New layered quaternary tantalum thiophosphates containing binuclear [Ta2S10] units: Synthesis and crystal structures of the two new compounds K0.42TaPS5 and Rb 0.42TaPS5

Article abstract of DOI:10.1002/zaac.200400388

The reactions of Ta with an in situ formed polythiophosphate melt of A ₂S₃ (A = K, Rb), P₂S₅, and S at 500°C yield the two new quaternary tantalum thiophosphates A _0.42(2)TaPS₅ (A = K (I) a

Full text of DOI:10.1002/zaac.200400388

New Layered Quaternary Tantalum Thiophosphates Containing Binuclear
Ta S ] Units: Synthesis and Crystal Structures of the Two New Compounds
[
2
10
K TaPS and Rb TaPS
0
.42
5
0.42
5
Andreas Gutzmann, Christian Näther, and Wolfgang Bensch*
Kiel, Institut für Anorganische Chemie der Christian-Albrechts Universität
Received September 3rd, 2004.
th
Dedicated to Professor Arndt Simon on the Occasion of his 65 Birthday
Abstract. The reactions of Ta with an in situ formed polythi-
ophosphate melt of A (A ϭ K, Rb), P , and S at 500 °C yield
the two new quaternary tantalum thiophosphates A0.42(2)TaPS
A ϭ K (I) and Rb (II)). The compounds are isostructural and
tion scheme leads to the formation of one type of cavities within
2
S
3
2
S
5
the layers which are occupied by the alkali metal cations. The layers
are stacked onto each other in a ···ABAB··· fashion and channels
run along [011], [0-11], [01-1], and [0-1-1] with approximate dimen-
5
(
˚
crystallize in the orthorhombic space group Fddd with Z ϭ 16.
sions of 4.1 · 7.9 A. The electron transfer from the alkali metals to
˚
Compound I has lattice parameters a ϭ 9.6983(6) A, b ϭ
2 10
the host material yields a short Ta-Ta distance within the [Ta S ]
units. The compounds were characterized by energy dispersive X-
ray analysis and infrared spectroscopy in the MIR region.
˚
˚
˚
1
4.373(2) A, c ϭ 21.642(2) A, and compound II a ϭ 9.878(2) A,
˚
˚
b ϭ 14.288(2) A, c ϭ 21.687(2) A. Each Ta atom is surrounded by
six S atoms in an octahedral environment. Two [TaS ] octahedra
share a common edge to form the dimeric [Ta 10] unit. These units
are linked by sharing common edges with four tetradentate [PS
groups yielding a two-dimensional layered structure. The connec-
6
2
S
4
]
Keywords: Tantalum; Thiophosphates; Crystal structure; Flux reac-
tion; Vibrational properties
Neue schichtartige quaternäre Tantalthiophosphate mit binuklearen [Ta S ]-Einheiten:
2
10
Synthese and Kristallstrukturen der beiden neuen Verbindungen K TaPS and
0
.42
5
Rb TaPS
0
.42
5
Inhaltsübersicht. Die Reaktion von Tantal mit einer in-situ gebilde-
ten Polythiophosphatschmelze aus A (A ϭ K, Rb), P und
Schwefel führte bei 500 °C zur Bildung der beiden neuen quaternä-
ren Tantalthiophosphate A0.42(2)TaPS (A ϭ K (I) und Rb (II)).
