Polymorphism of in5S5Cl - X-ray and HRTEM-Investigations

Article abstract of DOI:10.1002/zaac.200900414

In₅S₅Cl belongs to the group of mixed valence indium compounds with indium occurring simultaneously in three oxidation states (In₅S₅Cl = In⁺(In₂) ⁴⁺21n³⁺5S^2-Cr). It was shown in an earlier work that In₅S₅Cl obtained from InCl₃, indium and sulfur at 550 °C, crystallises in a monoclinic structure type in contrast to the orthorhombic bromide, In₅S₅Br. The main difference of both structure types is an ordered mutual exchange of In⁺ and (In₂)⁴⁺ in specific crystallographic positions. This exchange is possible due to the almost identical coordination pattern of both ions. A closer inspection of the real structure of monoclinic In ₅S₅Cl by High Resolution Transmission Microscopy (HRTEM) already showed the presence of small orthorhombic domains in the real structure of this compound. Now we also obtained macroscopic quantities of orthorhombic In₅S₅Cl by the reaction of InCl₃, indium and sulfur at reaction temperatures below 500 °C (Pmn2₁, a = 3.907( 1 ) A, b = 9.021 (2) A, c = 14.866(3) A, Z = 2). The new polymorph is analysed by X-ray single crystal and X-ray powder diffraction and HRTEM investigations.

Full text of DOI:10.1002/zaac.200900414

ARTICLE
DOI: 10.1002/zaac.200900414
Polymorphism of In S Cl – X-ray and HRTEM-Investigations
5
5
[a]
[a]
[b]
[c]
Vera Nickel, Hans-Jörg Deiseroth,* Lorenz Kienle,* Viola Duppel, and
Christof Reiner[
a]
Dedicated to Professor Arndt Simon on the Occasion of His 70th Birthday
Keywords: Phase transitions; Indium; Electron microscopy; Mixed-valent compounds; Chalcogens
5 5 5 5
Abstract. In S Cl belongs to the group of mixed valence indium com- of monoclinic In S Cl by High Resolution Transmission Microscopy
pounds with indium occurring simultaneously in three oxidation states (HRTEM) already showed the presence of small orthorhombic do-
+
4+
3+
2–
–
(
In
that In
lises in a monoclinic structure type in contrast to the orthorhombic InCl
bromide, In Br. The main difference of both structure types is an (Pmn2
ordered mutual exchange of In and (In
5
S
5
Cl = In (In
2
) 2In 5S Cl ). It was shown in an earlier work mains in the real structure of this compound. Now we also obtained
, indium and sulfur at 550 °C, crystal- macroscopic quantities of orthorhombic In Cl by the reaction of
, indium and sulfur at reaction temperatures below 500 °C
, a = 3.907(1) Å, b = 9.021(2) Å, c = 14.866(3) Å, Z = 2). The
in specific crystallographic new polymorph is analysed by X-ray single crystal and X-ray powder
5
S
5
Cl obtained from InCl
3
5 5
S
3
5
S
5
1
+
4+
2
)
positions. This exchange is possible due to the almost identical coordi- diffraction and HRTEM investigations.
