1,2-Bis(N-fluoro-p-toluenesulfon-amido)ethane chloroform solvate

Article abstract of DOI:10.1107/S0108270101007983

The title compound, N,N′-difluoro-N,N′-ethylenedi-p-toluenesulfonamide, C₁₆H₁₈F₂N₂O₄S₂ ·CHCl₃, is a novel stable compound of the N-F class of reagents containing two R₂

Full text of DOI:10.1107/S0108270101007983

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
1999) has shown that bis(N-halogeno) compounds, such as 1,2-
bis(N-bromo-2,5-dimethylbenzenesulfamido)ethane, are good
selective brominating agents and relatively accessible. We
report here an extension of that work to give the ¯uorinated
analogue, which has resulted in the ®rst structural character-
ization of an organic bis(NÐF)-containing compound.
ISSN 0108-2701
1,2-Bis(N-fluoro-p-toluenesulfon-
amido)ethane chloroform solvate
Khazaei Ardeshir,a R. Eric Banks,b Mohammed K.
Besheesh,b Alan K. Brisdonb* and Robin G. Pritchardb
aChemistry Department, Bu-Ali Sina University, Hamadan, Iran, and bDepartment of
Chemistry, UMIST, PO Box 88, Manchester M60 1QD, England
Correspondence e-mail: alan.brisdon@umist.ac.uk
The title compound, (I), may be synthesized by passing
dilute elemental ¯uorine through a CHCl3 solution of 1,2-
bis(benzenesulfonamido)ethane at low temperature. Crystal-
lization of (I) from a CHCl3 solution resulted in crystals of (I)
as the CHCl3 solvate which crystallizes in the space group
P2/n. A view of molecule (I) with the atomic numbering
scheme is shown in Fig. 1 and selected geometric parameters
are given in Table 1. The bond lengths obtained for compound
(I) are mostly in accord with anticipated values (Orpen et al.,
1994). Of particular interest are the two NÐF distances in this
molecule, which are the same within experimental limits, viz.
Received 3 April 2001
Accepted 14 May 2001
The title compound, N,N0-di¯uoro-N,N0-ethylenedi-p-tolu-
enesulfonamide, C16H18F2N2O4S2ÁCHCl3, is a novel stable
compound of the NÐF class of reagents containing two R2NÐ
F functionalities. The compound, as the chloroform solvate, is
the ®rst such bis(NÐF) compound to be structurally
characterized. It adopts a solid-state structure in which the
two aromatic rings are antiperiplanar and a combination of
weak CÐHÁ Á ÁFand CÐHÁ Á ÁO hydrogen bonds [distances and
Ê
1.428 (3) and 1.433 (3) A. These distances are comparable
with those found in related neutral NÐF-containing organic
systems, i.e. 1.435 (3) (Kakuda et al., 1997), 1.420 (4) (Davis et
Ê
al., 1998) and 1.437 (6) A (Batail et al., 1974), with an average
ꢁ
Ê
angles range from 3.265 (4) to 3.439 (4) A and 150 to 170 ,
Ê
of 1.431 (7) A. However, as expected, the NÐF distances are
longer than the distances found in molecules which formally
respectively] and ꢀ-stacking between the rings of different
Ê
molecules (separations of 3.717 and 3.926 A) results in a solid-
state structure containing well de®ned channels in which
CHCl3 solvent molecules are located. The NÐF distances are
Ê
1.428 (3) and 1.433 (3) A.
+
contain NÐF bonds, i.e. 1.106 (2) (Klapotke et al., 1993),
È
1.37 (2) (Banks, Pritchard & Sharif, 1993) and 1.406 (3) A
(Banks, Sharif & Pritchard, 1993), with an average of
Ê
Ê
1.29 (2) A. However, this average ®gure is distorted by the
È
very short NÐF distance observed by Klapotke for the
Comment
hexa¯uoroarsenate salt of N-¯uoro-2,4,6-trichlorotriazine,
which the authors describe as being unreliable due to severe
disorder problems.
The molecule is symmetric about the central CÐC bond;
this results in an overall Z-like shape and the two NÐF
moieties are located on opposite sides of the molecule. The
Fluorine and ¯uorine-containing substituents can exert a
profound in¯uence on the activity and selectivity of bio-
organic molecules. This realisation has lead to much work in
identifying reagents which can be used as site-selective ¯uor-
inating agents, and many of the more recent advances in this
area have involved compounds in which ¯uorine is bound to
an N atom. Included in this class of compounds are reagents
featuring neutral N atoms of the type R2NF, for example,
N-¯uoro-N-alkylsulfonamides (Barnett, 1984) and the elec-
trophilic ¯uorine-delivery agents [R3N+F], such as 1-chloro-
methyl-4-¯uoro-1,4-diazoniabicyclo[2.2.2]octane
bis(tetra-
¯uoroborate) (Banks et al., 1996; Banks, 1998). However, the
amount of structural data for such NÐF-containing systems is
quite limited. There are just 12 crystal structures in the
Cambridge Structural Database (Allen & Kennard, 1993) for
organic compounds containing NÐF bonds, six of which are
NF2-containing materials, i.e. formally organic derivatives of
NF3. Of the remaining six structures, three compounds contain
neutral NÐF moieties and the other three contain the +NÐF
group. There are no structures of compounds which contain
two separate single NÐF moieties (neutral or charged) within
the same organic molecule. Recent work (Ardeshir & Abbas,
Figure 1
A view of (I) with the atomic numbering scheme. Displacement ellipsoids
are drawn at the 50% probability level and H atoms have been omitted
for clarity.
ꢀ
970 # 2001 International Union of Crystallography
Printed in Great Britain ± all rights reserved
Acta Cryst. (2001). C57, 970±972