Die Verbindungen sind isostrukturell und kristallisieren in der or-
thorhombischen Raumgruppe Fddd mit Z ϭ 16. Verbindung I: a ϭ
4
dentat agierenden PS -Tetraedern über gemeinsame Kanten führt
2
S
3
2
S
5
zur zweidimensionalen Schichtstruktur. In den Schichten werden
durch dieses Verknüpfungsschema Löcher gebildet, welche von den
Alkalimetallkationen besetzt sind. Die Schichten sind in der Ab-
folge ···ABAB··· übereinander gestapelt. Kanäle mit einer ungefäh-
5
˚
ren Abmessung von 4.1 · 7.9 A verlaufen entlang [011], [0-11], [01-
˚
˚
˚
9
9
.6983(6) A, b ϭ 14.373(2) A, c ϭ 21.642(2) A, Verbindung II: a ϭ
1] und [0-1-1]. Der Elektronentransfer von den Alkalimetallen auf
das Wirtsgitter führt zu recht kurzen Ta-Ta-Abständen in den
Ta S10-Einheiten. Die Verbindungen wurden mit energiedispersiver
2
Röntgenfloureszenzanalyse und Infrarotspektroskopie im MIR-Be-
reich charakterisiert.
˚
˚
˚
.878(2) A, b ϭ 14.288(2) A, c ϭ 21.687(2) A. Jedes Tantalatom ist
-Ok-
10-Ein-
oktaedrisch von sechs Schwefelatomen umgeben. Zwei TaS
taeder sind über eine gemeinsame Kante zur dimeren Ta
6
2
S
heit verbunden. Die Verknüpfung dieser Einheiten mit vier tetra-
Introduction
quaternary thiophosphates [1Ϫ7]. We have shown that a
systematic variation of the reaction parameters leads to the
formation of new thiophosphates with interesting structural
features. The known ternary thiophosphates with group 5
metals [8Ϫ16] have long been of interest as potential host
materials for alkali metal intercalation with possible tech-
nological applications as cathode materials in batteries, like
the well known lithium intercalated derivatives of the lay-
In the last few years we investigated the A-M-P-S family
(A ϭ alkali metal, M ϭ group IV or V metal) and demon-
strated that the use of the alkali metal polythiosphate flux
method is a suitable synthetic tool for the synthesis of new
*
Prof. Dr. W. Bensch
ered MPX family (M ϭ transition metal; X ϭ S, Se)
3
Institut für Anorganische Chemie
Universität Kiel
Olshausenstr. 40
D-24098 Kiel
Fax: ϩ49 (0)431/880Ϫ1520
e-Mail: wbensch@ac.uni-kiel.de
[17Ϫ19]. Despite the favorable structural features of the ter-
nary thiophosphates only a few attempts were carried out
to incorporate alkali metals. The first experiments were
started with the compounds M PS (M ϭ V, Nb) and
2
10
V P S [20, 21], but neither an electrochemical process nor
2
4 13
524
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
DOI: 10.1002/zaac.200400388
Z. Anorg. Allg. Chem. 2005, 631, 524Ϫ529

New Layered Quaternary Tantalum Thiophosphates
the reaction in an eutectic alkali metal halide flux led to
the desired products. Very recently we synthesized the new
quaternary thiophosphates K0.38TaPS and Rb TaPS [7].
6
0.46
6
These compounds are the first structurally characterized al-
kali metal intercalated derivatives of the known ternary
TaPS phase [14] and demonstrate that the low-dimensional
6
host structures of group 5 thiophosphates are stable during
the intercalation process. A structure closely related to
TaPS6 is observed in the quaternary niobium thiophos-
phates ANb P S (A ϭ K, Rb, Cs) [22]. In all these com-
2
2 12
pounds the electron transfer from the alkali metals to the
host material leads to a significant shortening of the M-M
distances within the biprismatic [M S ] units (M ϭ Nb,
2
12
Ta). These results confirms the assumption that the low-
lying acceptor levels of the highly oxidized metals in the
bimetallic building blocks are responsible for the alkali me-
tal intercalation of the ternary M-P-S phases [20].
The successful synthesis of intercalated phases mentioned
above pointed out the high synthetic potential of the chem-
istry in alkali metal polythiosphate fluxes, and the forma-
tion of new interesting solid-state materials can be expected
which cannot be obtained by traditional methods.
Fig. 1 Crystal structure of K0.42TaPS
approximately along the crystallographic c axis.
