The Influence of the Counterions [AsF6]– and [GeF6]2– on the Structure of the [ClSO2NH3]+ Cation

Article abstract of DOI:10.1002/zaac.201800067

Chlorosulfonamide reacts in the superacidic solutions HF/GeF₄ and HF/AsF₅ under the formation of ([ClSO₂NH₃]⁺)₂[GeF₆]^2– and [ClSO₂NH₃]⁺

Full text of DOI:10.1002/zaac.201800067

Title: The Influence of the Counterions [AsF6]⁻ and [GeF6]2⁻ on the
Structure of the [ClSO2NH3]⁺ Cation
Authors: Dominik Leitz, Karin Stierstorfer, Yvonne Morgenstern, Florian
Zischka, and Andreas J. Kornath
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To be cited as: Z. anorg. allg. Chem. 10.1002/zaac.201800067
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10.1002/zaac.201800067
Zeitschrift für anorganische und allgemeine Chemie
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The Influence of the Counterions [AsF6]⁻ and [GeF6]2⁻ on the
Structure of the [ClSO2NH3]⁺ Cation
Dominik Leitz,[a] Karin Stierstorfer,[a] Yvonne Morgenstern,[a] Florian Zischka[a] and Andreas J.
Kornath[a]*
Abstract: Chlorosulfonamide reacts in the superacidic solutions
HF/GeF4 and HF/AsF5 under the formation of ([ClSO2NH3]⁺)2[GeF6]2⁻
and [ClSO2NH3]⁺[AsF6]⁻, respectively. The chlorosulfonammonium
salts were characterized by X-ray single crystal structure analysis as
well as vibrational spectroscopy and discussed together with quantum
chemical calculations. ([ClSO2NH3]⁺)2[GeF6]2⁻ crystallizes in the
triclinic space group P–1 with one formula unit in the unit cell.
[ClSO2NH3]⁺[AsF6]⁻ crystallizes in the monoclinic space group P21/n
with four formula units in the unit cell. Dependent on the counterion,
[AsF6]⁻ or [GeF6]2⁻, considerable structural differences of the
[ClSO2NH3]⁺ cation are observed. Furthermore, the hitherto unknown
X-ray single crystal structure of chlorosulfonamide is determined in
the course of this study. Chlorosulfonamide crystallizes in the
orthorhombic space group Pmc2 with four formula units per unit cell.
[AsF6]⁻ and [GeF6]2⁻ is discussed together with quantum chemical
calculations.
Results and Discussion
Synthesis and Properties of ([ClSO2NH3]⁺)2[GeF6]2⁻(I) and
[ClSO2NH3]⁺[AsF6]⁻(II) . The salts (I) and (II) were obtained
quantitatively according to Equation (1) and (2).
In the first step ClSO2NH2 was synthesized in situ in an FEP
reaction vessel. The synthesis was carried out by the reaction of
chlorosulfuryl isocyanate and formic acid as described in a
previous study.[12] Then an excess of anhydrous HF (aHF), which
serves as reagent as well as solvent, was condensed into the
reaction vessel followed by three equivalents of GeF4 or AsF5,
respectively. The reaction mixtures were allowed to warm up to
– 40°C and stored for 72 hours. Colorless crystals were obtained
and characterized by single-crystal X-ray structure analyses and
vibrational spectroscopy.
Introduction
Chlorosulfonamide is one of the simplest representatives of
sulfonamides and was synthesized by Graf for the first time.[1] The
title compound is well characterized by vibrational[2-3] and
theoretical studies.[4] However, surprisingly a single crystal X-ray
diffraction study has not been reported so far. Despite the
numerous studies on sulfonamide derivatives investigations of its
protonation sites are rarely described in literature[5-7] In these
studies protonations at the nitrogen site are indicated which is in
agreement with a theoretical study where it was confirmed that
the nitrogen site is favorable to the protonation.[8] In a previous
study methanesulfonamide was investigated in the superacidic
systems HF/MF5 (M=As, Sb).[9] It was found that the protonation
takes place selectively at the nitrogen atom. Herein we present a
study of chlorosulfonamide in the superacidic solutions HF/GeF4
and HF/AsF5. While the superacidic system HF/AsF5 is well
established the superacidic system HF/GeF4 is rarely described
in literature. However, it showed an acidity beyond sulfuric acid
and demonstrated an interesting structural versatility of the
formed fluoridogermanate anions.[10-11] We present the structural
investigations of ([ClSO2NH3]⁺)2[GeF6]2⁻ and [ClSO2NH3]⁺[AsF6]⁻
by vibrational spectroscopy and single-crystal X-ray structure
analyses. Furthermore the structural influence of the counterions
Crystal Structure of ([ClSO2NH3]⁺)2[GeF6]2⁻(I). In Table 1 bond
lengths and bond angles are summarized. (I) crystallizes in the
triclinic space group P–1 with one formula unit in the unit cell.
