K4VP2S9

Article abstract of DOI:10.1107/S0108270103026623

The new quaternary group V thiophosphate K₄VP₂S ₉ (tetrapotassium vanadium diphosphorus nonasulfide) was prepared by reacting a mixture of K₂S₃, VP, P₄S ₃ and S. The crystal structure consists of discrete [VS(PS ₄)₂]^4- anions and K⁺ cations. The V⁴⁺ cation is in a fivefold coordination of S atoms which form a square-pyramidal environment. Each VS₅ group shares a common edge with two bidentate [PS₄] tetrahedra, yielding the complete anion. The anions are stacked in the direction of the crystallographic b axis and are separated by the K⁺ ions.

Full text of DOI:10.1107/S0108270103026623

inorganic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
The crystal structure of K4VP2S9 is built up of discrete
[VS(PS4)2]4 anions which are well separated by K+ cations.
The V4+cation is in an unusual ®vefold coordination of S
atoms, forming a square-pyramidal environment. The VÐS
ISSN 0108-2701
Ê
distances range from 2.1132 (9) to 2.3823 (19) A. The mean
Ê
VÐS bond length of 2.324 A is in good agreement with the
K4VP2S9
2
sum of the ionic radii [1.84 A for S and 0.53 A for V
4+
Ê
Ê
(coordination number 5); Shannon, 1976]. The shortest VÐS
bond is observed to the non-coordinated terminal S1 atom at
Ê
the top of the pyramid. The Vatom is located 0.71 (1) A above
Andreas Gutzmann, Christian Nather and Wolfgang
È
Bensch*
the square plane of the pyramid formed by atoms S2±S5.
Each VS5 polyhedron shares common edges with two
bidentate [PS4]3 tetrahedra, forming the [VS(PS4)2]4 anion.
In both [PS4] tetrahedra, two types of PÐS bonds can be
distinguished, depending on how the S atoms are bonded.
Institut fur Anorganische Chemie, Christian-Albrechts-Universitat Kiel,
È
È
Olshausenstraûe 40, D-24089 Kiel, Germany
Correspondence e-mail: wbensch@ac.uni-kiel.de
Received 24 October 2003
Accepted 19 November 2003
Online 17 January 2004
Ê
They range from 1.9922 (17) to 2.100 (3) A, with the shorter
bond to the terminal S atoms. These differences in the PÐS
distances are a result of the partial double-bond character to
the terminal S atoms. Very similar bond distances are found in,
for example, P4S10 (Vos & Wiebenga, 1955), K4Pd(PS4)2
(Chondroudis et al., 1997) and K6[Cr2(PS4)4] (Derstroff et al.,
1998). The SÐPÐS angles deviate from ideal tetrahedral
geometry and range from 95.81 (10) to 114.76 (11)ꢀ for SÐ
P1ÐS and from 96.46 (10) to 113.88 (11)ꢀ for SÐP2ÐS. The
smallest SÐPÐS angles are observed for the S atoms which
are bound to the V atom.
The new quaternary group V thiophosphate K4VP2S9 (tetra-
potassium vanadium diphosphorus nonasul®de) was prepared
by reacting a mixture of K2S3, VP, P4S3 and S. The crystal
structure consists of discrete [VS(PS4)2]4 anions and K+
cations. The V4+ cation is in a ®vefold coordination of S atoms
which form a square-pyramidal environment. Each VS5 group
shares a common edge with two bidentate [PS4] tetrahedra,
yielding the complete anion. The anions are stacked in the
direction of the crystallographic b axis and are separated by
the K+ ions.
