Syntheses and structures of six compounds in the A2LiMS 4 (A = K, Rb, Cs; M = V, Nb, Ta) family

Article abstract of DOI:10.1016/j.jssc.2004.10.041

Six new compounds in the A₂LiMS₄ (A = K, Rb, Cs; M = V, Nb, Ta) family, namely K₂LiVS₄, Rb₂LiVS ₄, Cs₂LiVS₄, Rb₂LiNbS₄, Cs₂LiNbS₄, and Rb₂LiTaS₄, have been synthesized by the reactions of the elements in Li₂S/S/A ₂S₃ (A = K, Rb, Cs) fluxes at 773 K. The A and M atoms play a role in the coordination environment of the Li atoms, leading to different crystal structures. Coordination numbers of Li atoms are five in K₂LiVS₄, four in A₂LiVS₄ (A = Rb, Cs) and Cs₂LiNbS₄, and both four and five in Rb ₂LiMS₄ (M = Nb, Ta). The A₂LiVS₄ (A = Rb, Cs) structure comprises one-dimensional chains of _∞ ¹[LiVS₄] tetrahedra. The Rb₂LiMS₄ (M = Nb, Ta) structure is composed of two-dimensional _∞ ²[LiMS₄] layers. The Cs₂LiNbS₄ structure contains one-dimensional _∞¹[LiNbS ₄] chains that are related to the Rb₂LiMS₄ layers. The K₂LiVS₄ structure contains a different kind of _∞¹[LiVS₄] layer.

Full text of DOI:10.1016/j.jssc.2004.10.041

ARTICLE IN PRESS
Journal of Solid State Chemistry 178 (2005) 194–199
www.elsevier.com/locate/jssc
Syntheses and structures of six compounds in
the A2LiMS4 (A ¼ K, Rb, Cs; M ¼ V, Nb, Ta) family
Fu Qiang Huang, Bin Deng, James A. Ibers
Ã
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208-3113, USA
Received 16 July 2004; received in revised form 18 October 2004; accepted 29 October 2004
Abstract
Six new compounds in the A2LiMS4 (A ¼ K, Rb, Cs; M ¼ V, Nb, Ta) family, namely K2LiVS4, Rb2LiVS4, Cs2LiVS4,
Rb2LiNbS4, Cs2LiNbS4, and Rb2LiTaS4, have been synthesized by the reactions of the elements in Li2S/S/A2S3 (A ¼ K, Rb, Cs)
fluxes at 773 K. The A and M atoms play a role in the coordination environment of the Li atoms, leading to different crystal
structures. Coordination numbers of Li atoms are five in K2LiVS4, four in A2LiVS4 (A ¼ Rb, Cs) and Cs2LiNbS4, and both four
1
and five in Rb2LiMS4 (M ¼ Nb, Ta). The A2LiVS4 (A ¼ Rb, Cs) structure comprises one-dimensional chains of ½LiVS4Š
1
2
1
tetrahedra. The Rb2LiMS4 (M ¼ Nb, Ta) structure is composed of two-dimensional ½LiMS4Š layers. The Cs2LiNbS4 structure
1
1
contains one-dimensional ½LiNbS4Š chains that are related to the Rb2LiMS4 layers. The K2LiVS4 structure contains a different
1
kind of ½LiVS4Š layer.
1
r 2004 Elsevier Inc. All rights reserved.
Keywords: Alkali metal; Vanadium triad; Sulfide; Synthesis; X-ray structures
1. Introduction
Concomitant dimensional reduction occurs owing to the
predilection of K+ to achieve higher coordination
numbers than Cu+.
Since its discovery, the reactive-flux method [1] has led
to the syntheses of about 40 new A/M/M0/Q (A ¼ Na,
K, Rb, Cs, Tl; M ¼ Cu, Ag; M0 ¼ V, Nb, Ta; Q ¼ S, Se,
Te) quaternary compounds. Examples include
K3CuNb2Se12 [2], CsCu2MTe4 (M ¼ Nb, Ta) [3],
A2AgTaS4 (A ¼ Tl, Rb) [4,5], NaCu2NbS4 [6], and
Rb2CuVS4 [7]. In most of these compounds, the M and
M0 atoms are tetrahedrally coordinated by four Q
atoms. The dimensionality of these structures is reduced
as the ratio of alkali metal A to the transition metal (M,
M0) increases [8]. Take the K/Nb/Cu/Se system as an
example: as one goes from Cu3NbSe4 [9,10] to
KCu2NbSe4 [11] to K2CuNbSe4 [2] to K3NbSe4 [12]
the dimensionality of the structures reduces from three-
dimensional to two-dimensional to one-dimensional and
finally to a zero-dimensional salt. Conceptually, the
series presents the progressive substitution of K for Cu.