Figure 1 depicts the formula unit of (I).
*
Prof. Dr. A. Kornath
*E-mail: andreas.kornath@cup.uni-muenchen.de
Department Chemie
Figure 1. Formula unit of ([ClSO2NH3]+)2[GeF6]2–. (50% probability displacement
ellipsoids). Symmetry code:.i = –x, 1–y,–z.
[a]
Ludwig-Maximilians-Universität München
Butenandtstr. 5–13,
81377 Munich, Germany
The coordination sphere of the sulfur atom can be described as a
strong distorted tetrahedron. Compared to the neutral compound
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the bond angles O1–S1–O2 [122.7(2)°] and Cl1–S1–O1
[108.6(1)°] are increased by approximately 2° and the bond
angles Cl1–S1–N1 [99.6(1)°] and N1–S1–O1 [107.2(2)°] are
decreased by 7.2° and 1.8°, respectively. The S–Cl bond length
of 1.956(1) Å is slightly shorter than the S–Cl bond in SO2Cl2
(1.980 Å).[13] With 1.725(3) Å the S–N bond length is significantly
O1–S1–N1
O1–S1–Cl1
N1–S1–Cl1
107.2(2)
108.6(2)
99.6 (1)
104.9(1)
111.0(1)
100.3(1)
102.6
110.9
98.0
102.8
110.9
98.4
[a] Calculated at the PBE1PBE 6–311G++(3pd,3df) level of theory.
elongated
with
respect
to
the
starting
material
Crystal structure of ClSO2NH2 (III). Single crystals of (III) were
grown by slow evaporation of the solvent benzene in dynamic
vacuum. The compound crystallizes in the orthorhombic space
group Pmc2 with four formula units in the unit cell. Figure 3 shows
a view of the two symmetrically independent molecules. Selected
bond lengths and angles of (III) are summarized in Table 2.
[1.571(4)/1.583(4) Å] and slightly shorter than the S–N bond in the
CH3SO2NCl2⁺ cation.[14] The S–O bond lengths of 1.417(3) Å are
comparable to the S–O bonds in SO2Cl2 (1.418 Å)[13] In terms of
the approximately octahedral [GeF6]2⁻ anion the Ge–F bond
lengths are in the range from 1.783(2) Å to 1.789(2) Å which is in
accordance to a previous studies describing [GeF6]2⁻.[10]
Crystal Structure of [ClSO2NH3]⁺[AsF6]⁻ (II). Bond lengths and
bond angles are summarized in Table 1. (II) crystallizes in the
monoclinic space group P21/n with four formula units in the unit
cell (Figure 2).
Figure 3. Section of the crystal structure of ClSO2NH2. (50% probability
displacement ellipsoids). Symmetry codes: i : 1–x, y, z; ii : –x, y, z.
Figure 2. Asymmetric unit of [ClSO2NH3]⁺[AsF6]⁻. (50% probability
displacement ellipsoids).
The S–Cl bond lengths of 2.018(1) and 2.014(3) Å, respectively,
are in the range of regular S–Cl single bonds observed for
SO2Cl2.[13] The S–N bond distances of 1.571(4) Å and 1.583(4) Å,
respectively, are in the region between regular S–N single and
double bonds. The short S–N distance can be explained by
nN*(S–O) and nN*(S–N) interactions where the molecule is
predicted to provide 18 kJ/mol. This is in good agreement to a
previous study where sulfamide was theoretically investigated.[15]
The S–O bonds of 1.424(2) Å and 1.425(2) Å are slightly longer
than observed for the [ClSO2NH3]+ cation.