5 5
and Rb0.42TaPS with view
Interestingly, analyzing the structures of the ternary and
quaternary tantalum thiophosphates only [Ta S ] or
2
11
[
Ta S ] units and tetrahedral [PS ] groups are found as the
2 12 4
general structural motifs [2, 6, 7, 14, 15, 16, 23]. In our
ongoing investigations of the A-Ta-P-S system we have
obtained the quaternary tantalum thiophosphates
A0.42(2)TaPS (A ϭ K and Rb) in which a [Ta S ] unit is
5
2 10
observed for the first time. This unit is composed of two
TaS octahedra sharing a common edge. In the present con-
6
tribution the syntheses, crystal structures and vibrational
properties of these new compounds are reported.
Fig. 2 Environment of the [Ta
2
S10] units in the crystal structure of
Results and Discussion
K0.42TaPS
5
and Rb0.42TaPS
5
.
Crystal structures
˚
Table 1 Selected bond distances/A for
K
5
0.42TaPS (I) and
The two compounds K0.42(2)TaPS (I) and Rb0.42(2)TaPS5
5
Rb0.42TaPS (II). Estimated standards deviations are given in
5
(II) are isostructural and crystallize in the orthorhombic
parentheses.
space group Fddd with 16 formula units in the cell. In the
cell there are each one unique alkali metal, Ta, and P atom
and three crystallographically independent S atoms. A sec-
tion of one layer of the novel two-dimensional crystal struc-
ture is shown in Figure 1. The main feature of this new
structure type is the presence of binuclear [Ta S ] units
I
II
Ta - S(1)
Ta - S(2)
Ta - S(3)
Ta - Ta
2.467(3)
2.603(2)
2.336(3)
3.1194(6)
2.057(2)
2.028(2)
3.156(2)
3.429(4)
3.460(9)
3.949(3)
(x2)
(x2)
(x2)
2.463(3)
2.603(3)
2.341(3)
3.127(2)
2.059(4)
2.029(4)
3.228(3)
3.445(4)
3.641(6)
3.946(4)
(x2)
(x2)
(x2)
2
10
P
- S(1)
- S(2)
- S(1)
- S(1)
- S(2)
- S(2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
which are interconnected via tetrahedral [PS ] groups into
4
P
a layered structure.
A
A
A
A
The Ta atom is surrounded by two µ -S2Ϫ ions and four
2
S2Ϫ anions in a distorted octahedral environment (Fig. 2,
Table 1 and 2). Two [TaS ] octahedra share a common edge
6
to form dimeric [Ta S ] units with an average Ta-S distance
of 2.469 A for both compounds (Table 1 and Fig. 2). The
average Ta-S distances in the title compounds are compar-
2
10
˚
S2Ϫ anions bridging the two Ta atoms, whereas the longest
Ta-S distances are in trans position to the short Ta-S bonds
able with those found for the [TaS ] octahedra in
(Table 1 and Fig. 2). The [TaS ] octahedra in the two com-
6
6
CsTa P S [23] and in TaS [25]. The shortest Ta-S bonds
pounds are severely distorted as is evidenced by the S-Ta-S
angles (Table 2).
4
3
19
2
˚
˚
of 2.336(3) A (I) and 2.341(3) A (II) are observed to the µ -
2
Z. Anorg. Allg. Chem. 2005, 631, 524Ϫ529
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525

A. Gutzmann, C. Näther, W. Bensch
Table 2 Selected angles/° for K0.42TaPS
5 5
(I) and Rb0.42TaPS (II).
Estimated standard deviations are given in parentheses.