nation pattern of both ions. A closer inspection of the real structure
Introduction
states [6, 7]. In such compounds the indium species can be easily
distinguished because of their specific coordination and charac-
teristic distances to anions of their first coordination sphere. Ac-
cording to the classification of Robin and Day [8], all these solids
belong to group I mixed valence compounds. A peculiar case
with respect to this classification is the title compound In S Cl
The group 13 element indium forms a great variety of stable
mixed valence halides and chalcogenides. Beside the group spe-
cific oxidation numbers +I and +III of the isolated atoms, indium
forms cationic clusters of different type with specific average
oxidation numbers of the constituting atoms. The most common
5
5
which contains three different cationic indium species and two
4
+
cluster is an [In2] dumbbell, which occurs in several binary and
ternary solids, e.g. in InS [1] or in KInBr [2]. Further examples
+
4+
3+ 2–
–
different anionic ones: In S Cl (= In (In ) 2In 5S Cl ). In
5
5
2
+
4+
3
spite of apparent structural differences between In and (In )
2
(In : spherical ion, r ≈ 140 pm [9], (In ) : dumbbell shaped
5
+
7+
8+
are chainlike [In ] - (In Se , [3]), [In ] - and [In ] -units (both
+
4+
3
4
3
5
6
2
7+
in In Mo O , [4]), or the tetrahedral [In ] ion, which is ob-
11
40 62
5
ion with covalent In–In bonding (dIn–In ≅ 270 pm [9]) both ions
surprisingly have a more or less similar coordination of nine non-
metal atoms forming a tricapped trigonal prism. Because of this
peculiar geometrical situation, one can expect both ions to be
able to interchange their places at least in the sense of a partial
disorder. We could show in an earlier work [10] that this is actu-
served in Na In O [5]. All these clusters can be well under-
23
5 15
stood by simple two centre two electron bonds of the constituting
+
3+
atoms. Some of these clusters occur together with In or In
or simultaneously with both species in the above mentioned
mixed valence compounds. A typical example is In S
6
7
+
4+
3+ 2–
(
= In (In ) 3In 7S ) with indium in three different oxidation
+
4+
2
ally possible. A complementary interchange of In and (In ) on
2
specific positions resulting in two different ordered structure
types was found for monoclinic In Ch Cl (Ch = S, Se) “Cl-type”
5
5
*
Prof. Dr. H.-J. Deiseroth, Prof. Dr. L. Kienle
Fax: +49-271-7402555
and for orthorhombic In Ch Br (Ch = S, Se) “Br-type”.
5
5
+
+
E-Mail: deiseroth@chemie.uni-siegen.de
TlIn Se Br (with In completely substituted by Tl ), was the first
4
5
[
a] Institut für Anorganische Chemie
Universität Siegen
example to break this initially assumed “systematic” because it
crystallises in the monoclinic “Cl-type” [11]. In Cl presented
Adolf Reichwein Strasse 2
S
5 5
57076 Siegen, Germany
in this paper is the first dimorphic example of this series of solids
that forms two polymorphs (monoclinic “Cl type” and orthor-
hombic “Br-type”) depending on the synthesis conditions.
[
b] Heisenberg-Professur für Synthese und Realstruktur von
Feststoffen
Institut für Materialwissenschaften
Technische Fakultät
Christian-Albrechts-Universität Kiel
Kaiserstr. 2
Results and Discussion
General Remarks
24143 Kiel, Germany
[
c] Max-Planck-Institut für Festkörperforschung
As mentioned above, the compounds MIn Ch X (M = Tl, In,
Heisenbergstr. 1
4
5
70569 Stuttgart, Germany
Ch = S, Se, X = Cl, Br) of which TlIn S Br could not yet
4 5
Z. Anorg. Allg. Chem. 2010, 636, 79–84
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
79

V. Nickel, H.-J. Deiseroth, L. Kienle, V. Duppel, C. Reiner
ARTICLE
been obtained can be described in the mixed valence notation tions that the real structure of orthorhombic In S Br on an
5
5
+
4+
3+
2– –
MIn Ch X = M (In ) 2In 5Ch X . The hitherto known com- atomic scale is nearly free of chemical defects, whereas the
4
5
2
pounds crystallise either in the monoclinic “Cl-type” or in the monoclinic In S Cl exhibits multiple twinning, an intergrowth
5
5
orthorhombic “Br-type”. Neglecting the type of non-metals with In S in nanodimensions and thin, in rare cases more ex-
6
7
(
chalcogen or halogen) the first coordination spheres of the panded lamellar intergrowth of orthorhombic In S Cl [10],
5 5
different In/Tl-species are similar in both structure types: octa- which was not yet known as macroscopic phase at that time.
3
+
4+
hedral for In and tricapped trigonal prismatic for (In2) and Earlier experiments to enhance the size of the orthorhombic
+
M . The octahedra form two-dimensional units of cis- and domains in In S Cl by annealing “monoclinic” In S Cl at dif-
5
5
5 5
trans-edge sharing double-octahedra chains extending parallel ferent temperatures failed. In the course of a series of further
to the shortest axis of the respective structure type (b for the synthesis experiments in the system indium/sulfur/chlorine at
monoclinic, a for the orthorhombic type) (Figure 1).
lower temperatures we now obtained surprisingly orthorhom-
bic In S Cl in macroscopic quantities.