In comparison to (I) the distorted tetrahedral coordination of the
sulfur atom is slightly different. The S–O bond lengths are slightly
shorter whereas the S–N bond of 1.765(3) Å is significantly longer
than in (I). Each cation is connected with two [AsF6]⁻ anions by
strong hydrogen bonds with N(–H)∙∙∙F donor-acceptor distances
of 2.894 Å and 2.953 Å, respectively. The cations are connected
by N(–H)∙∙∙O hydrogen bonds of donor-acceptor distances of
3.139(3) Å forming zig-zag chains.
Table 1. Selected bond lengths and bond angles of ([ClSO2NH3]⁺)2[GeF6]2⁻
and [ClSO2NH3]⁺[AsF6]⁻.
[ClSO2NH3]⁺
[GeF6]2⁻
[AsF6]⁻
obsd.
[ClSO2NH3]⁺∙
HF
[ClSO2NH3]⁺
Table 2. Selected bond lengths and bond angles of ClSO2NH2.
obsd.
calcd.[a]
calcd.[a]
Bond lengths [Â]
Bond lengths [Å]
obsd.
calcd.[a]
S1–O1
S1–N1
S1–Cl1
1.417(3)
1.725(3)
1.956(1)
1.406(2)
1.765(3)
1.945(1)
1.405
1.820
1.964
1.404
1.854
1.959
S1–O1 / S2–O2
S1–N1 / S2–N2
1.424(2) / 1.425(2)
1.571(4) / 1.583(4)
1.416
1.617
Bond angles [°]
S1–Cl1 / S2–Cl2
2.018(1) / 2.014(1)
2.052
O1–S1–O2
122.7(2)
123.6(1)
126.3
126.3
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combination band of 5+8 is observed. At 1550 cm⁻1 (I) a NH
deformation mode is detected. The antisymmetric SO2 stretching
mode is observed at around 1450 cm⁻1. the symmetric SO2
stretching mode is splitted due to Fermi resonance and occurs at
around 1215 cm⁻1 and 1190 cm⁻1, respectively. The SN
stretching vibration occurs at around 485 cm⁻1 and is red-shifted
by 435 cm⁻1 compared to the neutral compound. This remarkable
shift can be explained by the significant elongation of the SN bond
length. As expected for the almost ideal octahedral [GeF6]2⁻ anion
three Raman lines and two IR bands are observed. In case of the
[AsF6]⁻ more lines and bands than expected are detected which
can be explained by the distortion of the octahedral structure
according to the findings in the crystal structure.
Bond angles [°]
O1–S1–O1 / O2–S2–O2
O1–S1–N1 / O1–S1–N1
O1–S1–Cl1 / O2–S2–Cl2
N1–S1–Cl1 / N2–S2–Cl2
120.7(1) / 119.8(1)
109.0(1) / 108.9(1)
105.3(1) / 105.8(1)
106.8(1) / 106.9(1)
123.8
107.8
105.7
104.4
[a] Calculated at the PBE1PBE 6–311G++(3pd,3df) level of theory.
Figure 4 shows the crystal packing of ClSO2NH2 molecules
connected by strong donor-acceptor interactions (N(–H)···O) of
2.926(3) Å and 2.952(3) Å, respectively, forming 14-membered
rings.
Figure 4. Low temperature vibrational Spectra of ([ClSO2NH3]⁺)2[[GeF6]2⁻: (a)
IR spectrum, (d) Raman spectrum; [ClSO2NH3]⁺[AsF6]⁻: (b) IR spectrum, (c)
Raman spectrum; ClSO2NH2: (e) Raman spectrum.
Figure 4. Crystal packing of ClSO2NH2 (50% probability displacement
ellipsoids). View along the b axis. Hydrogen bonds are represented by dashed
lines.
Vibrational Spectroscopy of ([ClSO2NH3]⁺)2[GeF6]2⁻ (I) and
[ClSO2NH3]⁺[AsF6]⁻ (II). The Raman and infrared spectra of (I)
and (II) are shown in Figure 5. In Table 3 the observed and
quantum-chemically calculated frequencies are summarized. For
(ClSO2NH3]⁺ with approximately Cs symmetry 18 fundamental
vibrations are expected. The assignment of the vibrational
frequencies is supported by quantum chemical calculations of
[ClSO2NH3]⁺∙HF. As expected, in case of the protonated species
three NH stretching vibrations are observed which occur in the
range from 3171 cm⁻1 to 2828 cm⁻1 and are significantly red-
shifted by approximately 200 cm⁻1 compared to the neutral
compound. In the IR spectra of (I) and (II) at 1726 cm⁻1
a
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Table 3. Observed vibrational frequencies [cm⁻1] of ([ClSO2NH3]⁺)2[GeF6]2⁻ ,[ClSO2NH3]⁺[AsF6]⁻ and calculated vibrational frequencies [cm⁻1] of [ClSO2NH2]⁺∙HF.