Comment
Group V transition metal thiophosphates have been exten-
sively investigated and are known for their low-dimensional
crystal structures and interesting physical properties. In the
structures of compounds in the A±M±P±S system (where A is
an alkali metal and M is a group V metal), the dimensionality
of the anionic parts varies from one-dimensional chains to
three-dimensional interconnected networks. In our investiga-
tions of the A±M±P±S family, we have demonstrated that a
systematic variation of the reaction parameters, e.g.
temperature, reaction time, stoichiometry and type of starting
materials, leads to the formation of new quaternary thio-
phosphates with interesting structural features. Very recently,
we have prepared new quaternary thiophosphates with group
V metals, such as Rb2Nb2P2S11 (Gutzmann & Bensch, 2002),
Rb4Ta4P4S24 (Gutzmann & Bensch, 2003) and Cs2Ta2P2S12
(Gutzmann et al., 2004), enhancing the rich structural chem-
istry. The structural features of the known two- and one-
dimensional quaternary vanadium thiophosphates 2D-
AVP2S7 (A is K or Rb; Kopnin et al., 2000; Durand et al., 1993),
1D-K2VP2S7 (Tremel et al., 1995) and 1D-NaV0.84P2S6 (Coste
et al., 2003) are VS6 octahedra connected by shared edges with
either other VS6 octahedra or with [PxSy]n units. Using a
molten alkali metal polythiophosphate ¯ux, we have synthe-
sized the ®rst quaternary vanadium thiophosphate containing
discrete [VS(PS4)2]4 anions, the title compound, K4VP2S9.
We report here the synthesis and structural characterization of
this new compound.
Figure 1
The crystal structure of the [VS(PS4)2]4 anion in K4VP2S9, with the
atomic labelling scheme. Displacement ellipsoids are drawn at the 50%
probability level.
The [VS(PS4)2]4 anions are stacked parallel to the crys-
tallographic b axis and a similar arrangement is also found
along the a axis, but the terminal S atoms of the [VS5] units
show an up±down±up orientation in the latter direction. The
four crystallographically independent K+ cations are in an
eightfold coordination. Cations K1 and K2 show an irregular
sulfur environment, whereas cations K3 and K4 are in an
approximately hexagonal±bipyramidal coordination. The
residual negative charge on the terminal S atoms leads to
shorter KÐS distances, due to the greater electrostatic
Ê
attraction. The mean KÐS distances are 3.42 (9) A for K1,
Ê
Ê
Ê
3.41 (9) A for K2, 3.30 (11) A for K3 and 3.31 (11) A for K4.
These values are in good agreement with the sum of the ionic
2
+
Ê
Ê
radii [1.84 A for S and 1.51 A for K (coordination number
8); Shannon, 1976].
Acta Cryst. (2004). C60, i11±i13
DOI: 10.1107/S0108270103026623
# 2004 International Union of Crystallography i11

inorganic compounds
Table 1
Selected geometric parameters (A, ).
It should be mentioned that the con®guration of K4VP2S9
allows interesting speculation concerning the possibility of
condensing several [VS(PS4)2] fragments via the bidentate
[PS4] tetrahedra or the terminal S1 atom to yield structures of
