Bi3In4S10 and Bi14.7In 11.3S38: Two new bismuth sulfides with interesting Bi-Bi bonding

Article abstract of DOI:10.1016/j.jssc.2010.08.028

Two new ternary bismuth chalcogenides, Bi₃In₄S ₁₀ and Bi_14.7In_11.3S₃₈, were synthesized from the reactions of binary sulfides via a two-step flux technique. Single-crystal X-ray diffraction analyses indicate that Bi₃In ₄S₁₀ crystallizes in the non-centrosymmetric space group Pm and Bi_14.7In_11.3S₃₈ crystallizes in the centrosymmetric space group P2₁/m. Both compounds adopt three-dimensional frameworks. A distinct structural feature in the two structures is the presence of chains of Bi atoms with alternating short BiBi bonds of around 3.1 and longer distances of around 4.6 . The optical band gaps of 1.42(2) eV for Bi₃In₄S₁₀ and 1.45(2) eV for Bi_14.7In_11.3S₃₈ were deduced from the diffuse reflectance spectra.

Full text of DOI:10.1016/j.jssc.2010.08.028

Journal of Solid State Chemistry 183 (2010) 2544–2551
Contents lists available at ScienceDirect
Journal of Solid State Chemistry
journal homepage: www.elsevier.com/locate/jssc
Bi In S and Bi14.7In S : Two new bismuth sulfides with interesting
3
4 10
11.3 38
Bi–Bi bonding
a,b,c
a,b,c
a,b,n
a,b
, Peizhen Fu , Yicheng Wu
a,b
Wenlong Yin
, Dajiang Mei
, Jiyong Yao
a
Center for Crystal Research and Development, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P.R. China
Key Laboratory of Functional Crystals and Laser Technology, Chinese Academy of Sciences, Beijing 100190, P.R. China
Graduate University of Chinese Academy of Sciences, Beijing 100049, P.R. China
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Two new ternary bismuth chalcogenides, Bi In S and Bi14.7In11.3S38, were synthesized from the
3
4 10
Received 7 June 2010
Received in revised form
reactions of binary sulfides via a two-step flux technique. Single-crystal X-ray diffraction analyses
indicate that Bi In 10 crystallizes in the non-centrosymmetric space group Pm and Bi14.7In11.3
crystallizes in the centrosymmetric space group P2 /m. Both compounds adopt three-dimensional
frameworks. A distinct structural feature in the two structures is the presence of chains of Bi atoms with
3
4
S
S
38
1
3 August 2010
1
Accepted 22 August 2010
Available online 27 August 2010
˚
˚
alternating short Bi–Bi bonds of around 3.1 A and longer distances of around 4.6 A. The optical band
Keywords:
Bismuth
gaps of 1.42(2) eV for Bi
reflectance spectra.
3
In
4
S
10 and 1.45(2) eV for Bi14.7In11.3
S
38 were deduced from the diffuse
Indium
&
2010 Elsevier Inc. All rights reserved.
Sulfide
Crystal structure
Optical
1
. Introduction
Bismuth chalcogenides are an interesting class of materials
In the Bi/In/Q (Q¼S, Se, Te) system, only four sulfides were
reported, namely BiInS
and only the crystal structures of Bi
determined. In Bi In
3
, Bi
2
In
4
S
9
, Bi
4
In
2
S
9
, and Bi
and Bi
3
In
5
S12 [17–20],
2
In
4
S
9
3
5
In S12 were
because they not only possess amazing structural and composi-
tional complexity [1] but also have potential applications as
nonlinear optical materials [2–4], photoelectrics [5], and thermo-
2
4
S
9
, Bi atoms are unusually coordinated to
five closest S forming an orthorhombic pyramid and there are
both octahedrally and tetrahedrally coordinated In atoms [19],
2
electrics [6–9]. The stereochemical activity of 6s lone pair of
3 5
while in Bi In S12 Bi atoms are eightfold (bicapped trigonal prism)
electrons of Bi affects both the structure and the properties of the
resulting compounds [4,7,8]. For this reason the exploratory
synthesis of new bismuth chalcogenides has been an active area
for decades and many bismuth chalcogenides with interesting
structures and properties have been discovered [4,7–14]. For
and sevenfold (monocapped trigonal prism) coordinated and In
atoms are octahedrally coordinated [20]. Both structures are
three-dimensional framework formed by these polyhedra. Con-
sidering the small number of compounds, especially the absence
of selenides and tellurides in the Bi/In/Q (Q¼S, Se, Te) system, we
carried out a detailed exploratory investigation in the Bi/In/Q
system, which has led to the discovery of two new bismuth
example, CsBi
electric properties and Cs
Te
4 6
[7] and K
2
Bi
BiP
8
Se13 [8] possess attractive thermo-
4
Se12 exhibits very large second
5
harmonic generation effect [4]. On the other hand, Indium
chalcogenides are another class of materials with important
indium sulfides: Bi
both contain chains of Bi atoms with alternating short Bi–Bi bonds
3 4
In S10 and Bi14.7In11.3S38. Interestingly, they
˚
˚
properties. For example LiInQ
2
(Q¼S, Se) are excellent IR nonlinear
are important solar cell
of around 3.1 A and longer distances of around 4.6 A. In this paper,
we report the syntheses, structural characterizations, and optical
optical materials [15], while CuInQ
2
materials [16]. Clearly, the macroscopic physical properties of these
compounds stem from both the bonding nature of microscopic
building blocks, i.e. the Bi–Q or In–Q polyhedra, and the packing of
these building blocks in the structure. Thus the combination of
bismuth and indium in one chalcogenide may generate compounds
with interesting structures and properties through the interplay of
the Bi–Q and In–Q polyhedral building blocks.
