Na3SbS3: Single crystal X-ray diffraction, raman spectroscopy, and impedance measurements

Article abstract of DOI:10.1002/zaac.201200511

Na₃SbS₃ was prepared by the reaction of anhydrous Na₂S, antimony, and sulfur in a ratio of 3:2:3 at 870 K. The pale yellow compound is air and moisture sensitive. A microcrystalline sample was obtained after annealing Na₃SbS₃ for two weeks at 720 K. The crystal structure of Na₃SbS₃ was determined by single-crystal X-ray diffraction at 123 K. Na₃SbS₃ crystallizes in the cubic space group P2₁3 (No. 198) with a = 8.6420(1) A, V = 645.42(1) A³ and Z = 4. The structure refinement converged to R = 0.0099 (wR = 0.0181) for 592 independent reflections and 23 parameters. Na₃SbS₃ is isotypic with Na ₃AsS₃. Sodium atoms are located on three different sites, which show a strongly distorted octahedral coordination sphere of sulfur. The coordination polyhedra of equivalent sodium sites share common vertices, whereas those of different sodium sites share common faces. Antimony and sulfur form trigonal SbS₃ pyramids, which coordinate sodium as a mono-, bi-, or tridentate ligand. Raman spectroscopic investigations result in stretching modes ν(Sb-S) at 334, 321, and 312 cm^-1, respectively. Thermoanalytical studies do not show any additional thermal effects up to the melting point of 875 K. Impedance spectroscopy on Na₃SbS₃ in a range from 325 to 570 K shows a temperature dependent Na⁺ conductivity, which is 1.9 × 10^-6 Ω^-1·cm^-1 at 570 K. Copyright

Full text of DOI:10.1002/zaac.201200511

ARTICLE
DOI: 10.1002/zaac.201200511
Na3SbS3: Single Crystal X-ray Diffraction, Raman Spectroscopy, and
Impedance Measurements
Constantin Pompe[a] and Arno Pfitzner*[a]
Dedicated to Professor Hartmut Bärnighausen on the Occasion of His 80th Birthday
Keywords: Chalcogenometalates; Sodium; Ion conductor; Crystal structure; Raman spectroscopy
Abstract. Na3SbS3 was prepared by the reaction of anhydrous Na2S,
antimony, and sulfur in a ratio of 3:2:3 at 870 K. The pale yellow
compound is air and moisture sensitive. A microcrystalline sample was
obtained after annealing Na3SbS3 for two weeks at 720 K. The crystal
structure of Na3SbS3 was determined by single-crystal X-ray diffrac-
strongly distorted octahedral coordination sphere of sulfur. The coordi-
nation polyhedra of equivalent sodium sites share common vertices,
whereas those of different sodium sites share common faces. Antimony
and sulfur form trigonal SbS3 pyramids, which coordinate sodium as
a mono-, bi-, or tridentate ligand. Raman spectroscopic investigations
tion at 123 K. Na3SbS3 crystallizes in the cubic space group P213 (No. result in stretching modes ν(Sb–S) at 334, 321, and 312 cm–1, respec-
198) with a = 8.6420(1) Å, V = 645.42(1) Å3 and Z = 4. The structure
refinement converged to R = 0.0099 (wR = 0.0181) for 592 indepen-
dent reflections and 23 parameters. Na3SbS3 is isotypic with Na3AsS3.
tively. Thermoanalytical studies do not show any additional thermal
effects up to the melting point of 875 K. Impedance spectroscopy on
Na3SbS3 in a range from 325 to 570 K shows a temperature dependent
Sodium atoms are located on three different sites, which show a Na+ conductivity, which is 1.9ϫ10–6 Ω–1·cm–1 at 570 K.
type. It shows an ionic conductivity of 5.4ϫ10–5 Ω–1·cm–1.[10]
In contrary, Na3SbSe3 crystallizes in the well-established
Na3AsS3 structure type and shows also an enhanced ionic con-
ductivity at elevated temperature.[11]
Introduction
Alkali metal pnicogen chalcogenides M3PnQ3 (M = Na, K,
Rb, Cs, Pn = As, Sb, Bi, and Q = S, Se, Te) are a well-estab-
lished group of compounds. Although the homologous ele-
Herein, we report on the structural characterization and the
ments differ significantly from each other in terms of ion radii
ionic conductivity of the corresponding thioantimonate,
and electronegativity, they form a whole series of isotypic
Na3SbS3. To date, only lattice parameters are known, which
crystal structures, and crystallize in the cubic space group
are based on Guinier powder data, and isotypism to Na3AsS3
P213. The structure type is named after the first representative
Na3AsS3.[1] Sommer and Hoppe as well as Bronger et al. had
has been proposed.[2]
a great merit on the synthesis and structural characterization
of the corresponding compounds. Sommer described the so- Results and Discussion
dium and potassium containing thioarsenates (Na3AsS3,
K3AsS3,) and thioantimonates (Na3SbS3, K3SbS3),[2] whereas
Structure Description and Discussion
Bronger and co-workers focused on the selenoarsenates
The crystal structure of Na3SbS3 was determined from sin-
gle-crystal X-ray diffraction data collected at 123 K. The title
compound crystallizes in space group P213. The cubic cell has
the parameters a = 8.6420(1) Å, V = 645.42(1) Å3 and Z = 4.