5
5
X-ray Powder Investigations of Monoclinic and Orthorhom-
bic In S Cl Samples
5
5
Monoclinic In S Cl can be obtained from mixtures of InCl ,
5
5
3
indium and sulfur with the total composition In S Cl which
5
5
are annealed above 500 °C (e.g. 550 °C). The product consists
of extremely thin (1–15 μm) orange-red transparent needles
with a length up to some mm. Scanning electron images show
that these needles typically are bundles of several crystals with
intergrowth along the needle axis [010]. X-ray powder patterns
of such samples in comparison to calculated patterns based
on single crystal data show a good agreement concerning the
positions of the reflection angles. Strong differences of intensi-
ties [10] are due to texture effects, which result from a pre-
ferred orientation of the needles on a flatbed holder or in a
capillary. A careful inspection of the resulting powder dia-
grams gives no evidence for the presence of additional orthor-
hombic In S Cl.
5
5
From mixtures of InCl , indium and sulfur with the total
3
composition In S Cl, which are annealed below 500 °C the
5
5
new orthorhombic modification of In S Cl is formed. Orthor-
5
5
hombic In S Cl can already be detected by powder X-ray dif-
5
5
fraction in samples which were annealed at 300 °C only. The
visible formation of needles, however, becomes more pro-
nounced with increasing temperature. At a higher magnifica-
tion and with a certain experience the needles of orthorhombic
In S Cl can even be distinguished from the monoclinic ones.
5
5
The orthorhombic ones show a more regular shape and less
intergrowth along the needle axis. X-ray powder patterns ex-
hibit only minor texture effects. Measured and calculated pat-
terns agree almost completely (Figure 2 a). In particular no
Figure 1. Projection of the monoclinic (above) and orthorhombic (be- reflections of the monoclinic modification of In S Cl are
5
5
5 5
low, left) In S X (X = Cl, Br) structure type with emphasis on the
+ 4+
present (Figure 2 b). Samples of orthorhombic In S Cl, which
5 5
tricapped trigonal prismatic coordination of In and (In
2
)
(below
are annealed at 550 °C show new reflections of the monoclinic
polymorph already within one day. After five days the transi-
right, in projection dark gray or light gray triangles). In the monoclinic
type the double octahedra (medium gray) are surrounded either by 4
+
4+
+
4+
In and 2 (In
2
) -dumbbells or by 2 In and 4 (In
2
) -dumbbells (“4,2” tion is complete. We assume that the sample recrystallises un-
or “2,4”-arrangement). In the orthorhombic type all double octahedra
are surrounded by 3 In and 3 (In
der participation of a gas phase reaction including molecular
+
4+
2
) -dumbbells (“3,3”-arrangement).
species like In Ch and InX. An alternative interdiffusion of
2
+
(
In2)4+ and In ions in the bulk seems to be unlikely. It is not
Both structure types can be easily distinguished in structure possible to transform monoclinic In S Cl back to the orthor-
5
5
projections along the short axis focusing on the local pattern hombic polymorph by annealing the monoclinic phase below
formed by the In(Ch/X) -octahedra and the surrounding trigo- 500 °C. This behaviour was checked at several temperatures
6
nal prisms as outlined in detail in [10] and summarised in Fig- in the range of 300–500 °C and with different annealing times
ure 1. In an earlier work we could show by HRTEM investiga- (up to 4 weeks). The volumes of the two polymorphs, which
8
0
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 79–84

5 5
Polymorphism of In S Cl – X-ray and HRTEM-Investigations
result from the refinements of X-ray powder patterns, show these temperatures represent in both cases the decomposition
only minor differences (Table 1). In differential thermal analy- of the solids.
ses both polymorphs exhibit a thermal effect in the same tem-
perature range (590 °C for orthorhombic and 605 °C for mon-
X-ray Single Crystal Investigation and Comparison of the
Polymorphs
oclinic In S Cl).
