Benzene trisulfonic acid (H3BTS) as analogue of trimesic acid for building open frameworks: The first rare earth examples [La(BTS)(H 2O)5] and [RE(BTS)(H2O)4] (RE = Nd, Sm, Eu)

Article abstract of DOI:10.1002/zaac.201000341

The reaction of benzene 1,3,5-trisulfonic acid (H₃BTS) with the hydroxides RE(OH)₃ (RE = La, Nd, Sm, Eu) in aqueous solution afforded the sulfonates [La(BTS)(H₂O)₅] and [RE(BTS)(H ₂O)₄] (RE = Nd, Sm, Eu). Single crystal investigations were performed for the lanthanum and the europium compound, respectively. [La(BTS)(H₂O)₅] is triclinic [P|{1}, Z = 2, a = 783.18(6) pm, b = 1056.94(8) pm, c = 1082.38(8) pm, α = 114.860(2)°, β = 96.655(3)°, γ = 104.402(3)°] whereas [Eu(BTS)(H₂O) ₄] exhibits monoclinic symmetry [P2₁/n, Z = 4, a = 767.61(5) pm, b = 1730.2(1) pm, c = 1134.06(8) pm, β = 108.375(8)°]. Despite these crystallographic differences, the structural features of the lanthanum and europium compounds are very similar. They show the metal ions connected by BTS anions to layers that are further linked by hydrogen bonds. Interestingly, only two of the three sulfonate groups are connected to rare earth ions, whereas the third remains uncoordinated and acts as acceptor within the hydrogen bonds. According to powder XRD measurements the neodymium and samarium sulfonates are isotypic with the europium compound. The thermal analyses of the compounds show the dehydration in a temperature range between 100 and 300 °C, whereas the decomposition of the organic ligands takes place at temperatures as high as 550 °C. Thus the anhydrous sulfonates are much more stable than comparable salts of trimesic acid. The residues of the thermal decompositions were identified by XRD experiments.

Full text of DOI:10.1002/zaac.201000341

ARTICLE
DOI: 10.1002/zaac.201000341
Benzene Trisulfonic Acid (H BTS) as Analogue of Trimesic Acid for
3
Building Open Frameworks: The First Rare Earth Examples
[
La(BTS)(H O) ] and [RE(BTS)(H O) ] (RE = Nd, Sm, Eu)
2
5
2
4
[
a]
[a]
[a]
Andrea Mietrach, Thomas W. T. Muesmann, Christian Zilinski,
[a]
[a]
Jens Christoffers,* and Mathias S. Wickleder*
Keywords: Metal-organic frameworks; Polysulfonic acids; Lanthanides; Aromatic substitution; Thermal analysis
Abstract. The reaction of benzene 1,3,5-trisulfonic acid (H
the hydroxides RE(OH) (RE = La, Nd, Sm, Eu) in aqueous solution sulfonate groups are connected to rare earth ions, whereas the third
afforded the sulfonates [La(BTS)(H
Nd, Sm, Eu). Single crystal investigations were performed for the lan-
thanum and the europium compound, respectively. [La(BTS)(H O)
is triclinic [P1, Z = 2, a = 783.18(6) pm, b = 1056.94(8) pm, c =
082.38(8) pm, α = 114.860(2)°, β = 96.655(3)°, γ = 104.402(3)°]
O) ] exhibits monoclinic symmetry [P2 /n, Z =
, a = 767.61(5) pm, b = 1730.2(1) pm, c = 1134.06(8) pm, β =
08.375(8)°]. Despite these crystallographic differences, the structural
3
BTS) with further linked by hydrogen bonds. Interestingly, only two of the three
3
2
5 2 4
O) ] and [RE(BTS)(H O) ] (RE =
remains uncoordinated and acts as acceptor within the hydrogen bonds.