From powder diffraction data of pure powder samples a cell
parameter of a = 8.7026(5) Å was determined at room tem-
perature. Crystallographic data are listed in Table 1. The struc-
ture refinement with anisotropic displacement parameters con-
verged to R1 = 0.0099 [23 parameters, 592 reflections with
I Ͼ 2σ(I)] and wR2 = 0.0181 (all reflections). Atomic coordi-
nates and equivalent isotropic displacement parameters Ueq are
listed in Table 2, the anisotropic displacement parameters Uij
in Table 3.
(Na3AsSe3,
K3AsSe3),
selenoantimonates
(K3SbSe3,
Rb3SbSe3, Cs3SbSe3), and the selenobismutates (K3BiSe3,
Rb3BiSe3, Cs3BiSe3).[3–6] The telluroantimonates Na3SbTe3
and K3SbTe3 were also reported in literature.[7,8] Jung firstly
investigated the conductivity of a compound of this series
M3PnQ3, i.e., K3SbTe3, which was reported to be a poor semi-
conductor.[9] Very recently the thioantimonate Li3SbS3 was
structurally characterized. It is the first member of this whole
group of materials, which crystallizes in a different structure
* Prof. Dr. A. Pfitzner
Fax: +49-941-943-814551
E-Mail: arno.pfitzner@chemie.uni-regensburg.de
[a] Institut für Anorganische Chemie
Universität Regensburg
The Na3AsS3 structure type and its relations to the NaClO3
as well as to the Th3P4 structure type has already been dis-
cussed in several publications.[2,6] Thus, we limit the dis-
Universitätsstraße 31
93040 Regensburg, Germany
296
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Z. Anorg. Allg. Chem. 2013, 639, (2), 296–300

Na3SbS3: Single Crystal X-ray Diffraction
Table 1. Crystallographic data for the structure analysis of Na3SbS3.
Table 3. Anisotropic displacement parameters Uij for Na3SbS3.
Na3SbS3
Atom U11
U22
U33
U23
U13
U12
Formula weight /g·mol–1
Color
Crystal system
286.90
pale yellow
cubic
P213 (No. 198)
8.6420(1)
645.42(1)
Na1 0.0167(3) U11
Na2 0.0117(3) U11
Na3 0.0119(3) U11
U11
U11
U11
U11
0.0005(3)
0.0005(3)
–0.0003(3) U23
–0.00044(4) U23
U23
U23
U23
U23
U23
U23
Space group
Sb
S
0.00775(6) U11
0.0092(2) 0.0101(2) 0.0116(2) 0.0005(2)
Lattice constant a /Å
Cell volume V /Å3
Number of formula units per unit cell Z
Calculated density ρcalc /g·cm–3
Temperature T /K
0.0025(2) 0.0005(2)
4
2.953
123
0.71073
cussion herein to the most important details. Distances and
angles are based on the data obtained at 123 K.
Wavelength λ /Å
The crystal structure of Na3SbS3 can be subdivided into two
structural motifs. Antimony and sulfur are arranged as trigo-
nal-pyramidal SbS3 units (see Figure 2) with an angle S–Sb–S
= 99.40(1)°, the distance d(Sb–S) is 2.4237(4) Å. So-called
secondary bonds are formed to three sulfur atoms at a distance
of 3.6890 Å. A detailed comparison with isotypic thioantimo-
nates(III) of the other alkali metals is not possible due to a
lack of precise structural data for some of them. However,
Li3SbS3 was synthesized recently.[10] It represents a com-
pletely different structure type as compared with the other
compounds of the series M3PnQ3. Nevertheless, the SbS3 units
therein show the typical bond lengths and angles, regardless
the fact that they do not have perfect trigonal symmetry in
Li3SbS3. The trigonal-pyramidal SbS3 motif was also found in
compounds like Cu3SbS3, (CuI)2Cu3SbS3, or (AgI)2Ag3SbS3.