5
5
For a single crystal measurement, a small red transparent
needle of orthorhombic In S Cl was selected from a heteroge-
5
5
neous sample, which was annealed at 550 °C for only one day
see above). The crystal was measured with a STOE IPDS I.
(
The analysis of the collected data with the programs RECIPE
and SPACE [12] showed the presence of three domains, which
were intergrown unsystematically. With the program TWIN
[12], overlapping reflections were rejected and the data of the
major domain were used for the structure solution and refine-
ment. A summary of the data collection, refinement details and
atomic positions is given in Table 2 and Table 3.
Table 2. Summary of data collection and refinement details for orthor-
hombic In S Cl.
5 5
Empirical formula
Formula weight /g·mol
Space group
5 5
In S Cl
–
1
769.85
Pmn2
1
Formula units per unit cell
Crystal shape
Z = 2
dark red needle
0.1 × 0.02 × 0.01
Crystal dimension /mm
lattice constants /Å
a = 3.907(1)
b = 9.021(2)
c = 14.866(3)
Volume /Å3
V = 524.0(2)
–
3
Density (calcd.) /g·cm
ρ = 4.880
–1
Absorption coefficient /mm
F(000)
Diffractometer
μ = 12.019
684
STOE-IPDS (Graphite monochroma-
tor)
Wavelength /Å
Temperature /K
0.71073 (Mo-K
T = 293
α
)
Figure 2. (a) Section of a measured X-ray powder pattern of orthor- Measured θ range /°
2.64–29.22
–5 ≤ h ≤ 4
–12 ≤ k ≤ 12
–20 ≤ l ≤ 20
1560
hombic In
culated from single crystal data). (b) Sections of a measured X-ray
5 5
S
Cl (above) in comparison to a calculated one (below, cal- Index ranges
5 5
powder pattern of orthorhombic In S Cl (above) in comparison to a
calculated one of monoclinic In
crystal data) [10].
5
S
5
Cl (below, calculated from single Measured reflections
Independent reflections
1380
Completeness to θ /%
96.6
R
int.
0.0652
Table 1. Comparison of the lattice constants for the monoclinic and Data/Restraints/Parameter
1560 / 1 / 70
orthorhombic polymorphs of In
internal standard (Si).
5
S
5
Cl obtained from powder data with R values (I ≥ 2σ(I))
R values (all data)
R
R
1
= 0.0335, wR
2
2
= 0.0719
= 0.0749
1
= 0.0421, wR
Weighting Scheme*
A = 0.0458 B = 0
Lattice constants /Å; /°; /Å3
Space group
P2 /m
GooF
0.976
Difference Fourier residuals /
ρmax. = 1.782; ρmin. = –1.222
In
5
5
S
S
5
5
Cl a = 8.944(2)
1
–3
e·Å
w = 1/[σ (F
b = 3.9111(8)
c = 14.985(4)
β = 93.60(3)
2
2
2
2) + 2F 2
c
)/3
*
o
) + (AP) + BP], P = (F
o
V = 523.1(2)
In
Cl a = 3.9031(1)
b = 9.010(3)
Pmn2
1
In contrast to monoclinic In S Cl, the structure refinement
5
5
c = 14.836(5)
V = 521.7(2)
of orthorhombic In S Cl does not show any significant anoma-
5 5
lies. This is somewhat surprising because In S Cl is the first
5
5
dimorphic example thus exhibiting ideal requirements for a na-
Powder investigations of samples, which are quenched from noscale intergrowth of both modifications. In order to ensure
temperatures slightly above these thermal effects, prove that this observation and to derive information about the homoge-
Z. Anorg. Allg. Chem. 2010, 79–84
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
81

V. Nickel, H.-J. Deiseroth, L. Kienle, V. Duppel, C. Reiner
ARTICLE
Table 3. Atomic coordinates, equivalent isotropic displacement param- Table 5. MAPLE values for monoclinic [10] and orthorhombic
2
eters Ueq /Å and occupancy for orthorhombic In
Wyckoff position 2a.
5
S
5
Cl, all atoms in In
5 5
S Cl.