Among ternary and quaternary metal chalcogenides
containing alkali metals, those incorporating Li are the
least common. Li generally adopts a lower coordination
number than do its higher congeners. In sulfides, the
coordination number of Li is often four (ALiS (A ¼ K,
Rb) [13,14], KLiMS2 (M ¼ Mn, Zn) [15], LiGaS2 [16]);
occasionally five (Li4GeS4 [17–19], Li3AsS3 [20]); and
often six (LiBiS2 [21,22], LiTiS2 [23]). Here we investi-
gate the substitution of Li for Cu in the K2CuNbSe4
structure type [2], which consists of one-dimensional
½CuNbSe24ꢀŠ chains of edge-sharing CuSe4 and NbSe4
1
1
tetrahedra. Six new compounds, namely K2LiVS4,
Rb2LiVS4, Cs2LiVS4, Rb2LiNbS4, Cs2LiNbS4, and
Rb2LiTaS4, have been synthesized. Li shows coordina-
tion numbers four or five in these compounds. Among
these compounds three are one-dimensional and three
are two-dimensional; three different space groups are
represented. Only Rb2LiVS4 and Cs2LiVS4 belong to the
K2CuNbSe4 structure type.
Ã
Corresponding author. Fax: +847 491 2976.
E-mail address: ibers@chem.northwestern.edu (J.A. Ibers).
0022-4596/$ - see front matter r 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jssc.2004.10.041

ARTICLE IN PRESS
F.Q. Huang et al. / Journal of Solid State Chemistry 178 (2005) 194–199
195
2. Experimental
2.2. Structure determinations
2.1. Syntheses
Single-crystal X-ray diffraction data were collected
with the use of graphite-monochromatized MoKa
radiation (l ¼ 0.71073 A) at 153 K on a Bruker Smart-
1000 CCD diffractometer [24]. The crystal-to-detector
distance was 5.023 cm. Crystal decay was monitored by
recollecting 50 initial frames at the end of data
collection. Data were collected by a scan of 0.31 in o
in four groups of 606 frames at j settings of 01, 901,
1801, and 2701. The exposure time was 5–15 s/frame.
The collection of the intensity data was carried out
with the program SMART [24]. Cell refinement and
data reduction were carried out with the use of the
program SAINT [24] and face-indexed absorption
corrections were performed numerically with the use of
the program XPREP [25]. Then the program SADABS
[24] was employed to make incident beam and decay
corrections.
The structures were solved with the direct methods
program SHELXS and refined with the full-matrix
least-squares program SHELXL of the SHELXTL suite
of programs [25]. Each final refinement included
anisotropic displacement parameters. One of the three
independent K atoms in the K2LiVS4 structure is
disordered over two sites. None of the other struc-
tures displays any disorder. Additional experi-
mental details are shown in Table 1 and in the
Supplementary material. Tables 2–5 present selected
metrical data.
The following reagents were used as obtained: K
(Alfa, 98%), Rb (Aldrich, 98+%), Cs (Aldrich, 99.5%),
V (Strem, 99.5%), Nb (Johnson Matthey, 99.8%), Ta
(Aldrich, 99.9%), S (Alfa, 99.5%), and Li2S (Aldrich,
98%). A2S3 (A ¼ K, Rb, Cs), the reactive fluxes
employed in the syntheses, were prepared by the
stoichiometric reactions of the elements in liquid NH3.
All these compounds were synthesized by the reaction of
1.0 mmol of M (M ¼ V, Nb, Ta), 1.0 mmol of S,
0.5 mmol of Li2S, and 1.0 mmol of A2S3 (A ¼ K, Rb,
Cs). A reaction mixture was loaded into a fused-silica
tube under an Ar atmosphere in a glove box. The tube
was sealed under a 10ꢀ4 Torr atmosphere and then
placed in a computer-controlled furnace. The sample
was heated to 773 K in 8 h, kept at 773 K for 72 h, cooled
at 3 K/h to 375 K, and then the furnace was turned off.
