Synthesis, structure, and physicochemical properties of K[VO 2(SeO4)(H2O)] and K[VO2(SeO 4)(H2O)2] ? H2O

Article abstract of DOI:10.1134/S0036023611080262

The vanadium(V) complexes K[VO₂(SeO₄)(H ₂O)] and K[VO₂(SeO₄)(H₂O) ₂] ? H₂O were synthesized using original procedures; their physicochemical properties were studied, and the crystal structure was determined on the basis of X-ray diffraction and neutron diffraction data. The structure of K[VO₂(SeO₄)(H₂O)₂] ? H₂O is composed of VO₆ octahedra connected to form infinite chains by bridging SeO₄ tetrahedra. Each VO₆ tetrahedron has short terminal V-O bonds forming the bent dioxovanadium group VO ₂ ⁺ The unit cell parameters of K[VO₂(SeO ₄)(H₂O)₂] ? H₂O are a = 6.4045(1) ?, b = 9.9721(2) ?, c = 6.6104(1) ?, β = 107.183(1)°, V = 403.34 ?³, Z = 2, monoclinic system, space group P2₁. The complex K[VO₂(SeO₄)(H ₂O)] forms a two-dimensional layered structure composed of highly distorted VO₆ octahedra having two short terminal V-O bonds and SeO₄ groups coordinated simultaneously by three vanadium atoms. This compound crystallizes in the monoclinic system (space group P2₁/c): a = 7.3783(1) ?, b = 10.5550(2) ?, c = 10.3460(2) ?, β = 131.625(1)°, V = 602.894(5) ?³, Z= 4. The vibrational spectra of the studied compounds are fully consistent with their structural features.

Full text of DOI:10.1134/S0036023611080262

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
ISSN 0036ꢀ0236, Russian Journal of Inorganic Chemistry, 2011, Vol. 56, No. 8, pp. 1168–1177. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © A.P. Tyutyunnik, V.N, Krasil’nikov, I.F. Berger, V.G. Zubkov, L.A. Perelyaeva, I.V. Baklanova, 2011, published in Zhurnal Neorganicheskoi Khimii, 2011,
Vol. 56, No. 8, pp. 1238–1247.
SYNTHESIS AND PROPERTIES
OF INORGANIC COMPOUNDS
Synthesis, Structure, and Physicochemical Properties
of K[VO2(SeO4)(H2O)] and K[VO2(SeO4)(H2O)2] · H2O
A. P. Tyutyunnik, V. N, Krasil’nikov, I.F. Berger, V. G. Zubkov,
L. A. Perelyaeva, and I. V. Baklanova
Institute of SolidꢀState Chemistry, Ural Branch, Russian Academy of Sciences,
ul. Pervomaiskaya 91, Yekaterinburg, 620219 Russia
Received December 22, 2009
Abstract—The vanadium(V) complexes K[VO2(SeO4)(H2O)] and K[VO2(SeO4)(H2O)2]
sized using original procedures; their physicochemical properties were studied, and the crystal structure was
determined on the basis of Xꢀray diffraction and neutron diffraction data. The structure of
K[VO2(SeO4)(H2O)2] H2O is composed of VO6 octahedra connected to form infinite chains by bridging SeO4
tetrahedra. Each VO6 tetrahedron has short terminal V–O bonds forming the bent dioxovanadium group
⋅
H2O were syntheꢀ
⋅
+
The unit cell parameters of K[VO2(SeO4)(H2O)2]
⋅
H2O are
a
= 6.4045(1)
Å
,
b
= 9.9721(2)
Å, c =
VO2.
6.6104(1)
Å
,
β
= 107.183(1)
°,
V
= 403.34 Å3
,
Z
= 2, monoclinic system, space group P
21. The complex
K[VO2(SeO4)(H2O)] forms a twoꢀdimensional layered structure composed of highly distorted VO6 octahedra
having two short terminal V–O bonds and SeO4 groups coordinated simultaneously by three vanadium atoms.
This compound crystallizes in the monoclinic system (space group P21/c): a = 7.3783(1) Å, b = 10.5550(2) Å,
c
= 10.3460(2)
Å
,
β
= 131.625(1)
°
,
V
= 602.894(5) Å3
,
Z= 4. The vibrational spectra of the studied compounds
are fully consistent with their structural features.