I
II
S(1) - Ta - S(1)
S(1) - Ta - S(2)
S(1) - Ta - S(2)
S(2) - Ta - S(2)
S(3) - Ta - S(1)
S(3) - Ta - S(1)
S(3) - Ta - S(2)
S(3) - Ta - S(2)
S(3) - Ta - S(3)
S(1) - P - S(1)
S(2) - P - S(1)
S(2) - P - S(1)
S(2) - P - S(2)
162.38(7)
77.83(5)
89.54(6)
88.83(8)
85.25(4)
106.69(4) (x2)
163.04(4) (x2)
89.83(5)
96.26(7)
107.3(2)
114.11(7) (x2)
102.56(6) (x2)
116.2(2)
163.1(2)
77.64(9)
90.2(2)
88.5(2)
84.42(7)
107.04(7) (x2)
162.02(7) (x2)
90.31(9)
96.2(2)
106.7(2)
114.9(2)
102.0(2)
116.4(3)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
(x2)
Fig. 4 View of the channels along [011] in the crystal structure of
5 5
K0.42TaPS and Rb0.42TaPS .
Fig. 3 Interconnection of the [Ta
the crystal structure of K0.42TaPS
2
S
10] units by [PS
and Rb0.42TaPS
4
] tetrahedra in
with atomic
5
5
Fig. 5 Crystal structure of K0.42TaPS
along the crystallographic a axis showing the stacking sequence
5 5
and Rb0.42TaPS with view
labeling. The dashed lines highlight the rectangular tunnel mentio-
ned in the text and the numbers are the distances between the
atoms in A measured from coordinate to coordinate.
···ABAB··· perpendicular to [001].
˚
The [Ta S ] units share common edges with four tetra-
The individual [TaPS ] layers extending in the (001) plane
2
10
5
˚
dentate [PS ] groups (Fig. 3). The arrangement of the [PS ]
are separated by about 3.72 (I) and 3.81 A (II) (measured
from coordinate to coordinate) and are stacked along [001]
in a sequence ···ABAB··· (Fig. 5). Consequently, the cavities
of neighboring layers are not located directly above each
other. But nearly rectangular channels are formed running
along [011], [0-11], [01-1], and [0-1-1] with approximate di-
4
4
groups with respect to the line joining two neighbored Ta
atoms leads to the formation of layers with one type of
cavities. The wall of the cavities is formed by the S(1) atoms
yielding a nearly rectangular opening. The dimensions of
˚
the openings measure about 4.07 · 5.1 A for I and 4.06 ·
˚
˚
5
.3 A for II (measured from coordinate to coordinate)
mensions of 4.1 · 7.9 A (Fig. 4).
(
Fig. 3).
The two new compounds represent the first tantalum thi-
ophosphates containing [Ta S ] units formed by edge-shar-
The average P-S bond lengths in the tetradentate [PS ]
4
˚
2 10
˚
tetrahedra amount to 2.043 A for compound I and 2.044 A
for compound II (Table 1). The average P-S distances are
in good agreement with values reported for [PS ] tetrahedra
ing of two [TaS ] octahedra. We note that [TaS ] octahedra
6
6
were also observed in the quaternary compound
CsTa P S [23]. But in contrast to the title compounds two
4
4 3 19
in Cs Ta P S and in the intercalated TaPS phases [6, 7].
[TaS ] groups are linked to a central [Ta S ] unit yielding
2
2
2
12
6
6
2 11
The [PS ] tetrahedra are significantly distorted as is evi-
a [Ta S (S )] fragment.
4
4
17
2
denced by the S-P-S angles (102.56(6) to 116.2(2)° in I and
102.0(2) to 116.4(3)° in II) (Table 2).
An interesting feature of the structure is the location of
the alkali metal cations. The inter-layer separation is too
526
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 524Ϫ529

New Layered Quaternary Tantalum Thiophosphates
ϩ
˚
small to accommodate the large cations [r(K ) ϭ 1.51 A,
ϩ
˚
r(Rb ) ϭ 1.61 A (CN ϭ 8)] [26]. Hence, they are situated
approximately in the middle of the rectangular openings
within the layers. The cations are surrounded by eight S
atoms forming irregular polyhedra. Two of the S atoms are
from one neighboring layer. The K-S bonds range from
.157 to 3.945 A (average K-S distance: 3.499 A; Table 1)
and Rb-S distances from 3.228 to 3.946 A (average Rb-S
distance: 3.565 A; Table 1). The average A-S distances (A ϭ
˚
˚
3
˚
˚
K, Rb) match well with the sum of the ionic radii [26].