3 4 38
properties of Bi In S10 and Bi14.7In11.3S .
2
. Experimental section
.1. Crystal growth
The following reagents were used as obtained: Bi (Sinopharm
2
n
Chemical Reagent Co., Ltd., 98+%), In (Sinopharm Chemical Reagent
Co., Ltd., 99.5%), S (Sinopharm Chemical Reagent Co., Ltd., 99.5%),
Corresponding author. Fax: +86 10 82543725.
E-mail address: jyao@mail.ipc.ac.cn (J. Yao).
0022-4596/$ - see front matter & 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.jssc.2010.08.028

W. Yin et al. / Journal of Solid State Chemistry 183 (2010) 2544–2551
2545
and KBr (Sinopharm Chemical Reagent Co., Ltd., 99.5%). The binary
starting materials, Bi and In , were synthesized by the
stoichiometric reactions of elements at high temperatures in sealed
S
2 3
2 3
S
ꢀ
3
silica tubes evacuated to 10 Pa. The annealing temperatures are
00 1C for Bi and 1000 1C for In , respectively.
Black single crystals of Bi In
obtained via a two-step flux technique [21]. For Bi
first step, a mixture of In (0.194 g) and Bi (0.153 g) in a molar
3
S
2 3
2 3
S
3
4
S10 and Bi14.7In11.3S38 were
3
In S10, in the
4
S
2 3
2 3
S
ratio of 2:1 was ground under Ar gas atmosphere in a drybox and
loaded into a fused-silica tube. The tube was then sealed under a
ꢀ
3
1
0
Pa atmosphere and placed in a computer-controlled furnace.
The reaction mixture was heated to 900 1C in 24 h and equilibrated
at this temperature for 48 h and finally cooled to room temperature
by switching off the furnace. The sample thus thermally treated
was used as precursor for the second-step reaction with the KBr
flux (0.70 g) to grow single crystals of new phases. Upon regrinding
and resealing, the precursor–flux mixture was heated to 850 1C in
2
3
4 h, kept at 850 1C for 96 h, then cooled at a slow rate of 4 1C/h to
00 1C, and finally cooled to room temperature. The reaction
product consisted of black long needles of Bi
which were manually selected for structure characterization.
Black needles of Bi14.7In11.3 38 were obtained in a similar two-
step procedure. The reagents, In (0.097 g) and Bi (0.153 g) in
3 4
In S10 single crystals,
S
2
S
3
2 3
S
a molar ratio of 1:1, were mixed and sealed in a fused-silica
ampoule under vacuum. The reacted precursor was reground with
0
.50 g KBr flux and then reheated using similar heating profiles
described above.
Analyses of the crystals with an EDX-equipped Hitachi S-3500
SEM showed the presence of Bi, In, and S. The two compounds are
stable in air for months.
2.2. Synthesis of pure polycrystalline materials
Fig. 1. Experimental (top) and simulated (bottom) X-ray powder diffraction data
3 4
of Bi In S10 (left) and Bi14.7In11.3S38 (right).
After the structural identification, the stoichiometric syntheses
of the polycrystalline compounds were carried out using reaction
mixtures as follows:
at 93 K on a Rigaku AFC10 diffractometer equipped with a Saturn
CCD detector. Crystal decay was monitored by re-collecting 50
initial frames at the end of data collection. The collection of the
intensity data was carried out with the program Crystalclear [22].
Cell refinement and data reduction were carried out with the use
of the program Crystalclear [22], and face-indexed absorption
corrections were performed numerically with the use of the
program XPREP [23].
6
In
2
S
3
+4Bi
2
S
3
+Bi-3Bi
3
In
4
S
10
(1)
(2)
3
39In
2
S
3
+421Bi
2
S
3
+40Bi-60Bi14.7In11.3S
38
Pure polycrystalline samples of Bi
were synthesized by solid-state reaction techniques. For the
synthesis of pure Bi In 10 powder, a mixture of In (1.995 g),
Bi (2.075 g), and Bi (0.209 g) in the molar ratio of 6:4:1 was
grounded and loaded into a fused-silica tube under an Ar
3 4 38
In S10 and Bi14.7In11.3S
3
4
S
2
S
3
The structures were solved with the direct methods program
SHELXS and refined with the least-squares program SHELXL of
4 10
the SHELXTL.PC suite of programs [23]. The structure of Bi In S
2 3
S
3
ꢀ
3
atmosphere in a glovebox. The tube was sealed under 10 Pa
atmosphere and then placed in a computer-controlled furnace.
The sample was heated to 650 1C in 20 h, kept at that temperature
was solved in the non-centrosymmetric space group Pm.
During the initial structural refinement of Bi In S10, the site
3
4
occupancies of Bi8 and Bi9 positions were allowed to refine since
0
˚
0
˚
for 48 h, and then the furnace was turned off. Pure Bi14.7In11.3
powder was prepared in a similar manner from a reaction mixture
of In (1.105 g), Bi (2.165 g), and Bi (0.084 g) in the molar
S
38
there were too short Bi8–Bi8 (0.615(5) A) and Bi9–Bi9 (0.669(5) A)
contacts. The resultant occupancies of Bi8 and Bi9 were
both around 0.49 and therefore they were then fixed to be
0.5 in the subsequent refinements. The flack parameter
was around 0.5, which suggested a racemic twin or a centrosym-
metric space group. Analysis of the atomic positions with the
use of the ADDSYM in the PLATON suite of programs [24] did
not reveal any additional symmetry. Thus the crystal was
refined as a racemic twin with the resultant twin ratio of
0.53:0.47.