According to powder XRD measurements the neodymium and sama-
rium sulfonates are isotypic with the europium compound. The thermal
analyses of the compounds show the dehydration in a temperature
range between 100 and 300 °C, whereas the decomposition of the or-
ganic ligands takes place at temperatures as high as 550 °C. Thus the
anhydrous sulfonates are much more stable than comparable salts of
2
5
]
¯
1
whereas [Eu(BTS)(H
4
1
2
4
1
features of the lanthanum and europium compounds are very similar. trimesic acid. The residues of the thermal decompositions were identi-
They show the metal ions connected by BTS anions to layers that are fied by XRD experiments.
Introduction
terephthalic acid (1) and trimesic acid (2), which are widely
[4,5]
used in MOF chemistry.
a convenient preparative route for the synthesis of benzene-
,4-disulfonic acid (3) (p-H BDS) and benzene-1,3,5-trisul-
Therefore, we recently developed
Metal-organic frameworks, so-called MOFs, have attracted
significant interest because they do not only display a fascinat-
ing structural chemistry but bear also potential to act as materi-
als in various applications.[ One of these applications that
were addressed to these compounds was their use as gas stor-
age media, especially for hydrogen.[ Usually carboxylic acids
were used to build up open framework structures. The advan-
tage of these acids is their commercial availability in a great
variety at relatively low costs. However, the drawback of
frameworks that are based on carboxylic acids is their thermal
lability, i.e. they decompose quite easily upon heating. This is
a great disadvantage with respect to gas storage applications
because the absorption and desorption of gas usually causes or
requires heating of the materials. One option to increase the
thermal stability of metal-organic frameworks is to switch
from carboxylate linkers to sulfonate linkers, which are known
to be thermally more robust.[ Unfortunately, the respective
polysulfonic acids – in contrast to carboxylic acids – are hardly
available. This is in particular true for the sulfo-analogues of
1
2
fonic acid (4) (H BTS) starting from commercially available
1]
3
[6]
and cheap starting materials (Figure 1). This route enables
us to prepare the acids in a multigram scale, which makes them
available for the performance of experiments to their imple-
mentation in MOF chemistry. Whereas our first attempts were
2]
[6]
devoted to copper compounds, we here describe our recent
results on rare earth elements. Building framework structures
with these elements is of great interest because of their unique
3]
*
*
Prof. Dr. J. Christoffers
E-Mail: Mathias.Wickleder@uni-oldenburg.de
Prof. Dr. M. Wickleder
Fax: +49-441-798-3873
E-Mail: mathias.wickleder@uni-oldenburg.de
[
a] Institut für Reine und Angewandte Chemie
Carl von Ossietzky-Universität Oldenburg
Postfach 2503
Figure 1. Carboxylic and sulfonic acids as linkers for metal-organic
frameworks.
26111 Oldenburg,Germany
Z. Anorg. Allg. Chem. 2011, 637, 195–200
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
195

J. Christoffers, M. S. Wickleder et al.
ARTICLE
spectroscopic and magnetic properties. Our former work has single crystal structure determination was performed, so that
shown that monosulfonates of these elements can be prepared the structure description of the tetrahydrates will be given for
[7]
and show a good thermal stability. In this paper we present this compound. The pentahydrate [La(H O) (BTS)] is triclinic
2 5
the first rare earth compounds of benzene-1,3,5-trisulfonic acid (see Table 2), but its structure is are very similar to those of
(4) and their thermal behavior.
the tetrahydrates. In both cases the rare earth ions are coordi-
nated by four monodentate BTS3– ions and the H O molecules.
2
The coordination polyhedron is a distorted tricapped trigonal
prism for La3+ whereas for the smaller Eu ion is a distorted
square anti-prism is found (Figure 2). The distances RE–O
within the polyhedra range from 251 up to 265 pm for the
3+
Results and Discussion
Crystal Structure
The lanthanum compound crystallizes with five, the trisulfo- lanthanum, and from 236 up to 245 pm for the europium com-
3+
3+
3+
nates of the smaller RE ions Nd , Sm and Eu with four pound, respectively (Table 3). No significant differences be-
molecules of crystal water per formula unit.[ With respect to tween the La–O distances originating from sulfonate groups or
8]
3–
XRD measurements the tetrahydrates [RE(BTS)(H O) ] (RE = water molecules are observed. The BTS ions of each polyhe-
2
4
3+
Nd, Sm und Eu) are isotypic and show monoclinic symmetry dron are linked to four further RE ions leading to sheets ac-
2
(
space group P2 /n) (Table 1). For the europium sulfonate a cording to the formulation [RE(BTS) (H O) ] (with x = 5
1
∞
4
/
4
2
x
/
1
Table 1. X-ray powder diffraction results for the rare earth benzene trisulfonates.