The reaction mixture was washed with N,N-dimethyl-
formamide. The products in the V reactions were
composed of red needles and plates; those in the Nb
and Ta reactions were pink blocks. Yields for the V
reactions were greater than 90%; those for the Nb and
Ta reactions were about 20%. Examination of selected
crystals with an EDX-equipped Hitachi S-3500 SEM led
to results consistent with the stated compositions. The
compounds are extremely air-sensitive. They decompose
in water and acetone.
Table 1
Crystal data and structure refinements for K2LiVS4, Rb2LiVS4, Cs2LiVS4, Rb2LiNbS4, Cs2LiNbS4, and Rb2LiTaS4
a
Compound
K2LiVS4
Rb2LiVS4
Cs2LiVS4
Rb2LiNbS4
Cs2LiNbS4
Rb2LiTaS4
487.07
Formula mass
Space group
Z
264.32
C2/c
357.06
Fddd
451.94
Fddd
399.03
¯
P1
493.91
¯
P1
¯
P1
8
8
8
4
2
4
a (A)
b (A)
10.4788(7)
8.4250(6)
17.9897(12)
90
5.813(1)
13.083(2)
23.164(4)
90
5.8316(5)
13.610(1)
24.177(2)
90
7.0285(4)
11.3919(7)
11.8129(7)
71.761(1)
87.877(1)
83.876(1)
893.18(9)
2.967
6.9186(8)
7.2518(8)
9.761(1)
96.650(2)
92.239(2)
91.279(2)
485.9(1)
3.376
7.0452(5)
11.3929(9)
11.8205(9)
71.747(1)
87.766(1)
83.652(1)
895.5(1)
3.613
c (A)
a (1)
b (1)
94.748(1)
90
90
90
90
90
g (1)
V (A3)
rc (g/cm3)
1582.8(2)
2.218
32.5
1761.7(5)
2.692
1918.8(3)
3.129
92.93
0.108/0.445
0.03
m (cmꢀ1
)
129.56
0.067/0.247
0.02
130.14
93.93
239.11
Tmin/Tmax
q
R(F)b
Rw (F2o)c
Sd
0.582/0.789
0.04
0.072/0.302
0.03
0.0293
0.117/0.310
0.025
0.0253
0.017/0.130
0.025
0.0353
0.0337
0.0823
1.27
0.0145
0.0356
1.17
0.0219
0.058
1.45
0.086
1.28
0.0629
1.16
0.1083
1.44
aT ¼ 153(2) K and l ¼ 0.71073 A.
P
bR(F) ¼ ||Fo|ꢀ|Fc||/|Fo| for Fo242s(F2o).
P
P
P
cRw(F2o) ¼ { [w(F2oꢀFc2)2] / wFo4}1/2 for all data. wꢀ1 ¼ s2(F2o)+(qP)2 and P ¼ [2Fc2+max(F2o, 0)]/3.
dLeast-squares goodness of fit: S ¼ { [w(Fo2ꢀFc2)2] /(nꢀp)}1/2, where n ¼ number of reflections and p ¼ number of parameters refined.

ARTICLE IN PRESS
F.Q. Huang et al. / Journal of Solid State Chemistry 178 (2005) 194–199
196
3. Results
Table 2
Selected bond lengths (A) and angles (1) for K2LiVS4
3.1. Synthesis
Li–S2
Li–S4
2.496(5)
2.497(5)
2.536(5)
2.661(5)
2.711(5)
2.1326(8)
2.1414(7)
2.1573(8)
2.1613(8)
S3–V–S4
S1–V–S2
S2–Li–S4
S2–Li–S3
S4–Li–S4
S4–Li–S3
S2–Li–S4
S2–Li–S3
S4–Li–S2
S2–Li–S2
S2–Li–S4
S3–Li–S4
110.70(3)
110.96(3)
82.7(1)
K2LiVS4,
Rb2LiVS4,
Cs2LiVS4,
Rb2LiNbS4,
Li–S2
Li–S3
84.8(2)
88.7(3)
Cs2LiNbS4, and Rb2LiTaS4 have been synthesized by
the reactions of the elements in Li2S/S/A2S3 (A ¼ K, Rb,
Cs) fluxes at 773 K. The yields of the V compounds were
over 90%; those of the Nb and Ta compounds were
about 20%. Attempts to prepare the other three
compounds in this series, namely K2LiNbS4, K2LiTaS4,
and Cs2LiTaS4, were unsuccessful. Failure to prepare
K2LiNbS4 or K2LiTaS4 as opposed to K2LiVS4 may be
a manifestation of the relatively small ionic radius of
V5+ compared with those of Nb5+ or Ta5+. But given
the minimal difference in ionic radii of the latter two
cations it is not clear why Cs2LiNbS4 could be prepared
but not Cs2LiTaS4.