MAPLE /kcal·mol–1
monoclinic
MAPLE /kcal·mol
orthorhombic
–1
Atom
x
y
z
U
eq /Å2
sof
3
+
In1
In2
In3
In4
In5
S1
0
0.8876(1)
0.40427(6)
0.52420(6)
0.30337(7)
0.25427(6)
0.11078(8)
0.3615(2)
0.6604(2)
0.5658(2)
0.4556(2)
0.2518(2)
0.4593(2)
0.0119(2)
0.0120(2)
0.0161(2)
0.0115(2)
0.0283(4)
0.0084(6)
0.0104(6)
0.0096(6)
0.0119(6)
0.0113(5)
0.0153(6)
1
In1 (In ) –873,53
–911,63
–808,78
–337,65
–318,64
–159,44
–463,59
–413,13
–443,57
–378,02
–368,18
–124,13
–4726,76
3+
1/2 0.5990(1)
1/2 0.1880(1)
1/2 0.48008(9)
1/2 0.8579(2)
1/2 0.7001(3)
1/2 0.4290(3)
1
In2 (In ) –831,28
2+
1
In3 (In ) –328,12
2+
1
In4 (In ) –341,63
+
0.951(6)
In5 (In )
S1
–149,57
–442,47
–473,40
–395,47
–461,87
–386,62
–78,44
1
1
1
1
1
1
S2
S2
S3
0
0.7674(3)
S3
S4
1/2 0.0642(4)
S4
S5
0
0
0.0296(3)
0.4096(3)
S5
Cl
Cl1
Σ
–4762,4
neity on a nanoscale, HRTEM investigations were carried out
(
see below).
clinic and orthorhombic In S Cl favours the monoclinic phase
5
5
As mentioned above, the crystallographically independent
over the new orthorhombic one (Δ ≈ 0.8 %, Table 5). The par-
tial MAPLE values of the octahedrally coordinated In3 ions
+
indium atoms have the same type of coordination in both poly-
morphs (Figure 1). The average and individual In–Ch/X distan-
ces are reasonable and show good internal and external agree-
ment (Table 3, Table 4). Nevertheless, a significant difference
(
In1 and In2) are more balanced for the monoclinic compound.
–
The small value for Cl in the monoclinic phase is remarkable.
In both structure types three of five crystallographically inde-
pendent chalcogen atoms have significant higher values than
two others. For the evaluation of this calculation one should
consider, that only the orthorhombic structure type does not
show chemical defects (see below).
+
in the first coordination sphere is observed for In5 (In ). In the
monoclinic phase the first coordination sphere of In5 consists
of six sulfur and three chlorine atoms whereas in the orthor-
hombic polymorph In5 has eight sulfur atoms and one chlorine
atom. All other indium atoms have the same S/Cl ratio in their
+
coordination sphere. The slight underoccupancy for In5 (In )
is a feature of all solids containing In . It is most likely due to HRTEM Investigations of Orthorhombic In
an interchange of a small fraction of In and (In ) . The Mad-
elung Parts of Lattice Energy (MAPLE, [13, 14]) for mono-
+
S
5
Cl
5
+
4+
2
The crystal structure of the chemically homogeneous sam-
ples was examined by electron diffraction techniques. All ana-
lysed selected areas (about 50) show Bragg intensities, which
can be indexed assuming the orthorhombic structure type. Par-
ticularly for zone axis [100], which correlates with the [010]
orientation of the monoclinic structure, exactly rectangular pat-
terns were recorded. This contrasts to monoclinic In S Cl,
Table 4. Comparison of selected distances /Å for monoclinic [10] and
orthorhombic In
In Cl, monoclinic
In1– S5
5 5
S Cl.
