)3 (A = K, Rb, Cs) joins
and the ALiMoO4–A2Ni2(MoO4)3 (A = K, Rb) join in
the subsolidus region of the Li2MoO4–A2MoO4–
NiMoO4 systems (Figs. 1, 1b). The ternary systems
were triangulated by the quasibinary joins revealed in
this way (Figs. 1c, 1d). These subsolidus data for the
Li2MoO4–A2MoO4–NiMoO4 (A = K, Rb, Cs) systems
up to
R = 0.0447 by least squares in the isotropic
approximation with an experimental weighting
scheme, but the corresponding absolute structure
parameter was
х = 0.99(4). After the structure was
inverted, it was refined anisotropically with a secondꢀ
ary extinction correction applied at the final stage.
This led to
R = 0.0082. The Xꢀray crystallographic
at 510 С indicate that the ternary systems involving
°
data are listed in Table 2. The coordinates and equivaꢀ
lent isotropic thermal parameters of the basis atoms
are presented in Table 3; interatomic distances, in
Table 4.
potassium and rubidium (Fig. 1c) are divided by four
quasibinary joins into five secondary triangles and the
ternary system involving cesium (Fig. 1d) is divided
into four ones.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

1220
ZOLOTOVA et al.
MoO4
b
a
c
NiO6
Cs
Fig. 2. General view of the Cs Ni (MoO ) structure.
2
2
4 3
In the Cs2Ni2(MoO4)3 structure, the molybdenum are similar to the same distances in the Cs2Co2(MoO4)3
[22] and Cs2Cd2(MoO4)3 [35] phases isostructural to
cesium nickel molybdate. The isolated NiO6 octaheꢀ
dra share vertices with MoO4 tetrahedra, forming an
open threeꢀdimensional framework (Fig. 2), whose
large cavities accommodate cesium ions.
atoms are crystallographically equivalent and are in
general position and the other metal atoms are on
threefold axes. The MoO4 tetrahedra are distorted only
slightly, with a mean Mo–O bond length of 1.761 Å.
The crystallographically independent cations Ni(1)
and Ni(2) are octahedrally coordinated. The inequivꢀ
alent cations Cs(1) and Cs(2) are inside 9ꢀ and 12ꢀverꢀ
tex polyhedra, respectively. The Cs–O distances here
It was mentioned above that all crystals and polyꢀ
crystalline samples of the nickelꢀcontaining molybꢀ
dates are yellow. Table 5 lists the color parameters of
the double molybdates for a source of light designated
D65. The relative spectral energy distribution of D65
and, accordingly, the correlated color temperature of
this light source at 6500 K are in good agreement with
the same characteristics of the total radiation from the
sky and the Sun measured on a horizontal surface. The
variation of the height of the Sun above the horizon
over the time interval between 2 h after sunrise and 2 h
before sunset and the changes in the sky conditions
from overcast to clear exert only a slight effect on the
relative spectral energy distribution of daylight inciꢀ
dent on a horizontal surface throughout the visible
spectral range [30]. For other light sources, the three
color parameters of the pigments vary within a narrow
range and are not presented here. The double molybdates
have sufficiently high color characteristics (Table 5) to be
usable as pigments [35].
Table 5. Color characteristics of alkaliꢀmetal nickel molybꢀ
dates
Color parameters
Compound
L
, %
C
, %
H, deg
Li2Ni2(MoO4)3
Na3.86Ni1.07(MoO4)3
Na2Ni2(MoO4)3
K2Ni(MoO4)2
84.6
79.9
67.7
84.1
82.9
83.5
83.4
83.3
50.8
61.4
59.2
56.2
49.5
54.6
58.6
66.8
81.4
74.5
68.2
83.1
79.5
82.5
83.1
84.3
K2Ni2(MoO4)3
Rb2Ni(MoO4)2
Rb2Ni2(MoO4)3
Cs2Ni2(MoO4)3
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

PHASE FORMATION
1221
16. R. F. Klevtsova, L. A. Glinskaja, S. F. Solodovnikov,
and P. V. Klevtsov, Z. Kristallogr., Suppl. 2, 98 (1990).
17. C. Gicquel, C. Mayer, and G. Perez, Rev. Chim. Miner.
12 (6), 537 (1975).
18. P. V. Klevtsov, V. G. Kim, and R. F. Klevtsova, Kristalꢀ
lografiya 25 (2), 301 (1980).
19. R. F. Klevtsova and L. A. Glinskaya, Zh. Strukt. Khim.
23 (5), 176 (1982).
20. P. V. Klevtsov, V. G. Kim, R. F. Klevtsova, et al., Kristalꢀ
ACKNOWLEDGMENTS
The authors are grateful to O.V. Matveev and
I.Yu. Filatova for their assistance in the study of triple
molybdates and to D.Yu. Naumov and N.V. Kurat’eva
for the Xꢀray diffraction analysis of crystals on an X8
Apex automated diffractometer.