higher complexity. This might be achieved if molecular
ꢀ
Ê
K1ÐS1i
K1ÐS6ii
K1ÐS7i
K1ÐS4iii
K1ÐS8iv
K1ÐS9v
K1ÐS5i
K1ÐS5ii
K2ÐS1
3.288 (2)
3.300 (2)
3.334 (2)
3.451 (3)
3.454 (2)
3.463 (2)
3.5005 (13)
3.5346 (13)
3.299 (2)
3.308 (2)
3.334 (2)
3.4202 (19)
3.4382 (19)
3.441 (3)
3.4810 (13)
3.5713 (13)
3.148 (3)
3.188 (3)
3.244 (2)
K3ÐS3ii
K4ÐS1
K4ÐS5viii
K4ÐS8i
K4ÐS9i
K4ÐS6vi
K4ÐS7
K4ÐS4vi
K4ÐS4
V1ÐS1
V1ÐS4
V1ÐS3
V1ÐS5
V1ÐS2
P1ÐS6
P1ÐS7
P1ÐS5
P1ÐS4
P2ÐS9
P2ÐS8
P2ÐS3
P2ÐS2
3.4894 (12)
3.143 (3)
3.220 (3)
3.233 (2)
3.274 (2)
3.278 (2)
3.329 (2)
3.4638 (13)
3.5007 (13)
2.1132 (9)
2.370 (3)
K2ÐS9vi
K2ÐS8
K2ÐS6iii
K2ÐS7vii
K2ÐS3i
K2ÐS2
K2ÐS2vi
K3ÐS1i
K3ÐS2
K3ÐS7iii
K3ÐS9ii
K3ÐS6iii
K3ÐS8i
K3ÐS3i
2.377 (3)
2.3774 (18)
2.3823 (19)
1.9922 (17)
1.9963 (18)
2.093 (3)
2.097 (3)
2.0042 (17)
2.0073 (17)
2.083 (3)
3.2659 (19)
3.274 (2)
3.3166 (19)
3.4811 (12)
2.100 (3)
S1ÐV1ÐS4
S1ÐV1ÐS3
S4ÐV1ÐS3
S1ÐV1ÐS5
S4ÐV1ÐS5
S3ÐV1ÐS5
S1ÐV1ÐS2
S4ÐV1ÐS2
S3ÐV1ÐS2
S5ÐV1ÐS2
S6ÐP1ÐS7
107.42 (9)
107.60 (8)
144.99 (3)
107.19 (4)
81.82 (7)
88.29 (9)
107.30 (4)
87.47 (9)
81.92 (7)
145.50 (3)
114.76 (11)
S6ÐP1ÐS5
S7ÐP1ÐS5
S6ÐP1ÐS4
S7ÐP1ÐS4
S5ÐP1ÐS4
S9ÐP2ÐS8
S9ÐP2ÐS3
S8ÐP2ÐS3
S9ÐP2ÐS2
S8ÐP2ÐS2
S3ÐP2ÐS2
112.47 (8)
112.70 (8)
109.58 (7)
109.86 (7)
95.81 (10)
113.88 (11)
109.17 (8)
109.31 (8)
113.08 (8)
113.45 (8)
96.46 (10)
Figure 2
The crystal structure of K4VP2S9, viewed in the direction of the
crystallographic b axis.
precursor compounds such as the title compound were used in
the synthesis. In that case, it would establish a new method for
the synthesis of interesting solid-state thiophosphates.
1
Symmetry codes: (i) 1 x; 1 y; z 12; (ii) 1 x; 2 y; z 21; (iii) ‡ x; 32 y; z; (iv)
2
3
2
1
1
2
1
3
2
1
1
2
x; 12 ‡ y; z
x; y 12; z
;
.
(v)
x; y 12; z
;
2
(vi) x; y 1; z; (vii) ‡ x; 12 y; z; (viii)
Experimental
2
2
The title compound, K4VP2S9, was obtained by the reaction of K2S3
(0.8 mmol), VP (0.4 mmol), P4S3 (0.2 mmol) and S (2.4 mmol). K2S3
was prepared from a stoichiometric ratio of the elements in liquid
ammonia under an argon atmosphere. VP was prepared by heating
stoichiometric amounts of the elements at 1073 K in an evacuated
silica tube. The starting materials were loaded into a glass ampoule,
which was evacuated (10 3 mbar; 1 mbar = 100 Pa) and ¯ame-sealed.
The ampoule was heated to 773 K at 25 K h 1. After 4 d, the sample
was cooled to 523 K at 2 K h 1 and then to room temperature within
10 h. To remove unreacted KxPySz, the resultant melt was washed
with dry N,N-dimethylformamide and diethyl ether. The product was
dried in vacuo and consisted of red crystals which are air- and
moisture-sensitive. The MIR spectra of K4VP2S9 display strong
absorptions at 499, 522, 577 and 619 cm 1. Two additional weak
absorptions are observed at 418 and 669 cm 1. These values are
comparable with those of K3Bi(PS4)2 (McCarthy & Kanatzidis, 1996)
and can be assigned to PÐS stretching vibrations. In the transformed
UV±Vis re¯ectance spectrum, the band gap was determined to be
2.03 eV, which is in agreement with the observed red colour of the
single crystals.