Li–S4
V–S3
93.1(2)
95.2(2)
95.4(2)
V–S1
V–S2
V–S4
112.7(2)
121.1(2)
126.1(2)
177.8(2)
S2–V–S4
S3–V–S2
S3–V–S1
S1–V–S4
106.85(3)
108.42(3)
109.66(3)
110.21(3)
Table 3
Selected bond lengths (A) and angles (1) for Rb2LiVS4, and Cs2LiVS4
3.2. Crystal structures
Bond/angle
Rb2LiVS4
Cs2LiVS4
There are no S–S bonds in the structures of the
compounds A2LiMS4 (A ¼ K, Rb, Cs; M ¼ V, Nb, Ta).
Accordingly, the formal oxidation states of A, Li, V, and
S are 1+, 1+, 5+, and 2ꢀ, respectively.
Li–S ꢁ 4
2.4030(4)
2.1595(4)
93.63(2)
2.3988(6)
2.1548(6)
93.18(3)
V–S ꢁ 4
S–Li–S ꢁ 2
S–Li–S ꢁ 2
S–Li–S ꢁ 2
S–V–S ꢁ 2
S–V–S ꢁ 2
S–V–S ꢁ 2
117.61(2)
118.24(2)
108.47(2)
109.61(2)
110.34(2)
118.09(3)
118.27(3)
107.94(3)
110.13(4)
110.35(3)
The crystal structure of K2LiVS4 (space group C2/c)
comprises two-dimensional ½LiVS24ꢀŠ layers separated
2
1
by K atoms. Each layer is built from edge-sharing
tetrahedra NbS4 and slightly distorted LiS5 trigonal
bipyramids (Fig. 1). The unit cell is displayed in Fig. 2.
Table 4
Selected bond lengths (A) and angles (1) for Rb2LiNbS4 and Rb2TaVS4
Bond/angle
Rb2LiNbS4
Rb2LiTaS4
Angle
Rb2LiNbS4
Rb2LiTaS4
Li1–S3
Li1–S2
2.381(8)
2.446(9)
2.481(9)
2.505(8)
2.466(9)
2.511(9)
2.528(9)
2.620(10)
3.013(10)
2.257(1)
2.264(1)
2.272(1)
2.276(1)
2.254(1)
2.259(1)
2.268(1)
2.288(1)
92.9(3)
2.39(1)
2.45(1)
2.47(1)
S1–Li2–S6
S6–Li2–S6
S6–Li2–S1
S1–Li2–S1
S8–Li2–S6
S8–Li2–S1
S8–Li2–S6
S8–Li2–S1
S1–Li2–S6
S1–Li2–S6
S6–M1–S1
S6–M1–S3
S5–M1–S1
S5–M1–S3
S5–M1–S6
S3–M1–S1
S7–M2–S2
S4–M2–S2
S7–M2–S8
S4–M2–S7
S8–M2–S2
S4–M2–S8
80.0(3)
82.8(3)
89.5(3)
80.0(4)
82.5(4)
89.3(5)
Li1–S7
Li1–S2
2.50(1)
2.47(1)
92.7(3)
97.9(3)
98.2(3)
92.9(5)
97.8(5)
98.5(5)
Li2–S8
Li2–S1
2.49(2)
2.53(1)
Li2–S6
Li2–S1
113.2(4)
122.1(4)
123.7(4)
163.8(4)
106.00(5)
108.51(3)
108.57(5)
110.00(5)
111.26(5)
112.45(5)
105.27(5)
108.79(5)
108.90(5)
110.60(5)
111.14(5)
111.93(5)
112.9(5)
122.6(6)
123.4(6)
163.6(5)
106.05(7)
108.58(8)
108.69(8)
110.07(7)
111.22(8)
112.18(8)
105.48(7)
108.73(8)
108.81(8)
110.63(8)
111.17(8)
111.84(7)
2.63(2)
3.05(2)
Li2–S6
M1–S5
2.257(2)
2.265(2)
2.269(2)
2.274(2)
2.257(2)
2.258(2)
2.264(2)
2.284(2)
93.3(4)
M1–S6
M1–S3
M1–S1
M2–S4
M2–S7
M2–S8
M2–S2
S7–Li1–S2
S2–Li1–S2
S3–Li1–S2
S3–Li1–S7
S3–Li1–S2
S2–Li1–S7
101.8(3)
108.9(4)
110.5(3)
113.6(3)
125.2(4)
102.2(5)
109.1(6)
110.7(5)
113.1(5)
125.0(6)

ARTICLE IN PRESS
F.Q. Huang et al. / Journal of Solid State Chemistry 178 (2005) 194–199
197
Table 5
Selected bond lengths (A) and angles (1) for Cs2LiNbS4
Li–S1
Li–S4
2.426(7)
2.468(7)
2.494(7)
2.538(7)
2.258(1)
2.262(1)
2.271(1)
2.292(1)