compound
space group
a /pm
b /pm
c /pm
α /°
β /°
γ /°
105.02(7)
¯
[
[
[
[
La(H
Nd(H
Sm(H
Eu(H
2
O]
O)
O)
O)
5
(BTS)]
4
P1
784.2(3)
769.4(5)
766.9(4)
767.4(4)
1057.8(8)
1738.0(8)
1729.8(5)
1730.0(2)
1083.3(2)
1138.3(4)
1134.8(4)
1133.8(6)
114.91(7)
96.92(6)
2
(BTS)]
P2
P2
P2
1
1
1
/n
/n
/n
108.38(5)
108.39(4)
108.36(6)
2
4
(BTS)]
2
4
(BTS)]
Table 2. Crystallographic data and their determination.
La(H O) (BTS)]
[
2
5
2 4
[Eu(H O) (BTS)]
lattice parameters
single crystal data)
a = 783.18(6) pm
b = 1056.94(8) pm
c = 1082.38(8) pm
α = 114.860(2)°
β = 96.655(3)°
a = 767.61(5) pm
b = 1730.2(1) pm
c = 1134.06(8) pm
(
β = 108.375(8)°
γ = 104.402(3)°
3
1429.4(1) Å3
4
cell volume
762.2(1) Å
no. of formula units
crystal system
space group
measuring device
radiation
2
triclinic
monoclinic
¯
P1 (Nr. 2)
1
P2 /n
BRUKER APEX II CCD
STOE IPDS I
Mo-K (graphite monochrom., λ = 71.07 pm)
153 K
Mo-K
153 K
α
(graphite monochrom., λ = 71.07 pm)
α
temperature
theta range
4.2° < 2θ < 72.6°
–12 ≤ h ≤ 13
17 ≤ k ≤ 17
18 ≤ l ≤ 17
6.1° < 2θ < 56.6°
–9 ≤ h ≤ 9
index range
–
–
–22 ≤ k ≤ 22
–15 ≤ l ≤ 15
0° < φ < 270°; 1.2°
225
rotation angle; φ increment
no. of exposures
exposure time
1.5 min
60 mm
detector distance
data corrections
absorption correction
μ
Polarization and Lorentz factors
numerical
Polarization and Lorentz factors
numerical
–
1
–1
32.8 cm
14503
4655
48.96 cm
measured reflections
unique reflections
18988
3350
with I
o
> 2σ (I)
4403
2789
no. of variables
269
0.0226
209
R
int
0.0430
structure determinations
scattering factors
goodness of fit
SHELXS-97 and SHELXL-97
Intern. Tables Vol. C
1.135
SHELXS-97 and SHELXL-97
Intern. Tables Vol. C
0.912
0.0176; 0.0377
0.0240; 0.0385
–1.53/1.03
R1; wR2 (I
o
> 2σ(I))
0.0252; 0.0642
R1; wR2 (all data)
0.0269; 0.0649
–
3
min./max. electron density / e·Å
–0.733/1.383
1
96
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 195–200

3
H BTS as Analogue of Trimesic Acid for Building Open Frameworks
Table 3. Selected bond lengths /pm and angles /° in the crystal struc-
tures of [La(BTS)(H O) ] and [Eu(BTS)(H O) ].
2
5
2
4
La1 –O1
245.2(2)
235.6(2)
239.9(2)
242.4(2)
–
–
–
–
–
–
–
O2
–O2
–O3
–O4
O3
O4
O5
O11
O12
O21
242.6(2)
237.6(2)
238.9(2)
240.5(2)
3
+
3+
–O22
Figure 2. Coordination of the La ions (left hand) and Eu ions (right
hand) in the crystal structures of [La(BTS)(H O) and
Eu(BTS)(H O) ], respectively.