Data collection
Stoe IPDS diffractometer
' scans
3999 independent re¯ections
3610 re¯ections with I > 2ꢃ(I)
Rint = 0.040
Absorption correction: numerical
[X-SHAPE (Stoe & Cie, 1998)
and X-RED (Stoe & Cie, 1998)]
Tmin = 0.510, Tmax = 0.753
16 873 measured re¯ections
ꢁmax = 28.0ꢀ
h = 25 ! 25
k = 8 ! 8
l = 16 ! 16
Re®nement
Re®nement on F2
R[F2 > 2ꢃ(F2)] = 0.048
wR(F2) = 0.127
S = 1.05
3999 re¯ections
Áꢄmax = 1.67 e A
3
Ê
3
Ê
1.20 e A
Áꢄmin
=
Extinction correction: SHELXL97
(Sheldrick, 1997)
Extinction coef®cient: 0.0048 (8)
Absolute structure: Flack (1983),
1913 Friedel pairs
147 parameters
w = 1/[ꢃ2(Fo2) + (0.1015P)2]
2
2
where P = (Fo + 2Fc )/3
(Á/ꢃ)max < 0.001
Flack parameter = 0.0 (4)
The crystal investigated was racemically twinned and, therefore, a
twin re®nement using SHELXL97 (Sheldrick, 1997) was performed,
yielding a ratio of 0.42 (7):0.58 (7) for the two individuals. A re®ne-
ment in the centrosymmetric space group Pnma was not successful.
Ê
The largest peak in the difference map is located 1.42 A from the V
atom.
Crystal data
K4VP2S9
Mr = 557.82
Orthorhombic, Pna21
Ê
a = 19.3587 (15) A
Ê
b = 6.7658 (5) A
c = 12.7869 (7) A
Ê
V = 1674.8 (2) A
Z = 4
Dx = 2.212 Mg m
Mo Kꢀ radiation
Cell parameters from 8000
re¯ections
ꢁ = 1.9±28.2ꢀ
1
ꢂ = 2.87 mm
T = 180 K
Data collection: IPDS (Stoe & Cie, 1998); cell re®nement: IPDS;
data reduction: IPDS; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND
Ê
3
Polyhedron, red
0.25 Â 0.20 Â 0.10 mm
3
ꢁ
i12 Andreas Gutzmann et al.
K4VP2S9
Acta Cryst. (2004). C60, i11±i13

inorganic compounds
Chondroudis, K., Kanatzidis, M. G., Sayettat, J., Jobic, S. & Brec, R. (1997).
Inorg. Chem. 36, 5859±5868.
Coste, S., Gautier, E., Evain, M., Bujoli-Doeuff, M., Brec, R., Jobic, S. &
Kanatzidis, M. G. (2003). Chem. Mater. 15, 2323±2327.
(Brandenburg, 1999); software used to prepare material for publi-
cation: CIFTAB in SHELXTL (Bruker, 1998).
Financial support by the state of Schleswig±Holstein and
the Deutsche Forschungsgemeinschaft (DFG) is gratefully
acknowledged.
È
Derstroff, V., Ksenofontov, V., Gutlich, P. & Tremel, W. (1998). Chem.
Commun. pp. 187±188.
Durand, E., Evain, M. & Brec, R. (1993). J. Solid State Chem. 102, 146±155.
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Supplementary data for this paper are available from the IUCr electronic
archives (Reference: AV1159). Services for accessing these data are
described at the back of the journal.
È
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Acta Cryst. (2004). C60, i11±i13
Andreas Gutzmann et al. K4VP2S9 i13