2
S
3
2 3
S
ratio of 339:421:40 at 600 1C for 72 h.
X-ray powder diffraction of the resultant powder sample was
performed at room temperature in the angular range of 2
with a scan step width of 0.021 and a fixed counting time of 1 s/step
y¼7ꢀ701
using an automated Bruker D8 X-ray diffractometer equipped with
˚
a diffracted monochromator set for CuK
a (l¼1.5418 A) radiation.
The experimental powder X-ray diffraction patterns were found to
be in good agreement with the calculated ones based on the single-
crystal crystallographic data (Fig. 1).
For the structure solution of Bi14.7In11.3S38, seven Bi, six In, and
nineteen S atoms were found by the direct methods. In the initial
refinement, the isotropic displacement parameters of In1 and In4
3
+
2.3. Structure determination
were close to zero, which indicated partial substitution of In by
3
+
Bi
at these sites. Subsequently disorder of Bi and In was
Single-crystal X-ray diffraction data were collected with the
use of graphite-monochromatized Mo Ka radiation (l
¼0.71073 A˚ )
introduced at In1 and In4 positions and the refinements showed
that Bi and In were disordered at the In1 and In4 positions with

2
546
W. Yin et al. / Journal of Solid State Chemistry 183 (2010) 2544–2551
Table 1
Bi/In ratios of 0.235/0.765 and 0.113/0.887, respectively. The
resultant R index R /wR decreased from 0.0363/0.0930 to 0.0277/
.0646 and the largest peak/hole in difference electron density
a
3 4 38
Crystal data and structure refinements for Bi In S10 and Bi14.7In11.3S .
1
2
0
Bi
3
In
4
S
10
Bi14.7In11.3S
38
ꢀ
3
˚
map was reduced from 13.41/ꢀ3.12 to 4.09/ꢀ2.99 e A
with
fw
1406.82
5587.75
this disorder model. No detectable disorder between Bi and In was
observed at other metal positions. The final stoichiometry was
a ( A˚ )
11.566(2)
11.386(2)
b ( A˚ )
c ( A˚ )
7.6427(15)
17.742(4)
3.8570(8)
34.103(7)
38
then refined to be Bi14.7In11.3S .
The final refinements included anisotropic displacement
parameters for both compounds and a secondary extinction
b
(deg)
98.03(3)
94.67(3)
V ( A˚ 3
1553.0(5)
1492.7(5)
)
Space group
Pm
P2
1
/m
3 4
correction for Bi In S10. The program STRUCTURE TIDY [25] was
Z
4
1
then employed to standardize the atomic coordinates. Additional
experimental details are given in Table 1 and selected metrical
data are given in Tables 2–5. Further information may be found in
Supplementary material.
3
r
m
c
(g/cm )
6.017
410.16
0.0498
0.1307
6.216
ꢀ
1
(cm
b
)
487.51
0.0276
0.0646
R(F)
2
c
W
o
R (F )
a
b
c
˚
For both T¼93(2) K and
l
¼0.71073 A.
P
P
2
2
2.4. Diffuse reflectance spectroscopy
R(F)¼ jjF
o
jꢀjF
c
jj/ jF
o
j for F 42
s
(F ).
o
o
P
P
2
2
o
2
c
2
4
1/2
ꢀ1
2
2
2
R
w
(F )¼{ [w(F ꢀF ) ]/ wF
}
for all data. w
¼s (F )+(zP) , where
o
o
o
2
o
2
c
P¼(Max(F , 0)+2F )/3; z¼0.07 for Bi
In
3 4
S
38
10 and 0.03 for Bi14.7In11.3S .
A
Cary 1E UV–visible spectrophotometer with a diffuse
reflectance accessory was used to measure the spectra of Bi In
38 over the range 200 nm (6.25 eV) to 2500 nm
3
4 10
S
and Bi14.7In11.3
S
Table 2
Atomic coordinates and equivalent isotropic displacement parameters ( A˚ 2) for
Bi In
(
0.50 eV).
3
4 10
S .
a
3. Results and discussion
Atom
x
y
z
U
eq
Bi1
Bi2
Bi3
Bi4
Bi5
Bi6
Bi7
Bi8
Bi9
In1
In2
In3
In4
In5
In6
In7
In8
In9
In10
In11
In12
S1
0.5702(2)
0.2772(2)
0.5075(2)
0.1312(2)
0.1304(2)
0.2534(2)
0.3718(2)
0.0670(3)
0.0660(3)
0.9075(4)
0.7759(4)
0.6958(4)
0.2230(4)
0.4168(4)
0.8988(4)
0.7362(4)
0.9441(4)
0.8607(4)
0.2208(4)
0.6920(4)
0.7762(4)
0.4993(13)
0.0364(14)
0.4351(15)
0.4348(14)
0.30018(14)
0.0000
0.73574(15)
0.80397(13)
0.98194(12)
0.25669(13)
0.25641(13)
0.79918(14)
0.43606(13)
0.50218(19)
0.50164(19)
0.8584(3)
0.2022(3)
0.5577(3)
0.0392(3)
0.1998(3)
0.8574(3)
0.3802(2)
0.6778(3)
0.0355(3)
0.0390(3)
0.5637(3)
0.2027(3)
0.8716(8)
0.8149(10)
0.0968(9)
0.0976(9)
0.0013(8)
0.4232(8)
0.5892(9)
0.2379(9)
0.1804(9)
0.8924(9)
0.0572(10)
0.5329(9)
0.7067(8)
0.6495(9)
0.6500(9)
0.0041(2)
0.0083(5)
0.0100(5)
0.0084(5)
0.0086(5)
0.0127(5)
0.0137(5)
0.0195(8)
0.0200(8)
0.0069(9)
0.0065(10)
0.0077(9)
0.0060(9)
0.0102(9)
0.0056(9)
0.0058(8)
0.0066(8)
0.0083(9)
0.0062(9)
0.0069(9)
0.0067(10)
0.008(3)
0.014(3)
0.006(3)
0.006(3)
0.006(3)
0.006(3)
0.008(3)
0.011(3)
0.010(3)
0.013(3)
0.008(3)
0.017(3)
0.007(3)
0.010(3)
0.011(3)
0.009(3)
0.010(3)
0.016(3)
0.002(3)
0.005(2)
0.025(4)
0.003(3)
0.003(3)
0.023(4)
0.018(4)
0.008(3)
0.004(3)
0.004(3)
0.007(3)
0.011(3)
3
.1. Syntheses
0.24816(12)
0.0000
3 4
Black single crystals of Bi In S10 and Bi14.7In11.3S38 were
0.5000
obtained with the aid of KBr as flux. This is the first time that
0.5000
0.25061(12)
0.0403(3)
0.4562(3)
0.5000
Table 3
Atomic coordinates and equivalent isotropic displacement parameters ( A˚ 2) for
0.0000
Bi14.7In11.3
38
S .