92.3(2)
S1–Li–S4
S1–Li–S3
S1–Li–S4
S4–Li–S2
S3–Nb–S4
S2–Nb–S4
S3–Nb–S1
S2–Nb–S1
S2–Nb–S3
S1–Nb–S4
110.5(3)
111.5(3)
114.4(3)
122.7(3)
105.69(4)
109.20(4)
109.38(4)
109.87(4)
110.43(4)
112.19(4)
Li–S3
Li–S4
Nb–S2
Nb–S3
Nb–S1
Nb–S4
S3–Li–S4
S4–Li–S4
101.7(3)
Fig. 3. The unit cell of Rb2LiVS4 down [100].
Fig. 4. The ½LiVS24ꢀŠ chain in Rb2LiVS4.
1
1
Fig. 1. The ½LiVS24ꢀŠ layer in K2LiVS4.
2
1
Fig. 5. The unit cell of Rb2LiNbS4 down [100].
Fig. 2. The unit cell of K2LiVS4 down [010].
2
½LiNbS4Š layers (Fig. 6) separated by Rb atoms. Each
½LiNbS4Š layer is built from vertex- and edge-sharing
1
2
Rb2LiVS4 and Cs2LiVS4 are isostructural and of the
K2CuNbSe4 structure type (space group Fddd). The
structure of Rb2LiVS4 is displayed in Fig. 3. It consists
1
NbS4 tetrahedra, Li1S4 tetrahedra, and distorted Li2S5
trigonal bipyramids.
The structure of Cs2LiNbS4 belongs to a new
of one-dimensional ½LiVS22ꢀŠ chains separated by Rb
1
1
atoms. Each chain is built from LiS4 and VS4 tetrahedra
¯
structure type (space group P1), as displayed in Fig. 7.
that share edges to form a ½LiVS22ꢀŠ chain along [100],
The structure consists of one-dimensional ½LiNbS42ꢀ
Š
1
1
1
1
as shown in Fig. 4.
Rb2LiNbS4 and Rb2LiTaS4 are isostructural, crystal-
chains separated by Cs atoms, as shown in Fig. 8. Each
chain is composed of vertex- and edge-sharing NbS4 and
LiS4 tetrahedra, different from the chain in Cs2LiVS4,
which is built solely from edge-sharing VS4 and LiS4
tetrahedra. The structure of Cs2LiNbS4 is related to that
of Rb2LiNbS4. The shape of the chain in Cs2LiNbS4
¯
lizing in a new structure type (space group P1) different
from the structure of A2LiVS4 (A ¼ Rb, Cs; space
group Fddd). The unit cell of Rb2LiNbS4 is shown in
Fig. 5. The structure is composed of two-dimensional

ARTICLE IN PRESS
F.Q. Huang et al. / Journal of Solid State Chemistry 178 (2005) 194–199
198
Rb2LiNbS4, Rb2LiTaS4, and Cs2LiNbS4 (Tables 3–5)
are somewhat less regular than the MS4 tetrahedra with
Li–S distances ranging from 2.381(8) to 2.538(7) A and
S–Li–S angles ranging from 92.9(3) to 125.2(4)1. The
Li–S distances in the LiS4 tetrahedra in Li3AsS3 range
from 2.39(2) to 2.58(2) A [20] whereas they are 2.52(2)
and 2.53(1) A in LiAuS [28]. Not surprisingly, the LiS5
trigonal bipyramids in K2LiVS4, Rb2LiNbS4, and
Rb2LiTaS4 are more distorted: Li–S distances range
from 2.466(9) to 3.013(10) A, Seq–Li–Seq angles range
from 112.7(2) to 126.1(2)1, and Seq–M–Sax angles
range from 80.0(3) to 98.5(5)1. The Sax– M–Sax angles
range from 163.6(5) to 177.8(2)1(Tables 2 and 4).