2
5
]
O1 –H11
71(7)
97(7)
96(7)
96(9)
85(4)
77(5)
79(4)
96(9)
95(6)
81(6)
O1 –H11
–H12
81(7)
83(6)
71(7)
68(8)
79(7)
77(7)
81(6)
78(7)
[
2
4
–
H12
O2 –H21
O2 –H21
–H22
–H22
for RE = La and x = 4 for RE = Eu). The linking pattern of
O3 –H31
–H32
O3 –H31
–H32
O4 –H41
–H42
3
–
3+
BTS anions and RE cations is shown in the Figure 3 and
O4 –H41
Figure 5, respectively. One of the sulfonate groups of the anion
–H42
(
“
S3 in the left part in Figure 3) remains uncoordinated. This
O5 –H51
H52
free” sulfo group might cause potential activity of such mate-
–
rials as Brønsted acidic catalysts. Each of the other two sulfo-
nate groups of the anion is coordinated by two oxygen atoms S1 –O11
146.2(2) S1 –O11
144.2(2)
145.9(2)
146.2(2)
177.3(2)
to two different RE3+ ions. This is in contrast to the findings
–O12
145.3(2)
145.7(2)
177.7(2)
–O12
–O13
–C1
–
–
O13
C1
for the structure of [Cu (BTS) (H O) ]·4H O with only one
3
2
2
12
2
[6]
coordinating oxygen atom per sulfonate group. The right
hand part of Figure 3 gives a larger section of this structure on S2 –O21
145.8(2) S2 –O21
144.5(2)
146.7(2)
146.5(2)
177.0(2)
–
O22
–O23
C3
146.1(2)
146.0(2)
176.8(2)
–O22
–O23
–C5
the example of the lanthanum compound. The very special
linking pattern of the BTS3– anions and La3+ cations generates
–
two different types of cavities or – in a three dimensional
view – channels along the a axis. Eight-membered rings are S3 –O31
146.3(2) S3 –O31
145.0(2)
146.7(2)
145.0(2)
178.0(2)
3+
formed by linking of two La ions by two sulfonate groups
of two different BTS3– ions. Only water molecules are present
–O32
–O33
–C5
146.4(2)
145.1(2)
177.4(3)
–O32
–O33
–C5
in these small channels. The distances between adjacent La3+
ions are about 602 pm, between sulfur atoms about 462 pm.
O11 –S1– O12 112.0(1) O11 –S1– O12 114.4(1)
O11 –S1– O13 111.3(1) O11 –S1– O13 111.8(1)
The second type of channels is surrounded by a larger ring of O12 –S1– O13 113.5(1) O12 –S1– O13 111.6(1)
3
+
3–
3+
O11 –S1– C1
O12 –S1– C1
O13 –S1– C1
106.4(1) O11 –S1– C1 107.4(1)
106.1(1) O12 –S1– C1 106.1(1)
107.0(1) O13 –S1– C1 104.7(1)
two La ions and two BTS ions. Distances between La
atoms are now about 706 pm. The distance of the carbon atoms
between the sulfonate groups define a channel diameter of
O21 –S2– O22 112.5(1) O21 –S2– O22 112.4(1)
2
8
90 pm. By stacking the ∞[La(BTS)4/4(H O)5/1] layers along O21 –S2– O23 112.4(1) O21 –S2– O23 113.0(1)
2
the [100] direction (Figure 4) the benzene rings are lying upon O22 –S2– O23 112.2(1) O22 –S2– O23 111.8(1)
O21 –S2– C3
O22 –S2– C3
O23 –S2– C3
106.3(1) O21 –S2– C5 107.6(1)
106.1(1) O22 –S2– C5 105.9(1)
106.8(1) O23 –S2– C5 105.5(1)
each other with a little displacement, but are turned by 60°
with respect to each other. As a result, the non-coordinating
sulfonate groups are pointing into the larger channels, which
O31 –S3– O32 110.8(1) O31 –S3– O32 111.8(1)
are moreover occupied by water molecules. The layers are con- O31 –S3– O33 113.7(2) O31 –S3– O33 114.4(2)
nected by hydrogen bonding, indicated as hatched lines in Fig-
ure 4. These bonds involve the H O molecules as donors and
O32 –S3– O33 112.8(2) O32 –S3– O33 112.2(2)
O31 –S3– C5
O32 –S3– C5
O33 –S3– C5
106.8(1) O31 –S3– C3 105.6(1)
106.5(1) O32 –S3– C3 105.9(1)
105.7(1) O33 –S3– C3 106.0(1)
2