0.5000
0.5000
a
Atom
x
y
z
U
eq
0.2499(2)
0.0000
Bi1
Bi2
Bi3
Bi4
Bi5
Bi6
Bi7
In1
Bi8
In2
In3
In4
Bi9
In5
In6
S1
0.03909(4)
0.18695(5)
0.76823(4)
0.20853(4)
0.8013
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.15474(16)
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.2500
0.390575(16)
0.500404(17)
0.927770(16)
0.761136(16)
0.714713(16)
0.805798(18)
0.16923(2)
0.00449(13)
0.01030(14)
0.00653(14)
0.00651(14)
0.00455(13)
0.01203(15)
0.0071(2)
0.0056(3)
0.0056(3)
0.0023(2)
0.0021(2)
0.0045(3)
0.0045(3)
0.0015(2)
0.0054(2)
0.0054(7)
0.0054(7)
0.0061(7)
0.0058(7)
0.0085(8)
0.0049(7)
0.0055(7)
0.0050(7)
0.0057(7)
0.0047(7)
0.0091(8)
0.0046(7)
0.0067(7)
0.0078(8)
0.0043(7)
0.0055(7)
0.0059(7)
0.0094(8)
0.0069(7)
0.2490(2)
0.2444(2)
0.2504(2)
0.0000
0.0000
0.5000
0.58740(5)
0.05958(6)
0.54612(7)
0.54612(7)
0.93103(8)
0.42596(8)
0.24912(7)
0.24912(7)
0.66177(8)
0.48289(8)
0.4828(3)
0.2371(3)
0.5775(3)
0.2580(3)
0.4714(3)
0.2535(3)
0.9400(3)
0.9929(3)
0.6986(3)
0.4175(3)
0.6118(3)
0.5735(3)
0.3041(3)
0.9496(3)
0.1295(3)
0.0253(3)
0.7227(3)
0.8257(3)
0.1898(3)
0.0000
S2
0.2483(8)
0.5000
0.54699(2)
S3
0.54699(2)
S4
0.0000
0.04141(3)
S5
0.5000
0.95815(3)
S6
0.5990(15)
0.5527(13)
0.6341(13)
0.9242(15)
0.7664(15)
0.7153(15)
0.8449(14)
0.7993(14)
0.0879(16)
0.0812(16)
0.0000
0.63621(3)
S7
0.2555(7)
0.2498(8)
0.2493(8)
0.2545(9)
0.5000
0.63621(3)
S8
0.13801(3)
S9
0.32877(3)
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
S20
S21
S22
S23
S24
S25
S26
S27
S28
S29
S30
0.88268(11)
0.22209(10)
0.20836(11)
0.12791(10)
0.62079(11)
0.33778(10)
0.53748(11)
0.91147(10)
0.31281(10)
0.03240(10)
0.47483(11)
0.72269(10)
0.43623(10)
0.24582(11)
0.01167(10)
0.65993(11)
0.06477(11)
0.41351(11)
0.83682(11)
S2
0.2510(15)
0.0000
S3
0.0000
S4
0.5000
S5
ꢀ0.0005(16)
0.4817(14)
0.1963(17)
0.7986(13)
0.3352(13)
0.3057(15)
0.3638(13)
0.3639(13)
0.3036(15)
0.2750(16)
0.7146(15)
0.8710(15)
0.8698(14)
0.5997(15)
0.1493(12)
0.0000
ꢀ0.0001(9)
0.8745(8)
0.1447(10)
0.7059(7)
0.7156(7)
0.5290(12)
0.2912(8)
0.2911(8)
0.5284(12)
0.9472(11)
0.0566(11)
0.3480(9)
0.3481(9)
0.4194(9)
0.3650(8)
S6
0.5000
S7
0.2503(7)
0.5000
S8
S9
0.2555(7)
0.0000
S10
S11
S12
S13
S14
S15
S16
S17
S18
S19
0.0000
0.5000
0.5000
0.2463(15)
0.0000
0.5000
0.0000
0.5000
0.2497(8)
a
a
U
eq is defined as one-third of the trace of the orthogonalized Uij tensor.
Ueq is defined as one-third of the trace of the orthogonalized Uij tensor.