Fig. 6. The ½LiNbS24ꢀŠ layer in Rb2LiNbS4.
2
1
The A–S coordination numbers and distance ranges
are: 7, 3.021(7)–3.772(6) A (K2LiVS4); 8, 3.3981(6)–
3.7259(6) A (Rb2LiVS4); 8, 3.5222(7)–3.8246(7) A
(Cs2LiVS4); 7, 3.388(1)–3.638(1) A (Rb2LiNbS4); 9,
3.491(1)–4.069(1) A (Cs2LiNbS4); and 7, 3.390(2)–
3.645(2) A (Rb2LiTaS4). These are comparable to those
in A2AgMS4 (A ¼ K, Rb, Cs; M ¼ Nb, Ta) [7].
4. Conclusions
The substitution of Li for Cu in the K2CuNbSe4
structure type [2], which consists of one-dimensional
Fig. 7. The unit cell of Cs2LiNbS4 down [100].
½CuNbSe24ꢀŠ chains of edge-sharing CuSe4 and NbSe4
1
1
tetrahedra, has generally affected not only the dimen-
sionality of the structure but also the structure type and
space group. Only Rb2LiVS4 and Cs2LiVS4 belong to
the K2CuNbSe4 structure type. In fact, among the six
compounds, namely K2LiVS4, Rb2LiVS4, Cs2LiVS4,
Rb2LiNbS4, Cs2LiNbS4, and Rb2LiTaS4, three are
one-dimensional and three are two-dimensional struc-
tures; there are three different space groups; there are
four different structure types; there is one compound in
which Li is five-coordinate; there are three in which Li is
four-coordinate; and there are two in which Li is both
four- and five-coordinate. It appears that the smaller the
transition metal the lower the dimensionality, and the
smaller the alkali metal the higher the dimensionality.
One wonders whether structural information on the
three other possible compounds in the series, namely
K2LiNbS4, K2LiTaS4, and Cs2LiTaS4, which we were
unable to synthesize, would have simplified or further
complicated these results.
Fig. 8. The ½LiNbS24ꢀŠ chain in Cs2LiNbS4.
2
1
2
1
(Fig. 8) is somewhat similar to that of the ½LiNbS4Š
layers in Rb2LiNbS4 (Fig. 6).
The VS4 tetrahedra in K2LiVS4, Rb2LiVS4, and
Cs2LiVS4 (Tables 2 and 3) are minimally distorted.
The range of V–S distances is 2.1326(8)–2.1613(8) A
and the range of S–V–S angles is 106.85(3)–110.96(3)1.
These may be compared to V–S distances of
2.141(1)–2.170(1) A and S–V–S angles of 108.54(4)–
111.86(6)1 in AVS4 (A ¼ Rb, Cs) [26]. Similarly, the
MS4 (M ¼ Nb, Ta) tetrahedra in Rb2LiNbS4,
Cs2LiNbS4, and Rb2LiTaS4 (Tables 4 and 5) are nearly
regular with M–S distances ranging from 2.254(1) to
2.292(1) A and S–M–S angles ranging from 105.27(5) to
112.45(5) A. These may be compared to M–S distances
of 2.262(6)–2.287(6) A and S–M–S angles of
107.71(4)–112.4(3)1 in A3MS4 (A ¼ Na, Rb; M ¼ Nb,
Ta) [27]. The LiS4 tetrahedra in Rb2LiVS4, Cs2LiVS4,
5. Supplementary material available
Crystallographic data in CIF format have been
deposited with FIZ Karlsruhe with the following CSD
numbers: K2LiVS4, 414184; Rb2LiVS4, 414185;
Cs2LiVS4, 414186; Rb2LiNbS4, 414189; Cs2LiNbS4,
414187; and Rb2LiTaS4, 414186. These data may be
obtained free of charge by contacting FIZ Karlsruhe at

ARTICLE IN PRESS
F.Q. Huang et al. / Journal of Solid State Chemistry 178 (2005) 194–199
199
+49 7247 808 666 (fax) or crysdata@fiz-karlsruhe.de
(E-mail).