([ClSO2NH3]⁺)2[GeF6]2⁻
[ClSO2NH3]⁺[AsF6]⁻
[ClSO2NH3]⁺
[ClSO2NH3]⁺∙HF
Assignment
(a)
IR
(d)
Raman
(b)
IR
(c)
Raman
calcd.[a]
calcd.[a]
3146 (m)
3048 (m)
2828 (m)
3171 (1)
3085 (4)
3514 (145/22)
3492 (142/29)
3389 (138/93)
3519 (134/21)
3446 (134/48)
3163 (948/143)
12
1
A’’



as(NH2)
iph(NH3)
ooph(NH3)
A’
A’
2828 (5)
1455 (9)
2828 (m)
1726 (w)
2
1726 (w)
1550 (w)

13
3

1612 (39/3)
1610 (35/3)
1548 (165/7)
1404 (162/0)
1264 (122/21)
1620 (30/2)
A’’
A’
A’’
A’
A’
 (NH2)
 (NH2)
1528 (m)
1451 (m)
1528 (2)
1608 (169/2)
1541 (168/7)
1450 (144/1)
1262 (120/21)
1458 (w)
1426 (s)
1218 (w)
1193 (m)
1062 (vw)
1016 (w)
562 (w)
1460 (14)
14
4
as(SO2)
 (NH2)
s(SO2)
1215 (1)
1216 (m)
1184 (m)
1066 (m)
1207 (33)
1188 (10)
1068 (24)
1012 (1)
562 (4)
5
1190 (27)
1068 (17)

943( 60/2)
936 (11/2)
596 (154/4)
569 (90/10)
448 (5/13)
417 (2/7)
1009 (39/2)
973 (8/2)
6
A’
A’’
A’
A’
A’
A’
A’’
A’’
A’
A’’
 (NH3)
 (NH2)
 (SO2)
 (ClSO)
 (SN)
15
7
560 (3)
618 (165/3)
592 (87/13)
469 (27/8)
421 (1/9)
8
485 (w)
438 (w)
486 (12)
484 (w)
484 (14)
9
420 (100)
421 (100)
10
16
17
11
18
 (SCl)
 (NSO)
 (SO2)
 (ClSN)
 (NH3)
351 (0/2)
361 (1/2)
281 (6/2)
285 (27/2)
273 (15/2)
162 (4/1)
198 (2)
233 (11/2)
162 (0/0)
716 (14)
697 (9)
688 (4)
584 (33)
401 (5)
275 (6)
248 (1)








[MF6]⁻
[MF6]⁻
[MF6]⁻
[MF6]⁻
[MF6]⁻
[MF6]⁻
[MF6]⁻
[MF6]⁻
596 (vs)
508 (w)
605 (15)
700 (s)
587 (m)
391 (m)
219 (2)
126 (28)
[a] Calculated at the PBE1PBE/6-311G++(3pd,3df) level of theory. IR intensity in km·mol⁻1 and Raman intensities in Å4·⁻1Abbrevations for IR intensities:
v=very, s=strong, m=medium, w=weak. Raman activity is normalized in which the most Raman active mode is normalized to be 100. M= Ge; As
Theoretical Calculations. Quantum chemical calculations were
carried out using the hybrid DFT method PBE1PBE employing the
6–311G++(3pd,3df) basis set. To support the vibrational
spectroscopic investigations of the [ClSO2NH3]+ cation the
frequencies were calculated in harmonic approximation.
[ClSO2NH3]+ was calculated as free cation as well as HF adduct
in the gas phase. Especially in case of the NH stretching
vibrations the calculated frequencies of the HF adduct show a
closer match to the observed frequencies summarized in Table 3.