DOI: 10.1134/S0036023611080262
M2O–V2O5–SO3–H2O systems (where M is an
alkali element except for lithium) model the active
component of vanadium sulfuric acid catalysts at the
hydrochemical stage of their synthesis [1]. A characꢀ
teristic feature of these and similar systems, where M
is an alkali metal, thallium(I), or ammonium, is the
formation of complexes of the following composition:
EXPERIMENTAL
The synthesis procedures of K[VO2(SeO4)(H2O)2]
H2O and K[VO2(SeO4)(H2O)] were based on the folꢀ
⋅
lowing reactions
KVO3 + 2H2SeO4 = KVO(SeO4)2 + 2H2O
↑
,
(1)
KVO SeO + 4H2O
(
)
4
2
(2)
(3)
M[VO2(SO4)(H2O)2]
3], M[VO2(SO4)(H2O)2] (M = Cs, NH4) [1, 3, 4],
0.67Na0.33[VO2(SO4)(H2O)2] (M = K, Rb, Cs, NH4
⋅
H2O (M = K, Rb, Tl, NH4) [1–
= K VO SeO H O ⋅ H O + H SeO ,
4 )(
(
)
]
[
2
2
2
2
4
2
KVO3 + H2SeO4 = K[VO2(SeO4)(H2O)].
M
)
[1, 5, 6]. The compounds were synthesized by crystalꢀ
lization from sulfuric acid solutions and by hydrolysis
of MVO(SO4)2 under saturated water vapor at room
temperature. Keeping KVO(SO4)2 in a saturated water
Reaction (2) was performed by keeping
KVO(SeO4)2 in a closed desiccator above water for a
week. The K[VO2(SeO4)(H2O)2]
⋅
H2O crystals thus
formed were separated from the mother liquor by vacꢀ
uum filtration, washed with acetone, dried at room
temperature and stored in bottles with little free volꢀ
ume. The synthesis of the monohydrate
K[VO2(SeO4)(H2O)] included the following operaꢀ
tions. Potassium metavanadate KVO3 was dissolved in
dilute selenic acid prepared from 85% reagent grade
H2SeO4, and the solution was heated to 70°C and conꢀ
centrated at this temperature to precipitate the crystals
of K[VO2(SeO4)(H2O)], which were collected on a
vapor atmosphere at 40°C for many hours gave the
monohydrate K[VO2(SO4)(H2O)], which was studied
by Xꢀray diffraction [7]. A similar selenate complex,
K[VO2(SeO4)(H2O)], is known to be formed upon sponꢀ
taneous dehydration of K[VO2(SeO4)(H2O)2] H2O at
⋅
room temperature [1]. Since no published data on the
structure and properties of K[VO2(SeO4)(H2O)] and
K[VO2(SeO4)(H2O)2] H2O were available, the key goal
⋅
of this work was to study the formation conditions,
crystal structure, and the physicochemical properties
of these compounds.
vacuum filter, washed with acetone, and dried at 40
In addition, this compound was obtained by spontaneꢀ
ous dehydration of K[VO2(SeO4)(H2O)2] H2O taking
°C.
⋅
1168

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
SYNTHESIS, STRUCTURE, AND PHYSICOCHEMICAL PROPERTIES
102, Å2) in the structure K[VO2(SeO4)(H2O)]
Uiso
1169
Table 1. Atom coordinates and thermal parameters (Uiso
Atom Position
×
x
/a
y
/b
z/
c
/
Ueq
×
102
K
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
4e
0.3370(3)
0.0759(3)
0.8999(2)
0.1139(8)
0.2269(8)
0.7956(8)
0.4527(8)
0.6796(8)
0.1311(7)
0.0200(8)
0.557(4)
0.0701(2)
0.0919(2)
0.1955(1)
0.1894(5)
0.9468(4)
0.0565(4)
0.1617(4)
0.2941(5)
0.0353(4)
0.2284(5)
0.146(3)
0.2528(2)
0.7440(2)
0.3615(1)
0.5729(5)
0.7186(5)
0.5858(6)
0.9096(5)
0.2918(5)
0.9136(5)
0.2760(6)
0.035(2)
5.7(2)
4.5(1)
4.6(1)
3.5(3)
4.0(3)
4.7(3)
4.8(3)
5.2(3)
4.7(3)
6.0(3)
5.00
V
Se
O(1)
O(2)
O(3)
O(4)H2
O(5)
O(6)
O(7)
H(1)
H(2)
0.551(4)
0.158(3)
0.876(3)
5.00
wRp
1.88
2.18
Rp
R
(
F2
)
CHI2
2.811
2.811
Xꢀrays
1.31
1.74
3.47
3.57
Neutrons
place on keeping the sample in a closed desiccator specialꢀpurity grade K2CO3 and V2O5. The completeꢀ
above a dehydrating agent (P2O5). Potassium metavanꢀ ness of conversion and the purity of products were
adate KVO3 needed for reaction (3) was synthesized by checked using a POLAM Sꢀ112 transmission light
solidꢀstate annealing of a stoichiometric mixture of polarization microscope and by Xꢀray diffraction. The
Δ
m, mg
(а)
(b)
315°С
0
Δ
m, mg
TG
0
316°C
2
4
1
2
3
4
5
6
TG
DTA
DTA
6
122
210
200
137
253
100
200
300
T, °С
100
300
T, °С
Fig. 1. TG and DTA curves for (a) K[VO (SeO )(H O)] and (b) K[VO (SeO )(H O) ] ⋅ H O powders.