Within the channels (see above) the cations are disordered,
and unusual short distances occur between neighbored
symmetry equivalent cations (see exp. Part). Obviously,
ϩ
fully occupied sites for the A ions would lead to a different
cation arrangement.
It is surprising that the b axis of the Rb compound is
shorter than that of the K compound. This contraction is
ϩ
the result of the space requirements of the larger Rb ion
and the response of the thiophosphate network. The Rb-
˚
S(1) distances (3.228 and 3.445 A) are longer than the anal-
˚
ogous K-S(1) bonds (3.157 and 3.434 A) which leads to a
lengthening of the S(1)···S(1) separation along the a-axis
˚
from 5.124 in I to 5.339 A in II. The expansion is ac-
companied by a significant contraction of the S(2)···S(2)
˚
separation along the b axis (8.245 vs. 8.135 A) (see Fig. 3).
ϩ
It is interesting to note that the replacement of K by the
ϩ
larger Rb not simply leads to an expansion of the inor-
ganic network, i.e. a lengthening of all axes. This obser-
vation implies that the strong covalent Ta-S and P-S bonds
are responsible for the rigidity of the network and the flexi-
bility is due to variable angles around Ta and P.
Another interesting feature of the compounds is an elec-
tron transfer from the alkali metal atoms to the host mate-
5
ϩ
rial. In the host lattice only the Ta cations can be reduced
by the electron transfer. Hence, the low-lying acceptor levels
5 0.42 5
Fig. 6 MIR spectra of K0.42TaPS (top) and Rb TaPS (bottom).
(
d-block bands) of the highly oxidized metals in the [Ta S ]
2 10
Vibrational properties
building blocks are responsible for the alkali metal intercal-
ation. The electron transfer leads to relatively short in-
teratomic Ta-Ta distances within the [Ta S ] groups which
amount to 3.1194(6) A for compound I and 3.127(2) A for
compound II (Table 1). These distances are significantly
The MIR spectra of K0.42TaPS and Rb TaPS are shown
in Figure 6. According to the results of the X-ray structure
determination the spectroscopic relevant units are tetra-
5
0.42
5
2
10
˚
˚
hedral [PS ] groups. The spectrum of compound I displays
4
5ϩ
Ϫ1
shorter than in compounds containing neighbored Ta
three strong absorption bands at 601, 574 and 545 cm ,
which may be assigned to P-S stretching vibrations. Ana-
0
(d ) atoms [2, 6, 14, 15, 16, 23] and are comparable with
those found in the intercalated phases K0.38TaPS6
(
logous bands are observed for II.
˚ ˚
3.142(2) A) and Rb TaPS (3.1011(5) A) [7]. The elec-
0.46 6
tronic situation in the title compounds may be described as
Experimental
ϩ
(5Ϫx)ϩ 5ϩ 2Ϫ
Ax Ta
P S5 (A ϭ K, Rb; x ϭ 0.42(2)).
Syntheses
In view of the present results, further investigations are
indispensable concerning the physical properties, the dein-
tercalation behavior of the compounds and the homogen-
eity range with respect to the alkali metal content. The de-
intercalation could be an elegant synthetic route to design
new materials which could serve as hosts for further inter-
calation experiments.
The compounds K0.42TaPS
by reacting a mixture of A
:8:3:10 molar ratio (Ta, 99.97 %, Fluka; P
Alfa; S, 99.99 %, Heraeus). A (A ϭ K, Rb) was synthesized by
5
(I) and Rb0.42TaPS
(A ϭ K, Rb), Ta, P
, 99.99 % purity,
5
(II) were prepared
2
S
3
2 5
S
, and S in a
1
2 5
S
2 3
S
the reaction of stoichiometric amounts of the elements (K, Rb >
99 %, Chempur) in liquid ammonia under argon atmosphere. The
reaction mixtures were thoroughly mixed in a N
2
-filled glove box
Z. Anorg. Allg. Chem. 2005, 631, 524Ϫ529
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© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 527

A. Gutzmann, C. Näther, W. Bensch
and loaded into glass ampoules. After evacuation to 10Ϫ3 mbar the
ampoule was flame-sealed and placed in a computer-controlled fur-
nace.