5
S
5
5 5
In S Cl, orthorhombic
5
5
2.57(1)
2.620(7)
2.61(1)
2.653(7)
2.621
2.54(1)
2.544(7)
2.59(1)
2.776(7)
2.628
2.50(1)
2.57(1)
2.547
2.517(7)
2.54(1)
2.527
2.723(4)
3.187(9)
3.206(9)
3.28(1)
3.34(1)
3.398(9)
3.93(1)
3.348
In1– S5
2.603(3)
2.634(2)
2.634(3)
2.661(2)
2.638
2.551(2)
2.540(3)
2.585(3)
2.769(2)
2.628
2.524(3)
2.539(2)
2.534
2.537(2)
2.546(3)
2.540
2.734(1)
3.103(3)
3.257(3)
3.301(3)
3.326(3)
3.446(3)
3.990(3)
3.345
which exhibits significant deviations from rectangularity and
orthorhombic symmetry. Diffuse scattering, particularly dif-
fuse streaks 00l indicating lamellar intergrowth phenomena,
was not observed. Strongly excited but kinematically forbid-
den reflections directed our attention to structural deviations
S2(2x)
S4(2x)
S1
S3
S1(2x)
Ø
S1(2x)
Ø
In2– S3
In2– S3(2x)
S4(2x)
S4
Cl(2x)
Ø
S2
from the orthorhombic model with space group Pmn2 . A care-
1
S1
ful comparison of different electron diffraction techniques led
to the conclusion that such violations (which are not observed
in the X-ray experiments) are produced by multiple scattering
effects. The intensity of the kinematically forbidden reflections
is strongly minimised when the crystal was tilted from the pre-
cise zone axis orientation or when precession electron diffrac-
tion was applied. In this case, an average of many tilted pat-
terns is recovered by moving the electron beam on a precession
cone [15]. One example is presented in Figure 3 for a thick
crystal along [110]. The serial reflection condition (00l with
l = 2n) is strongly violated in the SAED pattern, which was
performed with a fixed electron beam (a), cf. arrows. These
intensities are strongly reduced when switching to the preces-
sion mode (c). Moreover, the expected differences in reflection
Cl(2x)
Ø
In3– S2
In3– S4
S5(2x)
Ø
S5(2x)
Ø
In4– S3(2x)
In4– S2(2x)
S1
S1
Ø
Ø
In4– In3
In5– Cl(2x)
S5(2x)
S4
In4– In3
In5– S4(2x)
S5(2x)
Cl
Cl
S2(2x)
S3
S3(2x)
S1
S1
Ø
Ø
8
2
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 79–84

5 5
Polymorphism of In S Cl – X-ray and HRTEM-Investigations
intensity are more pronounced in the PED pattern and approxi-
mate well the simulated pattern of b).
Figure 3. a) SAED pattern, b) simulated PED pattern (precession an-
gle 3°, thickness: 20 nm), c) PED pattern. All zone axis [110].
The absence of stripes in brightfield contrast, the HRTEM
micrographs and the corresponding Fourier transforms proof
that lamellar structures based on chemical or polymorphic in-
tergrowth and twinning as described for the sample annealed
at 550 °C [10] were limited to exceptional cases. The single
layers are imaged edge-on in all zone axes orientations [uv0],
e.g. [100]. As specified above, only one type of layer is present
for the orthorhombic structure type and adjacent layers appear
shifted and inversed when projected along [100]. Conse-
quently, the characteristic contrasts representing the layers are
shifted and inversed as well cf. Figure 4. The cut-out in a) left
shows the contrast simulation for a single layer (Δf = –40 nm)
based on the model from X-ray analysis. On the right four of
these cut-outs are combined by applying a shift and an inver-
sion like for the consecutive layers in the orthorhombic struc-
ture. The experimental micrograph (Figure 4b) clearly shows In
the arrangement of the layers and the good correlation to the
inserted simulation proofs the 3,3-arrangement of the single
layers. A convincing agreement of simulated and experimental
micrographs is also found when varying the focus, e.g. when
selecting strong underfocus conditions, cf. Figure 4 c.
Figure 4. a) Cut-out of a simulated micrograph based on orthorhombic
Cl and composite image, see text; b) and c) experimental micro-
graphs and inserted simulations with Δf = –40 nm and Δf = –85 nm,
respectively (t = 3.9 nm). All zone axis [100], the images of a) were
scaled by 300 % with respect to b) and c).
5 5
S
filled glove box and transferred into evacuated dry quartz glass am-
poules (d = 12 mm, l = 60–80 mm). The samples were heated to the
final temperature and annealed for several days or weeks.