the sulfonate groups as acceptors. Furthermore, hydrogen
bonding is observed within the layers, with water molecules
acting as both acceptors and donors, and sulfonate groups as
acceptors. With respect to the observed distances between do-
nor and acceptor oxygen atom, the hydrogen bonds are me-
dium strong (272–284 pm) with two exceptions of 307 and
Thermal Decomposition
[9]
3
18 pm that hint at only weak interactions (Table 4). A simi-
The thermal decomposition of [La(BTS)(H O) ] occurs in
2
5
lar stacking is observed for the europium sulfonate with stack- several stages (Figure 7, for data see Table 5). The dehydration
2
ing of layers of the composition [Eu(BTS) (H O)4/1] (Fig- takes place between 115 and 295 °C and can be divided in
∞
4/4
2
ure 6). Again, linkage is achieved by hydrogen bonds. These three well defined steps, correlating to the loss of three, one,
are slightly different compared to those discussed above due and again one water molecule with respect to the observed
to the presence of only four water molecules. The respective mass loss. After dehydration the anhydrous compound remains
values are also given in Table 4.
stable up to 550 °C before the degradation of the sulfonate
Z. Anorg. Allg. Chem. 2011, 195–200
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J. Christoffers, M. S. Wickleder et al.
ARTICLE
3
–
Figure 3. Coordination of the BTS anions in the crystal structure of [La(BTS)(H
∞
2
O)
5
] (left hand) and their connection to sheets according to
2
[
2
La(BTS)4/4(H O)5/1].
2
∞
2
Figure 4. Linkage of the [La(BTS)4/4(H O)5/1] sheets shown in Fig-
ure 3 by hydrogen bonds (dashed violet lines).
2
Figure 5. Sheets according to [Eu(BTS)4/4(H
2
O)4/1] in the crystal
∞
takes place. XRD investigations of the residue show the pres-
structure of [Eu(BTS)(H
2 4
O) ]. Note, that the linkage of the anions is
the same as in [La(BTS)(H O) ] (cf. Figure 3).
ence of La O S and La S . The oxide sulfide as a decomposi-
2
2
2 3
2
5
tion product is not unexpected as it has also been observed
for the decomposition of the sulfonate La(CH SO ) ·2H O at
3
3 3
2
similar temperatures.[
7]
The dehydration process of [Eu(BTS)(H O) ] is similar to
2
4
that of the lanthanum compound. The water molecules are re-
leased in three separate steps and the anhydrous compound is
obtained at about 300 °C (Figure 8, Table 5). According to the
mass loss observed the first step is correlated to the loss of
two water molecules whereas each of the following steps can
be attributed to the loss of one H O molecule. For the euro-
2
pium compound the anhydrous material decomposes also at
about 550 °C proving the thermal stability of the sulfonate an-
ion. In contrast to the lanthanum compound different decompo-
sition products are observed in the powder diffraction pattern
of the residue. It could be unambiguously interpreted assuming
2
Figure 6. Linkage of the [Eu(BTS)4/4(H
2
O)4/1] sheets shown in Fig-
∞
[10]
[11]
a mixture of Eu O S
and the sulfide EuS.
The lattice ure 5 by hydrogen bonds (dashed violet lines).
2
2
1
98
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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3
H BTS as Analogue of Trimesic Acid for Building Open Frameworks
Table 4. Hydrogen bonding in the structure of [La(BTS)(H
2
O)
5 2 4
] and [Eu(BTS)(H O) ].