organic compounds
two aromatic rings are antiperiplanar, with torsion angles of
C3ÐS1ÐN1ÐC1 = 50.4 (3)ꢁ, N1ÐC1ÐC2ÐN2 = 179.4 (3)ꢁ
and C2ÐN2ÐS2ÐC10 = 52.2 (2)ꢁ. In the solid state, there
are weak hydrogen bonds between the electronegative F1 and
F2 atoms and the H atoms attached to the carbon centres C2
and C1, respectively, of the central aliphatic chain (Fig. 2). The
This combination of intermolecular interactions results in
the generation of channels running parallel to the a axis in
which solvent molecules may be located. In this case, mol-
ecules of CHCl3 solvent are located in the channels but are
disordered over two equally populated sites.
Ê
average CÐHÁ Á ÁF distance is 3.429 (6) A and the angle is
Experimental
The title compound was synthesized in two stages. 1,2-Bis(benzene-
sulfanamido)ethane was obtained by the dropwise addition of
diethylamine (6.21 g, 0.085 mol) to benzenesulfonyl chloride (30.0 g,
0.170 mol) at room temperature with vigorous stirring. The reaction
mixture was heated to 353 K for 30 min and then cooled and washed
with water (100 ml). The resulting white solid was ®ltered and
recystallized from boiling ethanol. 1,2-Bis(benzenesulfanamido)-
ethane (0.5 g, 1.5 mmol) was dissolved in chloroform (180 ml) and the
solution cooled to 195 K. Elemental ¯uorine (15 mmol, 5% in N2)
was bubbled through the cold stirred solution for 15 min. After
warming to room temperature, the solvent was removed under
vacuum and the crude solid was washed with diethyl ether. Crystals
suitable for X-ray diffraction studies were grown by slow evaporation
of the solvent from a CHCl3 solution.
Crystal data
3
C16H18F2N2O4S2ÁCHCl3
Dx = 1.532 Mg m
Mo Kꢂ radiation
Cell parameters from 25
re¯ections
Mr = 523.81
Monoclinic, P2=n
Figure 2
A view of the intermolecular hydrogen bonds in the crystal structure of
(I).
Ê
a = 10.9948 (10) A
b = 9.6922 (10) A
Ê
ꢃ = 12.7±17.2ꢁ
ꢄ = 0.63 mm
T = 293 (2) K
Ê
1
c = 21.381 (5) A
ꢁ = 94.815 (10)ꢁ
Ê
V = 2270.4 (6) A
Z = 4
3
Plate, colourless
0.35 Â 0.30 Â 0.10 mm
Data collection
Enraf±Nonius CAD-4 diffrac-
tometer
Rint = 0.017
ꢃmax = 25.0ꢁ
Non-pro®led ! scans
Absorption correction: scan
(North et al., 1968)
Tmin = 0.810, Tmax = 0.940
4222 measured re¯ections
3999 independent re¯ections
2572 re¯ections with I > 2ꢅ(I)
h = 0 ! 13
k = 0 ! 11
l = 25 ! 25
3 standard re¯ections
frequency: 60 min
intensity decay: 3%
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
S1ÐO1
S1ÐO2
S1ÐN1
S1ÐC3
S2ÐO4
S2ÐO3
S2ÐN2
1.417 (2)
1.418 (2)
1.712 (3)
1.740 (3)
1.417 (2)
1.419 (2)
1.706 (3)
S2ÐC10
N1ÐF1
N1ÐC1
N2ÐF2
N2ÐC2
C1ÐC2
C3ÐC4
1.739 (3)
1.428 (3)
1.451 (4)
1.433 (3)
1.456 (4)
1.507 (5)
1.382 (5)
Figure 3
A view of the crystal packing illustrating the resulting channels formed in
the solid-state structure of (I).
170ꢁ. Hydrogen bonding also occurs between the O atoms of
the SO2 groups and the ortho H atoms of the arꢁomatic rings
O1ÐS1ÐO2
O1ÐS1ÐN1
O2ÐS1ÐN1
O1ÐS1ÐC3
O2ÐS1ÐC3
N1ÐS1ÐC3
O4ÐS2ÐO3
O4ÐS2ÐN2
O3ÐS2ÐN2
121.33 (16)
105.35 (15)
101.20 (14)
110.51 (16)
110.60 (16)
106.26 (15)
121.78 (16)
105.39 (15)
101.51 (14)
O4ÐS2ÐC10
O3ÐS2ÐC10
N2ÐS2ÐC10
F1ÐN1ÐC1
F1ÐN1ÐS1
C1ÐN1ÐS1
F2ÐN2ÐC2
F2ÐN2ÐS2
C2ÐN2ÐS2
109.75 (16)
110.72 (16)
106.13 (15)
105.0 (3)
105.22 (18)
114.6 (2)
105.2 (3)
Ê
with (CÐHÁ Á ÁO)av values of 3.330 (7) A and 153 . These two
features result in a two-dimensional stack of molecules in an
alternate head-to-tail fashion in the a-axis direction. The
aromatic rings of one stack interweave with those of a second
stack, resulting in the generation of an approximately square
arrangement when viewed down the a axis. The next pair of
105.10 (19)
115.6 (2)
Ê
stacks is separated in the c direction by a distance of ca 3.8 A
between the aromatic rings and is offset (Fig. 3); the offset and
short distance are indicative of ꢀ-interactions between the
aromatic rings.
O2ÐS1ÐN1ÐF1
C3ÐS1ÐN1ÐC1
O3ÐS2ÐN2ÐF2
179.94 (19)
50.4 (3)
179.1 (2)
C10ÐS2ÐN2ÐF2
N1ÐC1ÐC2ÐN2
63.4 (2)
179.4 (3)
ꢀ
Acta Cryst. (2001). C57, 970±972
Khazaei Ardeshir et al.
C16H18F2N2O4S2ÁCHCl3 971