Table 3 Technical details of data acquisition and some refinement
results for K0.42TaPS
5
(I) and Rb0.42TaPS
5
(II).
Compound
I
II
Crystal system
orthorhombic
9.6983(6)
14.373(2)
21.642(2)
3016.8(3)
Fddd (no. 70)
16
3.418
black
16.33
orthorhombic
9.879(2)
14.288(2)
21.687(2)
3061.2(5)
Fddd (no. 70)
16
3.546
black
18.45
˚
a / A
˚
Synthesis of K0.42TaPS (I)
b / A
5
˚
c / A
˚
3
V / A
Compound I was prepared from a reaction mixture of K
2 3
S
Space group
Z
(
0.15 mmol), Ta (1.2 mmol), P (0.45 mmol) and S (1.5 mmol).
2 5
S
The mixture was heated to 500 °C within 18 h. This temperature
was kept for 4 days before the sample was cooled down to 250 °C
Ϫ3
Calc. density / g cm
Crystal color
Ϫ1
Ϫ1
µ / mm
with 2 °C h followed by cooling to room temperature within 10 h.
The residual K P S flux was removed with dry DMF and after
x y z
F(000)
Scan range
Index range
2811
2940
5° Յ 2θ Յ 56°
Ϫ12 Յ h Յ 12
Ϫ18 Յ k Յ 18
Ϫ28 Յ l Յ 28
7360
914
293
0.0519
0.0955/ 0.1613
745
41
0.0528
5° Յ 2θ Յ 51°
Ϫ11 Յ h Յ 11
Ϫ17 Յ k Յ 17
Ϫ25 Յ l Յ 25
5525
674
293
0.0736
0.0713/0.1290
509
40
0.0531
washing with ether black crystals were obtained (yield: ϳ85 %
based on Ta). Scanning electron micrographs of the product re-
vealed black crystals with a multi-faced polyhedra-like mor-
phology. The X-ray powder pattern of the product is dominated by
reflections of compound I and only very weak reflections of a se-
cond phase were present which could not be identified until now.
An EDX analysis of several selected crystals indicated the presence
of all four elements (K, Ta, P, S) and for all crystals the atomic
ratio was identical amounting to (ϳ1):2:2:10.
Reflections collected
Independent reflections
Temperature / K
R
int
Min./max. transm.
o
refl. with F >4σ(F )
o
Number of parameters
a)
x
R
1
for F
o
>4σ(F
o
)
0.0285
0.0352
wR for all reflections
2
0.0757
1.034
1.29 / Ϫ1.68
0.0866
1.057
1.35 / Ϫ2.36
GOOF
˚
Ϫ3
Synthesis of Rb0.42TaPS (II)
∆ρ /eA
5
a)
2
2
2
2,0) ϩ 2 · F 2) / 3
c
Single crystals of the isostructural compound II were prepared
w ϭ 1/[σ (F
o
) ϩ (x · P) ; P ϭ (Max (F
o
from a reaction mixture of Rb
(0.27 mmol) and S (0.9 mmol). The sample was heated to
00 °C within 18 hours and kept at this temperature for 4 days.
2 3
S (0.09 mmol), Ta (0.72 mmol),
P
5
2
S
5
Table 4 Atomic coordinates and equivalent isotropic displacement
˚
2
parameters Ueq (A ) for K0.42TaPS . Estimated standards devia-
5
Ϫ1
Afterwards the sample was cooled to 150 °C with 3 °C h and
then in 6 hours to room temperature. The residual Rb flux
tions are given in parentheses. The Ueq is defined as one third of
the trace of the orthogonalized Uij tensor (s.o.f. of K1 ϭ 0.42(2)).
x
P
y
S
z
was removed with dry DMF and after washing with ether black
polyhedra-like crystals were obtained (yield: ϳ70 % based on Ta).