This study was supported by the Russian Foundaꢀ
tion for Basic Research, grant no. 08ꢀ03ꢀ00384.
lografiya 33 (1), 57 (1988).
21. M. Müller, B. O. Hildmann, and Th. Hahn, Z. Kristalꢀ
REFERENCES
logr. 174 (1ꢀ4), 152 (1986).
22. S. F. Solodovnikov, R. F. Klevtsova, V. G. Kim, and
1. M. V. Mokhosoev and Zh. G. Bazarova, Complex
Oxides of Molybdenum and Tungsten with Group I–IV
Elements (Nauka, Moscow, 1990) [in Russian].
P. V. Klevtsov, Zh. Strukt. Khim. 27 (6), 100 (1986).
2. S. F. Solodovnikov, R. F. Klevtsova, and P. V. Klevtsov,
23. Zh. G. Bazarova, M. V. Mokhosoev, G. D. Tsyrenova,
Zh. Strukt. Khim. 35 (6), 145 (1994).
et al., Zh. Neorg. Khim. 35 (12), 3164 (1990).
3. A. K. IvanovꢀShits, A. V. Nistyuk, and N. G. Chaban,
Neorg. Mater. 15 (7), 891 (1999).
4. K. M. Begam, S. Selladurai, M. S. Michael, and
S. R. S. Prabaharan, Ionics 10 (1–2), 77 (2004).
5. V. A. Isupov, Ferroelectrics 322, 83 (2005).
6. V. Freitag and D. Stoie, Dyes, Coatings, and Solvents
(Professiya, St. Petersburg, 2007) [in Russian].
7. G. R. Rossman, R. D. Shannon, and R. K. Waring,
J. Solid State Chem. 39 (3), 277 (1981).
8. L. G. Van Uitert, R. C. Sherwood, H. J. Williams, et al.,
J. Phys. Chem. Solids 25 (12), 1447 (1964).
9. B. M. Wanklyn, F. R. Wondre, and W. Davidson,
24. T. M. Yanushkevich, V. M. Zhukovskii, and V. M. Ust’yantꢀ
sev, Zh. Neorg. Khim. 19 (7), 1932 (1974).
25. W. Guertler, Z. Anorg. Allg. Chem. 154 (1ꢀ4), 439
(1926).
26. A. M. Zakharov, Phase Diagrams of Binary and Ternary
Systems (Metallurgiya, Moscow, 1978) [in Russian].
27. A. M. Zakharov, Zh. Fiz. Khim. 17 (9), 2190 (1983).
28. G. M. Sheldrick, Acta Crystallogr., Sect. A 64, 112
(2008).
29. A. D. Sule, Colorage, No. 9, 23 (1992).
30. D. Judd and G. Wyszecki, Color in Business Science and
Industry (Wiley, New York, 1975; Mir, Moscow, 1978).
J. Mater. Sci. 11 (9), 1607 (1976).
31. F. Hoermann, Z. Anorg. Allg. Chem. 177 (2–3), 145
10. V. G. Penkova and P. V. Klevtsov, Zh. Neorg. Khim. 22
(1929).
(6), 1713 (1977).
32. I. N. Belyaev, Zh. Neorg. Khim. 6 (5), 1178 (1961).
11. M. Ozima, S. Sato, and T. Zoltai, Acta Crystallogr.,
Sect. B 33 (7), 2175 (1977).
12. S. F. Solodovnikov, Doctoral Dissertation in Chemistry
(Novosibirsk, 2000).
33. R. G. Samuseva, M. V. Bobkova, and V. E. Plyushchev,
Zh. Neorg. Khim. 14 (11), 3140 (1969).
34. A. Zemann and J. Zemann, Acta Crystallogr. 10 (6),
409 (1957).
13. V. A. Efremov, Yu. G. Petrosyan, and V. M. Zhukovskii,
Zh. Neorg. Khim. 22 (1), 175 (1977).
14. R. F. Klevtsova, S. V. Borisov, N. A. Bliznyuk, et al.,
35. Z. I. Khazheeva, G. D. Tsyrenova, M. V. Mokhosoev,
and Zh. G. Bazarova, Dokl. Akad. Nauk SSSR 303 (6),
1417 (1988).
Zh. Strukt. Khim. 32 (6), 127 (1991).
15. R. F. Klevtsova and P. V. Klevtsov, Kristallografiya 23 36. E. S. Zolotova, Z. A. Solodovnikova, S. F. Solodovniꢀ
(12), 261 (1978). kov, and B. M. Ayupov, Patent RU 2369621 (2009).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011