organic compounds
Re®nement
KA thanks the Research and Postgraduate Committee of
Bu-Ali Sina University for funding in order to visit UMIST.
Re®nement on F2
R(F) = 0.050
wR(F2) = 0.142
S = 1.04
3999 re¯ections
309 parameters
H-atom parameters constrained
w = 1/[ꢅ2(Fo2) + (0.0717P)2
+ 0.3412P]
where P = (Fo2 + 2Fc2)/3
(Á/ꢅ)max = 0.026
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: GG1055). Services for accessing these data are
described at the back of the journal.
3
Ê
Áꢆmax = 0.36 e A
3
Ê
0.30 e A
Áꢆmin
=
References
Table 2
Hydrogen-bonding geometry (A, ).
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ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C1ÐH1AÁ Á ÁF2i
C2ÐH2BÁ Á ÁF1ii
C4ÐH4Á Á ÁO3ii
C8ÐH8Á Á ÁO4i
C15ÐH15Á Á ÁO2i
0.97
0.97
0.93
0.93
0.93
2.46
2.48
2.47
2.56
2.39
3.418 (4)
3.439 (4)
3.311 (4)
3.415 (4)
3.265 (4)
169
170
150
152
157
3
2
Symmetry codes: (i)
x; y; 12 z; (ii) 21 x; y; 12 z.
Molecule (I) crystallized in the monoclininc system; space group
P2/n or Pn from the systematic absences. P2/n was chosen and
con®rmed by the successful re®nement. H atoms were treated as
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Ê
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channels within the structure exist as disordered pairs (50:50 occu-
pancy) around the crystallographic twofold axis. This leads to the Cl
atoms nearly coalescing with another from a symmetry-related mol-
ecule, so distorting the vibrational ellipsoids for these atoms.
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re®nement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms &
Wocadlo, 1995); program(s) used to solve structure: SHELXS97
(Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97
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È
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È
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ꢀ
972 Khazaei Ardeshir et al.
C16H18F2N2O4S2ÁCHCl3
Acta Cryst. (2001). C57, 970±972