From Table 1 it can be assumed that the cationic structure is
stronger influenced by [GeF6]2⁻ than by [AsF6]⁻ due to the closer
match of the structural parameters for the calculated [ClSO2NH3]⁺
cation. This finding prompted us to a further theoretical
investigation on the M06/aug-cc-pVTZ level of theory including all
anions showing contacts to the cation. Therefore the units
([ClSO2NH3⁺])2[GeF6]2⁻ and [([ClSO2NH3]⁺([AsF6]⁻)2]⁻ were
calculated using the structural parameters observed in the crystal
structures (Figure 5). A comparison of the calculated and the
observed bond angles and bond lengths is given in Table 3. The
quantum chemical calculations support the hypothesis that the
cationic structure of [ClSO2NH3]⁺, especially the S–N bond, is
remarkably influenced depending on the counterion.
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elongation of the sulfur-nitrogen bond. It was found that
depending on the counterion the sulfur-nitrogen bond is
significantly different, 1.725(3) Å in (I) and 1.765(3) Å in (II).
Quantum chemical calculations involving all interacting anions
confirm the significant influence of the counterions on the
structure of the [ClSO2NH3]⁺ cation.
Experimental Section
Caution! Avoid contact with any of these materials. HCl and HF are
formed through hydrolysis of these compounds, respectively. HF burns
skin and causes irreparable damage. Safety precautions should be taken
when using and handling these materials.
Apparatus and Materials. All experimental work was carried out by using
standard Schlenk techniques using a stainless-steel vacuum line. The
reactions were performed in FEP/PFA reactors which were closed with a
stainless-steel valve. Data collections for (I) and (II) were performed with
an Oxford Xcalibur3 diffractometer equipped with a Spellman generator
(voltage 50 kV, current 40 mA) and a KappaCCD detector, operating with
MoKradiation0,717 Å). Data collection was performed at 173(2) K
using the CrysAlisCCD software, the data reductions were carried out
using CrysAlis RED software.[16] The solution and refinement of the
structure was performed with the programs SHELXL[17] and SHELXS-97[18]
implemented in the WinGX software package[19] and checked with the
software PLATON.[20] The absorption correction was achieved with the
SCALE3 ABSPACK multi-scan method.[21] Infrared spectra were recorded
in the range between 4000 cm–1 and 350 cm–1 at a temperature of –196°C
using a Bruker Vertex 70V FTIR spectrometer. The Raman spectroscopic
studies were carried out with a Bruker MultiRAM which is equipped with a
Nd:YAG laser (=1064 nm). The spectra were recorded in a range
between 4000 cm–1 and 250 cm-1. Quantum chemical calculations were
carried out with the Gaussian 09 program package.[22] All calculations were
performed employing the hybrid method PBE1PBE and the base set 6–
311++G(3df,3pd). ClSO2NCO (Sigma Aldrich) was distilled several times
prior to use. HCOOH was dried over B2O3. GeF4 and AsF5 were
synthesized from the elements and purified by fractionated distillation.
Figure 5. Calculated units of ([ClSO2NH3⁺])2[GeF6]2⁻ (top) and
[([ClSO2NH3]⁺([AsF6]⁻)2]⁻ (bottom) on the M06/aug-cc-pVTZ level of theory.
Table 3. Comparison of the observed and calculated bond lengths and
bond angles of ([ClSO2NH3]⁺)2[GeF6]2⁻ and [ClSO2NH3]⁺[AsF6]⁻.
([ClSO2NH3]⁺)2
[GeF6]2⁻
[ClSO2NH3]⁺∙
[AsF6]⁻
obsd.
Bond lengths [Å]
calcd.[a]
obsd.
calcd.[a]
S1–O1
S1–N1
S1–Cl1
1.417(3)
1.725(3)
1.956(1)
1.421
1.733
2.023
1.406(2)
1.765(3)
1.945(1)
1.420
1.781
2.022
Synthesis of ClSO2NH2. An amount of 3.59 g (25.3 mmol) ClSO2NCO
was stirred at 0°C and 1.16 g (0.95 ml, 25.3 mmol) dry HCOOH was added
dropwise to the reaction vessel under dry nitrogen atmosphere. A colorless
solid was formed rapidly under gas formation.