Experimental Section
Synthesis
For temperatures above 723 K, fine needle-shaped crystals of mono-
5 5 5 5
The synthesis of the polymorphs of In S Cl was carried out from sulfur clinic In S Cl were observed. The crystals were dark red and not mark-
(
Chempur, pieces, 99,999 %), indium (Chempur, shots, 99,9999 %)
edly air sensitive. For temperatures between 573 K and 723 K, the
resulting red brown powder consisted of microcrystalline orthorhombic
3
and InCl (Heraeus, powder, 99,999 %) in stoichiometric amounts (ra-
tio 14:15:1) or from the powdered binary starting materials InS (prere-
acted from In and S), In (Alfa, powder, 99,999 %) and InCl in the formed. The annealing of a homogenised orthorhombic microcrystal-
ratio 2:1:1. The respective starting materials were weighed in an argon- line phase for one day at 723 K led to a partial transformation to the
5 5 5 5
In S Cl. Below an annealing temperature of 573 K, no In S Cl was
2
S
3
3
Z. Anorg. Allg. Chem. 2010, 79–84
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
83

V. Nickel, H.-J. Deiseroth, L. Kienle, V. Duppel, C. Reiner
(300 kV, LaB cathode). The EMS program package [18] was applied
for the simulation of HRTEM micrographs and electron diffraction
patterns. EDX (energy dispersive X-ray spectroscopy) was performed
in the scanning- and nanoprobe mode of CM30ST with a Si.Li-EDX
detector (Noran, Vantage System).
ARTICLE
monoclinic phase. Simultaneously monoclinic and orthorhombic nee-
dle shaped crystals suitable for single crystal analyses were formed.
6
X-ray Powder Investigations
X-ray powder measurements were carried out on a SIEMENS D5000
diffractometer (transmission mode) with Ge-monochromatised Cu-Kα1
radiation. To verify the lattice constants of the two modifications of Acknowledgement
5 5
In S Cl, X-ray powder diagrams were measured with an internal stand-
ard (silicon).
The authors would like to thank the Deutsche Forschungsgemeinschaft
for continuous financial support
X-ray Single Crystal Investigation
References
5 5
For X-ray structure determination of orthorhombic In S Cl, a needle-
shaped crystal with appropriate size was separated from the bulk, fixed
with grease on top of a glass capillary and mounted on a STOE IPDS
I imaging plate diffraction system using graphite monochromatised
[
1] R. Walther, H. J. Deiseroth, Z. Kristallogr. 1995, 210, 360–360.
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2
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[
[
[
[
[
3
1
A summary of crystal and experimental data as well as structure refine-
ment details for orthorhombic In S Cl is reported in Table 2–Table 4.
5 5
Further details of the crystal structure investigation are available from
the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopold-
shafen, Germany, on quoting the depository number CSD-421050, the
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Thermal Analysis
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–
1
cooling rates of 5 K·min . Orthorhombic In
5
S
5
Cl shows two endother-
[14] R. Hoppe, Angew. Chem. Int. Ed. Engl. 1966, 5, 95–106.
[
15] a) R. Vincent, P. A. Midgley, Ultramicroscopy 1994, 53, 271–
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Y. Andersson, Acta Crystallogr., Sect. A 2003, 59, 117–126; e) C.
Own PhD Thesis, Northwestern University Evanston Illinois De-
cember 2005.
–
1
5
73 K·min ), the resulting powder diagrams showed the presence of
In
In
6
S
S
7
as a decomposition product and reflections of orthorhombic
Cl.
5
5
[
[
[
16] G. M. Sheldrick, SHELXS-97, Program for the Solution of Crystal
Structures, Universität Göttingen, 1997.
HRTEM Investigation
17] G. M. Sheldrick, SHELXL-97, Program for the Refinement of
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All specimens were placed on copper grids, which were fixed in a side
entry, double tilt holder with the tilting limited to a maximum of ± 25°
in two directions. High resolution transmission electron microscopy
(
HRTEM), precession electron diffraction (PED) and selected area
Received: August 31, 2009
Published Online: October 28, 2009
electron diffraction (SAED) were performed with a Philips CM30ST
8
4
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 79–84