2
2
4
2
2
4
2
2
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
1170
TYUTYUNNIK et al.
) and bond angles ( ) in
Table 2. Interatomic distances (
K[VO2(SeO4)(H2O)]
d
ω
IR absorption spectra were measured on a Vertex 80
Bruker FT IR spectrometer in the range of 200–
4000 cm–1 for powdered samples (CsI pellets), the
Raman spectra were recorded using a RAMII
attachment module compatible with the Vertex 80
Bond
V–O(1)
d
, Å
Bond
d, Å
2.221(4) K–O(1)
2.011(5) K–O(2)
1.612(4) K–O(3)
2.210(4) K–O(3)
1.629(4) K–O(4)
2.016(5) K–O(5)
2.924(5)
3.035(4)
2.803(4)
2.776(4)
3.089(4)
3.285(5)
2.940(6)
2.771(4)
2.870(4)
3.012(5)
2.95
FT IR spectrometer ( = 1064 nm, Р = 500 mW).
λ
Thermogravimetric analysis was carried out on a
Shimadzu DTGꢀ60 thermal analyzer at a heating
rate of 10 K/min in air.
V–O(2)
V–O(3)
V–O(4)
V–O(6)
V–O(7)
Mean
The Xꢀray diffraction patterns were measured in
Cu
K radiation on a STADIꢀP automated diffractoꢀ
α
1
meter equipped with miniꢀPSD in the transmission
geometry with a scanning step = 0.02 in angle
range from 2° to 120°. Polycrystalline silicon (
5.43075(5) Å) was used as the external standard. The
possible impurity phases were identified using the
Powder Diffraction Database ICDD PDF2 (ICDD,
USA, Release 2007). The neutron diffraction patterns
were measured on a D7A setup of the IVV 2M reactor
Δ2θ
°
2θ
a
=
1.95
K–O(5)
K–O(6)
K–O(6)
V
+5 VI–O–2III* 1.90
(manufactured in the town of Zarechnyi) in
range from 5° to 135° with a step of 0.05 at the neuꢀ
tron wavelength = 1.532 Å. The crystal structures
2θ angle
Se–O(1)
Se–O(2)
Se–O(5)
Se–O(7)
Mean
1.642(4) K–O(7)
°
1.671(5) Mean
λ
were solved and refined using simultaneously neutron
and Xꢀray diffraction data and EXPO and GSAS softꢀ
ware [8, 9]. The line profile was approximated by the
1.640(5) K+ X–O–2III* 2.95
1.653(4)
pseudoꢀVoigt function
*G(2 ) ( and are the Lorentz and Gauss funcꢀ
tions, respectively), and the angular dependence of the
line width was approximated by the relation
FWHM)2 =
tan2
tan , where FWHM is the full width
at half maximum. The background level was specified
as a combination of fifteen Chebyshev polynomials.
The structural parameters obtained upon the refineꢀ
ment and the shortest interatomic distances and bond
angles are presented in Tables 1–4.