Bond angles [°]
O1–S1–O2
O1–S1–N1
O1–S1–Cl1
N1–S1–Cl1
122.7(2)
107.2(2)
108.6(2)
99.6 (1)
124.4
106.5
109.1
97.9
123.6(1)
104.9(1)
111.0(1)
100.3(1)
126.1
107.5
107.9
96.7
Syntheses of ([ClSO2NH3]⁺)2[GeF6]2⁻ (I) and [ClSO2NH3]⁺[AsF6]⁻ (II).
For the syntheses of (I) and (II) in the first step ClSO2NH2 was synthesized
through the reaction of equimolar amounts (in a typical reaction each
1.0 mmol) of ClSO2NCO and HCOOH were condensed in an FEP reactor
and allowed to warm up to 0°C. The formed colorless solid was then dried
overnight in dynamic vacuum. In the second step an excess of HF followed
by 3 equivalents of GeF4 (I) or AsF5 (II) were condensed at –196°C into
the FEP reaction vessel. The mixture was then allowed to warm up to
– 40°C and was stored for 72 hours at this temperature. Colorless crystals
precipitated during this time. Excess GeF4 and AsF6, respectively, as well
as HF were removed in dynamic vacuum at –78°C for a time period of
14 hours.
[a] Calculated at the M06/aug-cc-pVTZ level of theory.
Conclusions
In the course of this study salts containing the [ClSO2NH3]+ cation
were isolated for the first time using the two binary superacidic
systems
HF/GeF4
and
and
HF/AsF5,
[ClSO2NH3]⁺[AsF6]⁻
respectively.
are
([ClSO2NH3]⁺])2[GeF6]2⁻
characterized by single-crystal X-ray structure analyses and low
temperature vibrational spectroscopy supported by quantum
chemical calculations. The protonation takes selectively place at
the nitrogen atom and leads in both cases to a significant
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Table 4. Crystal data and structure refinement for ([ClSO2NH3]⁺)2[GeF6]2⁻ and
[ClSO2NH3]⁺[AsF6]⁻
Acknowledgements
Financial support of this work by the Lududwig-Maximilian-
University of Munich (LMU), by the Deutsche
Empirical formula
([ClSO2NH3]⁺)2
[GeF6]2⁻
[ClSO2NH3]⁺
[AsF6]⁻
ClSO2NH2
Forschungsgemeinschaft (DFG) and the F-Select GmbH is
gratefully acknowledged.
Mr
419.68
173(3)
305.46
123(2)
0.71073
monoclinic
P21/n
115.54
173(2)
0.71073
orthorhombic
Pmc2
T [K]
(Mo-K) [Å]
Crystal system
Space Group
a [Å]
0.71073
triclinic
P–1
Keywords: protonation • chlorosulfonamide • superacid
chemistry• single-crystal structure• vibrational spectroscopy
5.5686(4)
5.5718(5)
10.883(1)
82.637(8)
86.425(7)
61.069(9)
293.09(4)
1
4.9653(3)
7.4256(4)
19.3595(1)
90
7.7652(6)
5.7998(4)
8.7627(6)
90
[1]
[2]
R. Graf, Chem. Ber. 1959, 92, 509-513.
W. Schneider, G. Kessler, H. A. Lehmann, Z. anorg.allg. Chem.
1968, 356, 239-243.
b [Å]
c [Å]
[3]
R. M. S. Álverez, E. H. Cutín, H. G. Mack, C. O. D. Védova, J. Mol.
Struct. 1998, 440, 213-219.
[°]
[4]
[5]
H. M. Badawi, Spectrochim. Acta 2006, 65A, 453-458.
F. M. Menger, L. Mandell, J. Am. Chem. Soc. 1967, 89, 4424-
4426.
[°]
90.741(5)
90
90
[°]
90
[6]
[7]
[8]
R. G. Laughlin, J. Am. Chem. Soc. 1967, 89, 4268-4271.
A. Bagno, G. Scorrano, J. Phys. Chem. 1996, 100, 1545-1553.
B. A. Shainyan, N. N. Chipanina, L. P. Oznobikhina, J.Phys.Org.
Chem. 2012, 25, 738-747.
V[Å3]
713.73(7)
4
394.64(5)
4
Z
[9]
D. Leitz, M. Hopfinger, K. Stierstorfer, J. Axhausen, A. Kornath, Z.
anorg. allg. Chem. 2017, 643, 1202–1207.
T. Soltner, PhD Thesis 2011.
M. Hopfinger, K. Lux, A. Kornath, ChemPlusChem 2012, 77, 476-
481.