The distance Sb–S in Cu3SbS3 varies between 2.446 and
2.478 Å.[12] Shorter distances were observed in (CuI)2Cu3SbS3
(2.434 to 2.446 Å).[13] In silver containing analogue
(AgI)2Ag3SbS3, the distances range from 2.418 to 2.426 Å at
173 K.[14]
Diffractometer
Oxford Diffraction Gemini R
Ultra CCD, Mo-Kα (λ =
0.71073 Å)
5.308
Absorption coeff. μ /mm–1
Absorption correction
2θ range /°
Multi-scan[19]
6.66 Յ 2θ Յ 58.68
–11 Յ h Յ 10
–11 Յ k Յ 10
–11 Յ l Յ 11
9385, 0.0337
592
hkl-ranges
No. of reflections, Rint
No. of independent reflections
Structure solution
Structure refinement
No. of parameters
Final R, wR [I Ͼ 2σ(I)]
Final R, wR (all reflections)
GooF
SIR92[20]
SHELX-97[21]
23
0.0099, 0.0180
0.0106, 0.0181
1.099
Largest difference peak Δρmax and hole 0.451, -0.264
Δρmin /e·Å–3
Extinction parameter
Flack parameter
0.0016(2)
–0.04(2)
Table 2. Atomic coordinates and equivalent isotropic displacement pa-
a)
rameters Ueq for Na3SbS3.
Atom
Wyck. x
y
z
Ueq
Na1
Na2
Na3
Sb
4a
4a
4a
4a
12b
0.82507(8) x
0.56826(8) x
0.05968(8) x
0.28492(1) x
x
x
x
x
0.0167(3)
0.0117(3)
0.0119(3)
0.00775(6)
Figure 2. Coordination of antimony in the SbS3 units and sodium in
the next coordination sphere.
S
0.01647(5) 0.24997(4) 0.35818(5) 0.01027(9)
a) Ueq is defined as one third of the trace of the orthogonalized Uij
tensor.
Figure 1 shows the three different coordination modes of
SbS3 units to the three different sodium sites Na1, Na2, and
Figure 1. The distorted octahedral coordination of the three sodium sites Na1 (a), Na2 (b), and Na3 (c). Distances are given in Å.
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C. Pompe, A. Pfitzner
ARTICLE
Na3 in Na3SbS3. Na1 is coordinated exclusively by mono-
dentate and Na2 by bidentate SbS3 ligands, respectively. Na3
is coordinated by one tridentate as well as by three mono-
dentate ligands. These coordination modes result in three dif-
ferent distorted octahedral environments for the sodium atoms.
The interatomic distances in Table 4 quantify the distortions of
the NaS6 units. Several examples of SbS3 units acting as biden-
tate ligands to transition metals in competition with ammines
have been recently reported.[15–18] However, in these examples
only one coordination mode is observed.
Table 4. Selected interatomic distances /Å and angles /° for Na3SbS3
at 123 K.
Figure 3. The measured (top) and calculated X-ray powder diffraction
pattern for Na3SbS3 (down, inverted intensities). All measured lines
can be indexed with a cubic primitive cell with a = 8.7026(5) Å.
Sb–S
3ϫ
3ϫ
2.4237(4)
3.6890(4)
S–Sb–S
3ϫ
99.40(1)
Na1–S
3ϫ
3ϫ
3.0355(9)
3.1288(9)
S–Na1–S 3ϫ
S–Na1–S 3ϫ
S–Na1–S 3ϫ
S–Na1–S 3ϫ
S–Na1–S 3ϫ
83.65(3)
84.49(3)
86.79(1)
107.385(7)
164.53(1)
ure 4). The values agree quite well with the spectra for related
compounds like Li3SbS3 (333–301 cm–1) or Ag3SbS3 (330–
303 cm–1).[10,14] Therein SbS3 pyramids are not completely
isolated from each other, which means corresponding distances
dsecondary(Sb–S) are about 3.7 Å. In this case the secondary
bonding interactions between the SbS3 units and the next-near-
est sulfur atoms cause a typical red shift in comparison to com-
pounds, in which the SbS3 units are separated from each other.