The X-ray powder pattern of the product is dominated by reflec-
tions of compound I and weak reflections of a second phase were
present which could not be identified until now. An EDX analysis
of several selected single crystals always yields the same ratio for
the elements, i.e. within the margin of error and the limits of the
method the crystals have an identical chemical composition.
Wyckoff
position
x
y
z
U
eq
K(1)
Ta(1)
P(1)
S(1)
S(2)
S(3)
16g
16f
16g
32h
32h
16g
1/8
5/8
3/8
0.3816(2)
0.5516(2)
5/8
5/8
0.5165(1)
3/8
0.4902(1)
0.3871(1)
5/8
0.1588(5)
1/8
0.1530(1)
0.0967(1)
0.2025(1)
0.2054(1)
69(3)
23(1)
25(1)
30(1)
32(1)
30(1)
Table 5 Atomic coordinates and equivalent isotropic displacement
˚
2
Single crystal X-Ray diffraction
parameters Ueq (A ) for Rb0.42TaPS . Estimated standards devia-
5
tions are given in parentheses. The Ueq is defined as one third of
Single crystal X-ray work was performed using a STOE Imaging
the trace of the orthogonalized U tensor (s.o.f. of Rb1 ϭ 0.42(2)).
ij
Plate Diffraction System (IPDS) (MoKα radiation;
λ ϭ
˚
0.71073 A). The raw intensities were treated in the usual way apply-
Wyckoff
x
y
z
U
eq
position
ing a Lorentz, polarization and a numerical absorption correction.
Structure solution was performed with SHELXS-97 [24]. Refine-
Rb(1)
Ta(1)
P(1)
S(1)
S(2)
S(3)
16g
16f
16g
32h
32h
16g
1/8
5/8
3/8
0.3872(3)
0.5489(3)
5/8
5/8
0.5156(1)
3/8
0.4903(2)
0.3851(2)
5/8
0.1509(3)
1/8
0.1519(2)
0.0952(1)
0.2012(1)
0.2054(2)
70(2)
30(1)
34(1)
37(1)
41(1)
37(1)
2
ment was done against F using SHELXL-97 [24]. All atoms were
refined with anisotropic displacement parameters. For compound
I an extinction correction was performed. The K and Rb content
in the two compounds was refined yielding K0.42(2)TaPS
5
and
Rb0.42(1)TaPS . Within the accuracy of the method and 3 esd’s the
5
composition of the two compounds is identical. Concerning the
disorder of the alkaline metal cations long exposed images of the
crystals were made. From these investigations there are no hints for
a superstructure or diffuse intensities.
Physical property measurements
MIR spectra (4000-400 cmϪ1, 2 cmϪ1 resolution) were collected on
a Genesis FT-spectrometer (ATI Mattson). The compounds were
ground together with KBr in a N
a transparent pellet.
2
-filled glove box and pressed into
Technical details of the data acquisition as well as some refinement
results for compounds I and II are summarized in Table 3, atomic
coordinates and equivalent isotropic displacement parameters are
given in Table 4 for compound I and in Table 5 for compound II.
EDX analysis was performed with a Philips ESEM XL 30 scanning
electron microscope equipped with an EDAX analyzer.
528
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 524Ϫ529

New Layered Quaternary Tantalum Thiophosphates
Acknowledgements. We thank I. Jeß for the single crystal work. Fin-
ancial support by the State of Schleswig-Holstein and the Deutsche
Forschungsgemeinschaft (DFG) is gratefully acknowledged.
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Z. Anorg. Allg. Chem. 2005, 631, 524Ϫ529
zaac.wiley-vch.de
© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
529