D–H
2 5
La(BTS)(H O) ]
d(D–H) /pm
d(H···A) /pm
<DHA /°
d(D···A) /pm
A
[
O1–H11
O1–H12
O2–H21
O2–H22
O3–H31
O3–H31
O3–H32
O4–H41
O4–H42
O4–H42
O5–H51
O5–H52
71
97
96
96
85
85
77
79
96
96
95
81
265
179
195
202
223
258
198
207
212
226
184
204
132.9
163.8
142.6
143.3
126.3
118.1
159.7
156.4
130.2
111.6
157.4
176.7
318
273
277
284
281
307
272
280
284
276
274
284
O13
O13
O33
O3
O1
O13
O23
O23
O13
O5
O32
O31
[
2 4
Eu(BTS)(H O) ]
O1–H11
O1–H12
O2–H21
O2–H22
O3–H31
O3–H31
O4–H41
O4–H42
O4–H42
81
83
71
68
79
77
81
78
78
201
195
200
206
205
199
216
225
233
158.4
162.9
177.1
171.8
161.9
164.6
158.5
141.9
133.2
277
275
271
274
281
274
293
290
292
O21
O11
O33
O32
O32
O31
O31
O11
O21
2 5 2 4
Table 5. Data for the thermal decomposition of [La(BTS)(H O) ] and [Eu(BTS)(H O) ].
Compound
Stage
Tonset /°C
Tend /°C
Tmax /°C Mass loss obs. Mass loss calcd.
[
La(BTS)(H
2
O)
5
]
1. loss of three equiv. of H
2
O
O
86
139
198
312
570
115
175
295
560
8.6 %
3.9 %
3.6 %
63.5 %
9.9 %
3.3 %
3.3 %
62.4 %
2
3
4
. loss of one equiv. of H
2
2
2
158
256
548
. loss of one equiv. of H
O
. decomposition to La
2
O
S and La
2
S
3
[
Eu(BTS)(H
2
O)
4
]
1. loss of two equiv. of H
2
O
O
O
110
175
240
574
175
240
320
591
160
205
280
586
6.8 %
3.7 %
3.7 %
50.2 %
6.7 %
3.3 %
3.3 %
47.3 %
2
3
4
. loss of one equiv. of H
2
2
. loss of one equiv. of H
. decomposition to Eu
2
S
2
O and EuS
2 5
Figure 7. Thermal analysis of [La(BTS)(H O) ].
2 4
Figure 8. Thermal analysis of [Eu(BTS)(H O) ].
¯
parameter refinement for these phases gave: Eu O S, P3m1,
2
2
Conclusions
¯
a = 387.1(3) pm, c = 668.9(6) pm; EuS, Fm3m, a = 597.2(2)
pm. According to the mass loss observed both compounds are
obtained in an almost 1:1 ratio.
The convenient synthesis of benzene-1,3,5-trisulfonic acid
(H BTS) as an analogue of trimesic acid in a multigram scale
3
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199

J. Christoffers, M. S. Wickleder et al.
ARTICLE
–
1
is the crucial step for the implementation of this acid in build- (10 K·min ) up to 800 °C under flowing argon using the thermo ana-
lyzer METTLER TOLEDO SDTA 851e. The data were processed with
ing metal-organic frameworks. In this paper we have demon-
the software of the analyzer.[
17]
strated this on the example of the first lanthanide trisulfonates
[
La(BTS)(H O) ] and [RE(BTS)(H O) ] (RE = Nd, Sm, Eu),
2 5 2 4
which show layer type structures with one of the sulfonate
groups remaining uncoordinated. Thermoanalytical investiga- Acknowledgement
tions show that after dehydration these compounds are stable
The authors are grateful to Wolfgang Saak for collecting the X-ray
up to nearly 550 °C. This is a significantly higher decomposi-
tion temperature compared to the related carboxylates and
proves that sulfonic acids are good candidates to build ther-
mally robust frameworks.
data.
References
[
1] a) Reviews: S. Kaskel, Nachr. Chem. 2005, 53, 394–399; b) U.