W. Yin et al. / Journal of Solid State Chemistry 183 (2010) 2544–2551
2547
Table 4
Table 5
Selected bond lengths ( A˚ ) for Bi
3
In
4
S
10
.
Selected bond lengths ( A˚ ) for Bi14.7In11.3
S .
38
In-1S2
2.615(13)
2.615(13)
2.619(16)
2.612(14)
2.612(14)
2.820(15)
2.650(13)
2.650(13)
2.627(14)
2.627(14)
2.581(19)
2.664(17)
2.609(12)
2.609(12)
2.647(15)
2.647(15)
2.730(14)
2.549(16)
2.522(16)
2.547(18)
2.720(14)
2.720(14)
2.657(16)
2.657(16)
2.674(12)
2.661(11)
2.510(15)
2.601(19)
2.633(11)
2.632(11)
2.653(14)
2.653(14)
2.604(13)
2.604(13)
2.759(15)
2.632(16)
2.658(12)
2.633(15)
2.824(16)
2.585(12)
2.565(12)
2.639(12)
2.516(18)
2.664(16)
2.607(11)
2.596(13)
2.605(13)
2.670(10)
In9-S5
In9-S9
2.639(12)
2.573(16)
2.620(16)
2.608(12)
2.631(13)
2.615(13)
2.547(16)
2.557(19)
2.720(14)
2.720(14)
2.623(16)
2.623(16)
2.573(16)
2.611(12)
2.611(11)
2.717(15)
2.717(15)
2.665(15)
2.652(13)
2.652(13)
2.635(13)
2.635(13)
2.579(19)
2.658(16)
3.506(11)
2.601(17)
3.351(16)
3.596(12)
3.184(12)
3.159(13)
2.713(15)
3.054(2)
Bi4-S9
3.208(14)
3.208(14)
2.932(15)
2.932(15)
2.674(15)
3.624(17)
2.695(11)
2.695(11)
3.207(14)
3.207(14)
2.928(15)
2.928(15)
2.685(15)
3.606(18)
2.701(11)
2.701(11)
3.205(15)
3.205(15)
3.082(16)
2.788(17)
2.643(11)
2.643(11)
3.245(17)
3.245(17)
3.285(14)
3.190(16)
2.705(14)
3.196(12)
3.193(12)
2.702(14)
3.298(14)
2.703(12)
3.143(17)
3.498(16)
2.610(16)
2.753(17)
3.321(16)
3.169(15)
3.520(14)
3.179(4)
In1-S5
2.721(4)
2.630(4)
2.700(3)
2.700(3)
2.607(2)
2.607(2)
2.613(2)
2.613(2)
2.551(3)
2.696(3)
2.696(3)
2.563(3)
2.704(4)
2.542(4)
2.628(2)
2.628(2)
2.642(2)
2.642(2)
2.627(4)
2.632(3)
2.632(2)
2.736(3)
2.662(3)
2.662(3)
2.596(2)
2.596(2)
2.656(4)
2.646(4)
2.660(2)
2.660(2)
In6-S5
In6-S6
In6-S9
In6-S12
In6-S12
Bi1-S6
Bi1-S7
Bi1-S7
Bi1-S13
Bi1-S16
Bi1-S16
Bi1-S18
Bi2-S7
Bi2-S7
Bi2-S7
Bi2-S11
Bi2-S11
In6-S5
Bi2-S13
Bi2-S18
Bi2-S18
Bi3-S1
Bi3-S4
Bi3-S4
Bi3-S8
Bi3-S10
Bi3-S10
Bi3-S15
Bi3-S15
Bi4-S3
2.608(3)
2.655(3)
2.559(3)
2.651(3)
2.651(3)
3.149(3)
3.114(3)
3.114(3)
3.281(4)
2.649(2)
2.649(2)
2.612(3)
2.678(2)
2.678(2)
3.176(4)
3.060(3)
3.060(3)
2.608(3)
2.654(4)
3.525(3)
3.525(3)
3.480(4)
2.706(3)
2.706(3)
2.662(3)
3.241(3)
3.241(3)
2.991(3)
2.991(3)
3.213(3)
Bi4-S9
Bi4-S9
Bi4-S14
Bi4-S14
Bi4-S19
Bi5-S2
Bi5-S2
Bi5-S6
Bi5-S6
Bi5-S12
Bi5-S14
Bi5-S14
Bi5-S16
Bi6-S1
Bi6-S2
Bi6-S2
Bi6-S3
Bi4-S3
Bi6-S3
Bi6-S4
Bi6-S4
Bi6-S12
Bi7-Bi7
Bi7-S2
Bi7-S4
Bi7-S8
Bi7-S8
Bi7-S14
Bi7-S19
Bi7-S19
3.410(3)
In1-S2
Bi4-S9
In1-S11
In1-S11
In1-S11
In1-S13
In1-S13
In2-S8
3.410(3)
2.636(2)
2.636(2)
2.607(4)
2.951(3)
2.951(3)
2.670(3)
2.670(3)
2.629(3)
3.600(3)
3.600(3)
3.282(3)
2.967(4)
2.988(3)
2.988(3)
2.707(3)
3.213(3)
2.707(2)
3.359(3)
3.359(3)
2.826(4)
3.1222(14)
2.622(4)
2.783(3)
3.178(3)
3.597(3)
3.010(4)
3.232(3)
3.644(3)
In1-S5
In9-S10
In9-S11
In9-S16
In9-S26
In10-S4
Bi4-S18
Bi4-S18
Bi4-S22
Bi4-S28
Bi4-S30
Bi4-S30
Bi5-S9
In1-S10
In1-S10
In1-S19
In2-S8
In2-S8
In10-S16
In10-S18
In10-S18