I(2θ)
=
η*L(2θ) + (1 –
1.65
η
)
θ
L
G
Se+6 IV–O–2III* 1.64
(
U
θ
+
V
θ
+ W
Angle
ω
, deg
Angle
ω
, deg
O(1)VO(2)
O(1)VO(3)
O(1)VO(4)
O(1)VO(6)
O(1)VO(7)
O(2)VO(3)
O(2)VO(4)
O(2)VO(6)
O(2)VO(7)
O(3)VO(4)
O(3)VO(6)
VO(1)Se
82.8(2) O(3)VO(7)
93.1(2) O(4)VO(6)
72.7(2) O(4)VO(7)
162.8(2) O(6)VO(7)
80.9(2)
96.9(2)
90.1(2)
81.3(2)
95.8(2)
RESULTS AND DISCUSSION
Microscopic analysis showed that spontaneous
dehydration of K[VO2(SeO4)(H2O)2] ·H2O whose powꢀ
98.0(2) O(1)SeO(2)
80.5(2) O(1)VO(5)
95.6(2) O(1)VO(7)
158.4(2) O(2)VO(5)
165.9(2) O(2)VO(7)
104.1(2) O(5)VO(7)
124.2(2) VO(7)Se
125.0(3)
110.6(2)
114.0(2)
109.8(2)
106.8(2)
104.2(2)
11.1(2)
der is deeply yellowꢀcolored affords slightly colored
yellowish phase of K[VO2(SeO4)(H2O)]; the originally
coarse prismatic crystals of the trihydrate are conꢀ
verted to agglomerates of very small particles of the
new compound. By crystallization from a selenium
acid solution, we isolated wellꢀformed crystals of
K[VO2(SeO4)(H2O)] as skewꢀangle plates and up to
50 mꢀlong prisms colored intensely yellow, as
μ
opposed to K[VO2(SO4)(H2O)], which is colored
orange [7]. The cleavage of the crystals of
K[VO2(SeO4)(H2O)] is perfect on pinacoid (010) and
moderate in other orientations; the refractive indices
are Ng = 1.757 (lightꢀyellow), Nm = 1.692 (colorless),
and Np = 1.656 (colorless). The wellꢀformed prismatic
121.8(3)
VO(2)Se
* The mean values are shown in bold and the sums of crystal radii
according to [12] are given in italis.
crystals of K[VO2(SeO4)(H2O)2] · H2O are a combinaꢀ
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011

Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
SYNTHESIS, STRUCTURE, AND PHYSICOCHEMICAL PROPERTIES
102, Å2) in the structure K[VO2(SeO4)(H2O)2
1171
Table 3. Atom coordinates and thermal parameters (Uiso
×
]
⋅
H2O
102
U
Atom
Position
x
/a
y
/b
z/
c
Uiso/
×
eq
K
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
0.2971(8)
0.6110(5)
0.0737(4)
0.464(2)
0.320(2)
0.448(2)
0.306(2)
0.917(2)
0.308(2)
0.015(2)
0.959(2)
0.137(2)
0.770(4)
0.115(4)
–0.009(3)
0.672(3)
0.784(4)
0.544(4)
0.8465(7)
0
0.8081(8)
0.3823(5)
0.2721(4)
0.860(2)
0.470(2)
0.735(2)
0.313(2)
0.417(2)
0.428(2)
0.060(2)
0.782(2)
0.788(2)
0.675(4)
0.927(2)
0.677(3)
0.246(5)
0.824(3)
0.676(5)
2.9(2)
0.9(1)
2.5(1)
2.1(1)
2.1(1)
2.1(1)
2.1(1)
2.1(1)
2.1(1)
2.1(1)
2.1(1)
2.1(1)
3.7(3)
3.7(3)
3.7(3)
3.7(3)
3.7(3)
3.7(3)
V
Se
–0.0022(7)
0.538(1)
0.627(1)
0.286(1)
0.378(1)
0.947(1)
0.981(1)
0.916(1)
0.659(1)
0.139(1)
0.793(2)
0.128(3)
0.133(3)
0.724(2)
0.920(2)
0.226(3)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
H(1)
H(2)
H(3)
H(4)
H(5)
H(6)
wRp
2.77
1.05
Rp
R
(
F2
)
CHI2
2.187
2.187
Xꢀrays
2.04
0.83
4.81
4.61
Neutrons
tion of three pinacoids, (100), (010), and (001), and
two rhombic prisms, (110), (011). The acute angle
between the faces of the rhombic prism (011) at the
bisecting line of Np is close to 64°. Pleochroism is
weakly manifested with color change from light yellow
The dehydration of K[VO2(SeO4)(H2O)] occurs in
two stages, which are characterized by minima in the
DTA curve at 210 and 253
TG curve (Fig. 1a). The exotherm in the DTA curve
with a maximum at 315 is caused by crystallization
°C and an inflection in the
°C
(
Ng) to colorless (Np). The refractive indices of the
of the amorphous dehydration product of the nominal
composition KVO2SeO4. The slight inflection in the
TG curve is caused by partial decomposition of the
compound with removal of selenium dioxide and oxyꢀ
K[VO2(SeO4)(H2O)2] H2O crystals are much lower
·
than those for the monohydrate: Ng = 1.656 (light yelꢀ
low), Nm =1.619 (colorless), and Np = 1.575 (colorꢀ
less).
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 56 No. 8 2011