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Angew. Chem. 2008, 120, 8285–8289; Angew. Chem. Int. Ed.
2008, 47, 8164–8168.
Experimental Section
Preparation of [La(BTS)(H O) ] and [RE(BTS)(H O) ]
2
5
2
4
(RE = Nd, Sm, Eu)
3
For the synthesis of each compound a solution of H BTS (0.1 g) in
water (10 mL) was used. At a temperature of 50 °C, the rare earth [2] Review: J. L. C. Rowsell, O. M. Yaghi, Angew. Chem. 2005, 117,
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3
hydroxides RE(OH) (RE = La, Nd, Sm, Eu) were slowly added to
[
[
[
3] G. K. H. Shimizu, R. Vaidhyanathan, J. M. Taylor, Chem. Soc.
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crystals separated from the solutions after a few days. They showed
the colors of the respective rare earth ions (lanthanum: colorless, neo-
dymium: violet, samarium: yellow, europium: light yellow) and were
collected by filtration. With respect to their powder XRD patterns the
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X-ray Crystallography
[
8] CCDC-766201
[La(BTS)(H O)
data for this paper. These data can be obtained free of charge via
([Eu(BTS)(H
2
O)
4
])
and
CCDC-766202
For the structure determinations, single crystals of [La(BTS)(H
2 5
O) ]
(
2
5
]) contain the supplementary crystallographic
and [Eu(BTS)(H O) ], respectively, were glued onto glass fibers and
2
4
intensity data were collected with an image plate diffractometer (STOE
IPDS I) for the europium compound and a CCD diffractometer
www.ccdc.cam.ac.uk,
or
by
emailing
data_re-
quest@ccdc.cam.ac.uk, or by contacting The Cambridge Crystal-
lographic Data Centre, 12, Union Road, Cambridge CB2 1EZ,
UK; Fax: +44-1223-336033.
(
BRUKER APEX II) for the lanthanum compound. The structure solu-
¯
tion and refinement was successful in space group P1 (La) and P2
(
respectively.
1
/n
Eu) using the programs SHELXS97 and SHELXL97, [9] G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford Uni-
[12, 13]
versity Press, Oxford, 1997.
A numerical absorption correction was applied to
[14, 15]
[10] H. A. Eick, J. Am. Chem. Soc. 1958, 80, 43–44.
the data with the help of the programs X-RED and X-SHAPE.
[
11] W. Nowacki, Z. Kristallogr. 1938, 99, 339–341.
12] G. M. Sheldrick, SHELXS97, Program for the Solution of Crystal
Structures, Göttingen 1997.
Details of the data collection and the crystallographic parameters are
summarized in Table 2. For all compounds X-ray powder diffraction
measurement were performed on fine powdered samples of the sub-
stances using a flat sample holder. Reflections were detected in the
[
[13] G. M. Sheldrick, SHELXL93, Program for the Refinement of
Crystal Structures, Göttingen 1993.
range from 5° to 90° with the diffractometer STADI P (STOE) using [14] X-RED 1.07, Data Reduction for STADI4 and IPDS, Stoe & Cie
Cu-K
α
radiation (λ = 154.18 pm). Lattice parameter refinement was
Darmstadt 1996.
[
16]
performed with the help of the diffractometer software.
The same [15] X-SHAPE 1.01, Crystal Optimization for Numerical Absorption
Correction, Stoe & Cie Darmstadt 1996.
technique and the same powder diffractometer were used for the char-
acterization of the residues of the thermal decomposition.
POW
POWPOW
[
16] VISUAL X
3.01
, Software Package for the STOE Pow-
der Diffraction System, Stoe & Cie, Darmstadt, Germany, 1996.
17] Thermal analysis for the analyzer SDTA 851e, METTLER
TOLEDO, Germany, 2006.
[
Thermal Analysis
For the investigation of the thermal behavior the respective compound
Received: September 12, 2010
Published Online: December 2, 2010
(about 10 mg) was placed into a corundum container that was heated
2
00
www.zaac.wiley-vch.de
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 195–200