In10-S25
In10-S25
In11-S6
In11-S7
In11-S7
In11-S12
In11-S12
In11-S13
In12-S8
In12-S8
In12-S9
In12-S9
In12-S11
In12-S27
Bi1-S1
In2-S8
In2-S9
In2-S15
In2-S15
In2-S15
In2-S17
In3-S1
In2-S9
Bi5-S9
In2-S26
In2-S28
In3-S7
Bi5-S18
Bi5-S18
Bi5-S23
Bi5-S27
Bi5-S30
Bi5-S30
Bi6-S2
In3-S7
In3-S10
In3-S10
In3-S10
In3-S17
In3-S17
In4-S5
In3-S12
In3-S12
In3-S19
In3-S29
In4-S3
Bi6-S2
Bi6-S15
Bi6-S17
Bi6-S20
Bi6-S20
Bi6-S25
Bi6-S25
Bi7-S6
In4-S5
In4-S9
In4-S18
In4-S18
In4-S25
In4-S25
In5-S3
In4-S9
In4-S16
In4-S18
In4-S18
In5-S1
In5-S4
Bi1-S7
Bi7-S7
In5-S1
In5-S8
Bi1-S10
Bi1-S13
Bi1-S17
Bi1-S19
Bi1-S20
Bi1-Bi1
Bi2-S1
Bi7-S21
Bi7-S22
Bi7-S23
Bi7-S24
Bi7-S29
Bi7-S30
Bi8-S12
Bi8-S12
Bi8-S14
Bi8-S21
Bi8-S28
Bi8-S30
Bi8-S30
Bi8-Bi9
Bi9-S12
Bi9-S12
Bi9-S15
Bi9-S24
Bi9-S27
Bi9-S30
Bi9-S30
In5-S3
In5-S18
In5-S22
In5-S23
In6-S2
In5-S17
In5-S19
In5-S19
In6-S2
In6-S10
In6-S10
In6-S13
In6-S16
In7-S6
2.679(16)
3.399(15)
3.399(15)
3.260(16)
2.649(10)
2.649(10)
3.165(17)
3.165(17)
2.718(10)
3.005(13)
3.000(13)
3.581(19)
3.219(14)
2.697(10)
2.674(19)
3.194(14)
Bi2-S2
(
Fig. 4). Bi1, Bi8, and Bi9 are coordinated to a distorted bicapped
trigonal prism (btp) of seven S and one Bi, while all other Bi atoms
are coordinated in a distorted btp of eight S atoms. The 6s lone
pair is stereochemically active for each Bi atom with the Bi–S
Bi2-S2
Bi2-S14
Bi2-S20
Bi2-S20
Bi2-S25
Bi2-S25
Bi3-S1
2
In7-S8
In7-S12
In7-S27
In7-S28
In7-S29
In8-S2
˚
˚
distances ranging from 2.601(17) to 3.624(17) A (Table 4), which
3 5
are comparable to those of 2.619(4) to 3.397(5) A in Bi In S12 [19].
3.114(17)
3.499(16)
2.636(16)
2.744(18)
3.303(16)
3.155(15)
3.538(13)
Two Bi1(Bi1)(S)
from a [Bi1
stacked along the b direction by edge-sharing. The Bi8(Bi9)(S)
and Bi9(Bi8)(S) btps are connected in a similar manner via the
Bi8–Bi9 bond. Such connectivity produces a row of Bi1 atoms
7
btps are connected by the Bi1–Bi1 bond to
unit and these [Bi1
Bi3-S3
2
0ꢀ
20ꢀ
Bi3-S4
2
S
12
]
2
S
12
]
units are further
In8-S12
In8-S13
In8-S14
In8-S15
In8-S19
Bi3-S10
Bi3-S11
Bi3-S17
Bi3-S25
Bi3-S26
7
7
along the b direction with alternating short and long distances of
˚
3
.054 (2) and 4.588(2) A and another row of Bi8 and Bi9 atoms
˚
with alternating distances of 3.178(3) and 4.464(3) A (Fig. 5). The
short BiyBi distances represent Bi–Bi bonds, which are unusual
in bismuth chalcogenides. Other chalcogenides possessing Bi–Bi
crystals can be grown using the flux method in the Bi/In/Q (Q¼S,
Se, Te) system. In the past, crystals were only grown by the vapor
transport method with the use of iodine or chlorine as the
transporting agent [19,20], which might easily led to the
formation of bismuth halide. According to this study, the flux
method may be a valuable method for isolating new phases in the
Bi/In/Q system. Furthermore, the successful syntheses of pure
polycrystalline samples indicate that these two compounds are
thermodynamically stable phases.