R. Appel, G. Berger, Chem. Ber. 1958, 91, 1339-1341.
D. Mootz, A. Merschenz-Quack, Acta Cryst. 1988, C44, 924-925.
R. Minkwitz, P. Garzarek, F. Neikes, A. Kornath, H. Preut, Z.
anorg. allg. Chem. 1997, 623, 333-339.

calcd, [gcm–3
[mm–1
MoK[Å]
]
2.378
2.843
1.945
[10]
[11]
]
3.508
5.507
1.313

0.71073
204
0.71073
0.71073
[12]
[13]
[14]
F(000)
T[K]
584
232
173(2)
123(2)
173(2)
[15]
[16]
[17]
[18]
E. Hansen, E. Limé, P.-O. Norrby, O. Wiest, J. Phys. Chem 2016,
A120, 3677-3682.
CrysAlisRED, Version 1.171.35.11 (release 16–05–2011 CrysAlis
171.NET), Oxford Diffraction Ltd., UK, 2011.
hkl range
–6:6;–6;6;–
13:10
–6:6;–10:10;–
26:25
–6:10;–7:7;–11:9
refl. measured
refl. unique
Rint
2160
6331
1778
G. M. Sheldrick, SHELXL-97, Program for the Refinement of
Crystal Structures, University of Göttingen, Germany, 1997.
G. M. Sheldrick, SHELXS-97, Program for Crystal Structure
Solution, University of Göttingen, Germany, 1997.
L. Farrugia, Journal of Applied Crystallography 1999, 32, 837-838.
A. L. Spek, PLATON, A Multipurpose Crystallographic Tool, U.
Utrecht University, The Netherlands, 1999., 1999.
SCALE3 ABSPACK, An Oxford Diffraction Program, O. Diffraction,
Ltd., UK, 2005.
H. B. S. G. W. T. M. J. Frisch, G. E. Scuseria, M. A. Robb, J. R.
Cheeseman, J.A. Montgomery, T. V. Jr., K. N. Kudin, J. C. Burant,
J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M.
Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E.
Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R.
Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C.
Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P.
Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D.
Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K.
Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S.
Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P.
Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-
Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W.
Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J. A. Pople,
Gaussian, Inc. 2003, Pittsburgh PA.
1181
1920
871
0.0194
0.0337
0.0293
[19]
[20]
parameters
R(F)/wR(F2)a)
weighting schemeb)
S(GooF)c)
91
121
63
0.0290/0.0706
0.0251/0.5437
1.096
0.0325/0.0606
0.0221/0.1433
1.093
0.0334/ 0.0469
0.0121/0.0000
1.020
[21]
[22]
residual
0.559/–0.576
Oxford
0.416/–0.793
Oxford
0.323/–0.271
Oxford
device type
solution/refinement
SHELXS-97[18]
SHELXL-97[17]
SHELXS-97[18]
SHELXL-97[17]
SHELXS-97[18]
SHELXL-97[17]
CCDC
1574006
1574004
1574005
a) R1 = Σ||Fo|−|Fc||/Σ|Fo|; b) wR2 = [Σ[w(Fo2−Fc2)2]/Σ[w(Fo)2]]1/2; w =
[σc2(Fo2)+(xP)2+yP]−1; P = (Fo2+2Fc2)/3 c) GoF = {Σ[w(Fo2−Fc2)2]/(n−p)}1/2 (n =
number of reflexions; p = total number of parameters).
This article is protected by copyright. All rights reserved.

10.1002/zaac.201800067
Zeitschrift für anorganische und allgemeine Chemie
FULL PAPER
Entry for the Table of Contents
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FULL PAPER
The protonation of
Protonated Chlorosulfonamide
chlorosulfonamide in the binary
superacidic systems HF/AsF5 and
HF/GeF4 leads to the formation of
salts containing the [ClSO2NH3]⁺
cation. The protonation causes a
remarkable elongation of the S–N
bond length which is furthermore
influenced by the anions.
Dominik Leitz, Karin Stierstorfer,
Yvonne Morgenstern, Florian Zischka,
Andreas Kornath*
Page No. – Page No.
The Influence of [AsF6]⁻ and [GeF6]2⁻
on the Structure of the [ClSO2NH3]⁺
Cation *
This article is protected by copyright. All rights reserved.