(AgI)2Ag3SbS3 e.g., shows resonances between 357 and
316 cm–1.[14]
Na2–S
Na3–S
3ϫ
3ϫ
2.8580(7)
3.0465(9)
S–Na2–S 3ϫ
S–Na2–S 3ϫ
S–Na2–S 3ϫ
S–Na2–S 3ϫ
S–Na2–S 3ϫ
77.46(2)
84.12(3)
95.63(3)
105.998(7)
157.76(2)
3ϫ
3ϫ
2.8461(8)
3.082(1)
S–Na3–S 3ϫ
S–Na3–S 3ϫ
S–Na3–S 3ϫ
S–Na3–S 3ϫ
S–Na3–S 3ϫ
73.71(3)
86.93(2)
94.29(3)
105.368(8)
160.17(3)
The distances d(Na–S) in Na3SbS3 vary between 2.846 and
3.129 Å. A calculated distance of dcalc(Na–S) = 2.86 Å results
from ionic radii.[22] Typically compounds adopting the
Na3AsS3 structure type show two alkali metal sites with bond
lengths in the range of those calculated from ionic radii and
one with significantly longer distances to coordinating chalco-
gen atoms.[11] This is also the case in the title compound with
the longer distances observed for Na1, compare Table 4.
Figure 4. The Raman spectrum shows the bands of the of the Sb–S
Powder X-ray Diffraction
stretching modes at 334, 321, and 312 cm–1.
In Figure 3 the pattern, calculated from single crystal struc-
tural data, is opposed as inverted intensities to the experimental
pattern. A high background in the experimental pattern is due
to the measurement in a sealed glass capillary. The comparison
between both patterns indicates the purity of the sample, which
was subsequently used for impedance measurements. The re-
fined cell constant a = 8.7026(5) Å matches the value, which
was presented by Sommer and Hoppe.[2]
Differential Thermal Analysis (DTA)
A pure, finely powdered sample of Na3SbS3 was used for
DTA. The melting and the crystallization curves show one
maximum, respectively. The melting point of Na3SbS3 is ob-
served at 876 K. The compound crystallizes at 724 K. Similar
dystectic behavior was reported for the selenide analogue
Na3SbSe3.[11] An additional endothermic effect was reported
Raman Spectroscopy
The bonding interactions between antimony and sulfur can for heating curves of Na3SbS3 and a high-temperature modifi-
be estimated by the resonance of the Sb–S stretching vibrations cation was suggested in reference [23] without further charac-
of the SbS3 units.[13] In case of Na3SbS3 they lead to domina- terization. Further experiments, e.g., high-temperature X-ray
ting bands in the range between 334 and 312 cm–1 (see Fig- diffraction will clarify this inconsistency.
298
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Z. Anorg. Allg. Chem. 2013, 296–300

Na3SbS3: Single Crystal X-ray Diffraction
Impedance Measurement
Experimental Section
Synthesis: Pure samples of Na3SbS3 for X-ray powder diffraction and
impedance spectroscopy were obtained from stoichiometric mixtures
of Na2S, antimony (99.9999%, Chempur) and sulfur (99.999%, Chem-
pur) in a 3:2:3 ratio, which were heated to 870 K in evacuated silica
ampoules for 7 d. The ampoules were coated with graphite by pyroly-
sis of acetone prior to use. Anhydrous Na2S was obtained by reaction
of stoichiometric quantities of distilled sodium (99%, Merck) and sul-
fur in dry ammonia.[27] Due to their air and moisture sensitivity, all
procedures with Na2S and Na3SbS3 were performed in an atmosphere
of dry argon. For the structure determination of Na3SbS3, pale yellow
single crystals were obtained after a second annealing period of two
weeks at 720 K.
For the determination of the total electric conductivity of
Na3SbS3 frequency dependent impedance spectroscopy was
performed in a temperature range from 325 to 570 K. The
Nyquist plot in Figure 5 shows the relation between the real
and imaginary part of the impedance at 570 K. The linear arc
for frequencies below 1 kHz is generated by ionic conductivity,
which increases from 1ϫ10–9 Ω–1·cm–1 at 325 K to
2ϫ10–6 Ω–1·cm–1 at 570 K.
Crystal Structure Analysis: A transparent, pale yellow single crystal
of Na3SbS3 was measured in a drop of mineral oil. A nitrogen jet
cooled the sample down to 123 K in order to fix the crystal during
the data collection. Diffraction data were collected with an Oxford
Diffraction Gemini
R Ultra CCD with Mo-Kα radiation (λ =
0.71073 Å). Absorption correction was carried out by multi-scans.[19]
The crystal structure was solved by direct methods with SIR92.[20]
SHELX-97 was used for full-matrix least-squares structure refinement,
applying anisotropic displacement parameters for all atoms.[21] An ex-
tinction parameter was introduced in the final stage of the refinement.