bonds include (Bi
(M¼Nb, Ta) [29,30], Bi
CsBi Te [7,9]. The arrangements of the Bi–Bi bonds in these
compounds are compared in Fig. 5. In BiSe, a typical member of
the (Bi (Bi)
(Q¼Se, Te) family, each Bi is connected to three
Bi atoms to form a metallic Bi layer inserted between the Bi Se
layers [27], while in CsBi Te and (BiS)1.1NbS the Bi–Bi bonds are
separated faraway by the (Bi Te ) block [7,9] and the (BiS) block
30], respectively. As for Bi Ga , although the Bi(Bi)(S) square
2
Q
3
)
m
(Bi)
n
(Q¼Se, Te) [26,27,28], (BiS)1.1MS
2
2
4 8
M Q
(M¼Al, Ga; Q¼S, Se) [31], and
4
6
2
Q
3
)
m
n
2
3
4
6
2
4
6
[
2
4
S
8
4
pyramid form a pair through the Bi–Bi bond, these pairs are not
further connected to each other, but are separated by GaS4
3.2. Structures
˚
tetrahedra at a distance of 8.8876 (17) A [31]. So even the Bi
Bi In 10 crystallizes in a new three-dimensional structure
3
4
S
atoms may be viewed as aligned in a chain with alternating short
type (Fig. 2). Each In atom is coordinated to an octahedron of six S
atoms with In–S bond lengths ranging from 2.510(15) to
and long distances in Bi
bonding Bi atoms (8.8876(17) A) is much longer than those of
2 4 8
Ga S , the distance between the non-
˚
˚
˚
2
.824(16) A, which are consistent with those of 2.508 (6)–2.833
4.588(2) and 4.464(3) A in Bi
3
In
(3.054 (2) A) and Bi8–Bi9 bond length (3.178(3) A) in Bi
comparable to those of 3.053(2), 3.238(1), 3.124(5), and
4
S10. The Bi1–Bi1 bond length
˚
˚
˚
(5) A in Bi
3
In
5
S12 [19]. The InS
6
octahedra are connected to each
3 4
In S10 are
other by corner and edge-sharing to form the three-dimensional
In–S sublattice (Fig. 3) with channels along the b direction, which
are occupied by the isolated one-dimensional Bi–S sublattice
˚
3.144(1) A in BiSe, CsBi
4
Te
6
, (BiS)1.1NbS
2
, and Bi
2
Ga
4
S
8
, respec-
tively.

2
548
W. Yin et al. / Journal of Solid State Chemistry 183 (2010) 2544–2551
3 4
Fig. 2. Structure of Bi In S10 viewed along [010].
3 4 10.
Fig. 4. Structure of the Bi–S sublattice in Bi In S
8
The remaining BiS btps form four chains along the b direction
by face sharing. All these chains together with the Bi1 btpyBi1
btpyBi1 btpyBi1 btp chain and the Bi8 btpyBi9 btpyBi8
btpyBi9 btp chain are connected to each other by bridging S
atoms and form an one-dimensional Bi–S sublattice along the b
direction (Fig. 4). This Bi–S sublattice is then incorporated into the
empty channels in the In–S sublattice to generate the three-
dimensional framework (Fig. 1).
There is no S–S bond or any detectable disorder among In and
Bi. From the description of the crystal structure, it is evident that
Bi2, Bi3, Bi4, Bi5, Bi6, Bi7, and all In atoms are 3+, while Bi1, Bi8,
and Bi9 are 2+. In this way the charge balance can be achieved by
2
+
3+
3+
2ꢀ
the formula (Bi )(Bi
)
2
(In
)
4
(S
10
) .
The structure of Bi14.7In11.3
S
38 is illustrated in Fig. 6. It is also a
3
+
three-dimensional framework. In
is partially substituted by
at the In1 and In4 positions. Similar substitution was
observed in Pb In Bi l3 [32] and Pb 1n Bi l8 [33]. However,
the amounts of Bi at the In1 and In4 positions are relatively small
23.5% and 11.3%), these two positions will be treated as the In
3
+
Bi
4
2
4
S
4
3
7
S
(
positions in the discussion to simplify the structure description.
Each In atom is coordinated to an octahedron of six S atoms with
˚
the normal In–S bond lengths of 2.551(3)–2.736(3) A. The
structure of the In–S sublattice is shown in Fig. 7. In1S , In4S
and In6S octahedra are connected to each other by corner
and edge-sharing to form a chain along the b direction, while
In2S , In3S , In5S octahedra are connected through corner and
6
6
,
6
6
6
6
edge-sharing to generate a two-dimensional layer parallel to the
ab plane.
Bi1 and Bi4 are coordinated to a distorted monocapped
trigonal prism (mtp) of seven S atoms, and Bi2, Bi3, Bi4, Bi5, and
Bi6 are coordinated to a distorted btp of eight S atoms, while Bi7 is
3 4 10
Fig. 3. Structure of the In–S sublattice in Bi In S .

W. Yin et al. / Journal of Solid State Chemistry 183 (2010) 2544–2551
2549
Fig. 5. Arrangements of Bi–Bi bonds in chalcogenides: (a) Bi1–Bi1 bond in Bi
3
In
4
S
10, (b) Bi8–Bi9 bond in Bi
Ga
3 4
In S
10, (c) Bi7–Bi7 bond in Bi14.7In11.3
S
38, (d) Bi–Bi bond in BiSe,
(
e) Bi–Bi bond in CsBi Te , (f) Bi–Bi bond in (BiS)NbS , and (g) Bi–Bi bonds in Bi
4
6
2
2
4 8.
S
Fig. 6. Structure of Bi14.7In11.3S38 viewed along [010].
2
coordinated to a distorted btp of seven S and one Bi7. The 6s lone
other to generate a two-dimensional layer parallel to the ab plane.
pair also exhibits its stereochemical activity in each Bi atom with
Two such layers, related by a center of inversion, are then linked
˚
the Bi–S bond distances ranging from 2.607(4) to 3.644(3) A
Table 5). Just as the Bi1(Bi1)(S) btps in Bi In 10, two Bi7(Bi7)(S)
7 8
by the Bi1S mtps and Bi2S btps (Fig. 8). The one-dimensional
(
7
3
4
S
7
void produced in this way is occupied by the chain of InS
octahedra, while the Bi–S layers are connected to layers of InS
6
6
btps in Bi14.7In11.3
S
38 are connected by the Bi–Bi bond to from a
2
1
0ꢀ
20ꢀ
[
Bi7
2
S
] unit and these [Bi7
2
S
] units are further connected
octahedra to generate the three-dimensional framework (Fig. 6).