[13] H. Sabrowsky, A. Thimm, P. Mertens, Z. Naturforsch. B: Anorg.
Chem. Org. Chem. 40 (1985) 733–735.
[14] H. Sabrowsky, K. Hippler, R.-D. Hitzbleck, S. Sitta, A. Thimm,
P. Vogt, R. Wortmann, Z. Naturforsch. B: Chem. Sci. 44 (1989)
893–895.
Acknowledgments
[15] D. Schmitz, W. Bronger, Z. Anorg. Allg. Chem. 553 (1987)
248–260.
[16] J. Leal-Gonzalez, S.S. Melibary, A.J. Smith, Acta Crystallogr.
Sect. C: Cryst. Struct. Commun. 46 (1990) 2017–2019.
[17] Y. Matsushita, M.G. Kanatzidis, Z. Naturforsch. B: Chem. Sci.
53 (1998) 23–30.
This research was supported by the MRSEC program
of the National Science Foundation (DMR00-76097) at
the Materials Research Center of Northwestern Uni-
versity.
[18] R. Kanno, T. Hata, Y. Kawamoto, M. Irie, Solid State Ion. 130
(2000) 97–104.
[19] M. Murayama, R. Kanno, Y. Kawamoto, T. Kamiyama, Solid
State Ion. 154–155 (2002) 789–794.
References
[20] D.-Y. Seung, P. Gravereau, L. Trut, A. Levasseur, Acta Crystal-
logr. Sect. B: Struct. Sci. 54 (1998) 900–902.
[1] S.A. Sunshine, D. Kang, J.A. Ibers, J. Am. Chem. Soc. 109 (1987)
6202–6204.
[21] O. Glemser, M. Filcek, Z. Anorg. Allg. Chem. 279 (1955)
321–323.
[2] Y.-J. Lu, J.A. Ibers, Inorg. Chem. 30 (1991) 3317–3320.
[3] J.A. Cody, E.J. Wu, C.M. Cheung, J.A. Ibers, J. Solid State
Chem. 121 (1996) 225–229.
[22] G. Gattow, J. Zemann, Z. Anorg. Allg. Chem. 279 (1955)
324–327.
[4] K.O. Klepp, D. Sturmayr, Eur. J. Solid State Inorg. Chem. 34
(1997) 1133–1142.
[23] J.R. Dahn, W.R. McKinnon, R.R. Haering, W.J.L. Buyers,
B.M. Powell, Can. J. Phys. C 212 (1980) 207–213.
[24] Bruker, SMART Version 5.054 Data Collection and SAINT-Plus
Version 6.45a Data Processing Software for the SMART System,
2003. Bruker Analytical X-ray Instruments, Inc., Madison, WI,
USA.
[5] K.O. Klepp, G. Gabl, Eur. J. Solid State Inorg. Chem. 34 (1997)
1119–1131.
[6] C. Rumpf, C. Nather, I. Jeb, W. Bensch, Eur. J. Solid State Inorg.
¨
Chem. 34 (1997) 1165–1177.
[7] C. Rumpf, R. Tillinski, C. Nather, P. Durichen, I. Jeb, W.
[25] G.M. Sheldrick, SHELXTL Version 6.14, 2003. Bruker Analy-
tical X-ray Instruments, Inc., Madison, WI, USA.
[26] M. Emirdag-Eanes, J.A. Ibers, Z. Kristallogr. New Cryst. Struct.
216 (2001) 489–490.
¨
¨
Bensch, Eur. J. Solid State Inorg. Chem. 34 (1997) 1187–1198.
[8] Y.-J. Lu, J.A. Ibers, Comments Inorg. Chem. 14 (1993) 229–243.
[9] G. Busch, B. Hilti, E. Steigmeier, Comp. Soc. Suis. Phys. 31
(1961) 379–382.
[27] R. Niewa, G.V. Vajenine, F.J. DiSalvo, J. Solid State Chem. 139
(1998) 404–411.
[10] Y.-J. Lu, J.A. Ibers, J. Solid State Chem. 58–62.
[11] Y.-J. Lu, J.A. Ibers, J. Solid State Chem. 94 (1991) 381–385.
[12] M. Latroche, J.A. Ibers, Inorg. Chem. 29 (1990) 1503–1505.
[28] F.Q. Huang, Y. Yang, C. Flaschenriem, J.A. Ibers, Inorg. Chem.
40 (2001) 1397–1398.