The Flack parameter of almost 0 did not indicate any inversion twin-
ning.
Figure 5. Impedance spectrum of Na3SbS3 at 570 K. The spectrum
shows the typical frequency dependency in case of an ionic conductor
with ion blocking electrodes.
The dependency of ionic conductivity on temperature is il-
lustrated by the Arrhenius plot in Figure 6. The activation en-
ergy is 0.49 eV. The presented results for Na3SbS3 differ in
some case from the recently published values for Na3SbSe3.
The ionic conductivity of the selenide compound reaches a
slightly higher value (3ϫ10–6 Ω–1·cm–1 at 570 K).[11] The
conductivities of both sodium antimony chalcogenides are well
comparable for example to sodium tetrathiophosphate, which
shows an ionic conductivity of 4ϫ10–6 Ω–1·cm–1 at 323 K.[24]
However, Na3SbSe3 shows a significant higher activation en-
ergy of 0.69 eV than Na3SbS3. Ionic conductivity was not de-
tectable below 380 K. Jansen reported decreasing activation
energies of the low-temperature modification for the series
Na3PO4S4–x (x = 0, 1, 2, 3, 4). This observation is explained
by the increasing polarisability of the anion lattice from
Na3PO4 to Na3PS4.[25] Another example for this trend are the
silver ion conducting compounds Ag5Te2–ySeyCl (y = 0–0.7),
whose activation energies decrease with an increasing content
of tellurium.[26] Our studies on Na3SbS3 and Na3SbSe3 result
in a contrary tendency so far. Therefore further investigations
on compounds with a mixed chalcogenide lattice are in pro-
gress.
Powder X-ray Diffraction: Finely ground samples were sealed in an
argon atmosphere in a glass capillary (diameter 0.2 mm). X-ray pow-
der patterns were measured with a STOE Stadi P diffractometer with
monochromatic Cu-Kα1 radiation (λ = 1.540598 Å) and a Ge-mono-
chromator at room temperature. The intensities were collected in a 2θ
range from 8.0° to 90° and evaluated with the STOE program package
WINXPOW.[28]
Further details of the crystal structure investigations may be
obtained from the Fachinformationszentrum Karlsruhe, 76344 Egg-
enstein-Leopoldshafen, Germany (Fax: +49-7247-808-666; E-Mail:
crysdata@fiz-karlsruhe.de, http://www.fiz-karlsruhe.de/request for de-
posited data.html) on quoting the depository number CSD-425458.
Raman Spectroscopy: Raman spectra were recorded with a Varian
FTS 7000e Spectrometer with a Nd:YAG laser (λ = 1064 nm) and a
germanium detector cooled by liquid nitrogen. Samples were sealed in
glass capillaries (diameter 0.5 mm) and measured in back-scattering
mode. The signals were Fourier transformed by a Varian FT-Raman
module and analyzed with the software Varian resolutions pro.[29]
Differential Thermal Analysis: The thermal behavior was recorded
with a Setaram DTA-TG 92–16.18. A small amount of the powdered
sample was filled in a capillary tube (diameter 1.5 mm) and sealed
under vacuum. The tube was heated up from 298 to 1073 K and cooled
down again to room temperature with a heating/cooling rate of
10 K·min–1. Onset temperatures of the melting and crystallization pro-
cess are derived from the respective curves.
Impedance Spectroscopy: Frequency dependent impedance spec-
troscopy of Na3SbS3 was carried out with an experimental set-up de-
scribed earlier in a silica tube in an atmosphere of dry argon.[30] The
heating cycles proceeded in a temperature range from 325 to 570 K in
steps of 10 K. During a measurement the applied frequency was raised
from 1 Hz to 1 MHz with an IMd6A from Zahner Elektrik. Data were
collected and analyzed with the software Thales Flink.[31] Na3SbS3
Figure 6. The Arrhenius plot shows an exponential dependency of the
specific ionic conductivity on the reciprocal temperature.
Z. Anorg. Allg. Chem. 2013, 296–300
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299

C. Pompe, A. Pfitzner
ARTICLE
was cold pressed (20 min, 7000 kg·cm–2) to a pellet with 93% of the
calculated density. It was inserted in the spring-loaded conductivity jig
according to the scheme Pt|Au|Na3SbS3|Au|Pt, where gold acts as ion
blocking electrode.
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Received: November 22, 2012
Published Online: February 11, 2013
300
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Z. Anorg. Allg. Chem. 2013, 296–300