The disorder between Bi and In at the In1 and In4 positions has
no influence on the charge balance since both Bi and In are 3+ at
these two positions. There are no S–S bonds in the structure.
2
12
by two bridging S atoms (Fig. 5). In this way, the Bi7 atoms form a
chain along the b direction with alternating short Bi7–Bi7 bonds
˚
˚
of 3.120(1) A and long distances of 4.594(1) A. All the Bi–S prisms
are stacked along b, forming chains parallel to b. The Bi3 btp, Bi4
btp, Bi5 btp, Bi6 btp, and Bi7 btp chains are connected to each
2
+
3+
Based on the bonding in the structure, a formula of (Bi
)
2
(Bi
)
9.3
3
+
2ꢀ
(In
)14.7(S
)38 can be achieved with the balanced charge.

2
550
W. Yin et al. / Journal of Solid State Chemistry 183 (2010) 2544–2551
38
Fig. 7. Structure of the In–S sublattice in Bi14.7In11.3S .
38
Fig. 8. Structure of the Bi–S sublattice in Bi14.7In11.3S .
3 4
Bi In S10 and 1.45(2) eV for Bi14.7In11.3S38 were deduced by the
straightforward extrapolation method [34].
4. Conclusion
Exploratory investigation in the Bi/In/Q system by means of a
two-step flux method has led to the successful discovery of two
new compounds, namely Bi In 38. They adopt
3
4
S10 and Bi14.7In11.3S
two new types of three-dimensional framework and a character-
istic feature in them is the presence of chains of Bi atoms with
˚
alternating short Bi–Bi bonds of around 3.1 A and longer distances
˚
of around 4.6 A. This is the first time that such chains of Bi atoms
are found in chalcogenides. Based on the bonding in the structure,
2
+
3+
charge balance can be achieved by the formula (Bi )(Bi
)
2
3
+
2ꢀ
2+
3+
3+
2ꢀ
(
In
)
4
(S
)10 for Bi
3
In
4
S10 and (Bi
)
2
(Bi
)9.3(In
)
14.7(S )
38
for Bi14.7In11.3 38. Our successful syntheses of the powder samples
S
according to the above formulas further prove the correctness of
the stoichiometry. From the diffuse reflectance measurements,
the optical band gaps are 1.42(2) eV for Bi
38, respectively.
3 4
In S10 and 1.45(2) eV
Fig. 9. Diffuse reflectance spectra of Bi
In
3 4
S
10 and Bi14.7In11.3
S
38
.
for Bi14.7In11.3S
3.3. Experimental band gap
Acknowledgment
The diffuse reflectance spectra of Bi
are shown in Fig. 9. The optical band gaps of 1.42(2) eV for
3
In
4
S
10 and Bi14.7In11.3
S
38
This research was supported by the National Basic Research
Project of China (no. 2010CB630701).

W. Yin et al. / Journal of Solid State Chemistry 183 (2010) 2544–2551
2551
Supplemental information
[9] D.-Y. Chung, T.P. Hogan, R.-L. Melissa, P. Brazis, J.R. Ireland, C.R. Kannewurf,
M. Bastea, C. Uher, M.G. Kanatzidis, J. Am. Chem. Soc. 126 (2004) 6414.
10] D.-Y. Chung, K.-S. Choi, L. Iordanidis, J.L. Schindler, P.W. Brazis,
C.R. Kannewurf, B. Chen, S. Hu, C. Uher, M.G. Kanatzidis, Chem. Mater. 9
(1997) 3060.
11] J. Yao, B. Deng, D.E. Ellis, J.A. Ibers, Inorg. Chem. 41 (2002) 7094.
12] F.Q. Huang, R.C. Somers, A.D. McFarland, R.P. Van Duyne, J.A. Ibers, J. Solid
State Chem. 174 (2003) 334.
[
3 4
The crystallographic data for Bi In S10 and Bi14.7In11.3S38 have
been deposited with FIZ Karlsruhe as CSD numbers 421865 and
21866. These data may be obtained free of charge by contacting
FIZ Karlsruhe at +497247808666(fax) or crysdata@fiz-karlsruhe.de
e-mail).
[
[
4
(
[13] F.Q. Huang, K. Mitchell, J.A. Ibers, J. Alloys Compd. 325 (2001) 84.
[
[
14] A. Mrotzek, M.G. Kanatzidis, Acc. Chem. Res. 36 (2003) 111, 36.
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B: Lasers Opt. 78 (2004) 543.
[
[
16] R. Klenk, J. Klaer, R. Scheer, M.Ch. Lux-Steiner, I. Luck, N. Meyer, U. Ruehle,
Thin Solid Films (2005) 480.
17] V. Kr a¨ mer, Thermochim. Acta 86 (1985) 291.
Appendix A. Supplementary material
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.jssc.2010.08.028.
[18] V. Kr a¨ mer, Thermochim. Acta 15 (1976) 205.
[
[
[
19] V. Kr a¨ mer, Acta Crystallogr. B36 (1980) 1922.
20] G. Chapuis, C.H. Gnehm, V. Kr a¨ mer, Acta Crystallogr. B28 (1972) 3128.
21] H.-Y. Zeng, H. Mattausch, A. Simon, F.-K. Zheng, Z.-C. Dong, G.-C. Guo,
J.-S. Huang, Inorg. Chem. 45 (2006) 7943.
[
[
[
[
22] CrystalClear, Rigaku Corporation, Tokyo, Japan, 2008.
23] G.M. Sheldrick, Acta Crystallogr. A 64 (2008) 112.
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