The anilinium chloride adduct of 4-bromo-N-phenylbenzene-sulfonamide

Article abstract of DOI:10.1107/S0108270106022104

The title compound anilinium chloride-4-bromo-N-phenylbenzenesulfonamide (1/1), C₆H₈N⁺·Cl ^-·C₁₂H₁₀BrNO₂S, displays a hydrogen-bonded ladder motif with four independent N-H...Cl bonds in which both the NH group of the sulfonamide molecule and the NH₃ group of the anilinium ion [N...Cl = 3.135 (3)-3.196 (2) A and N-H...Cl = 151-167°] are involved. This hydrogen-bonded chain contains two independent R₄²(8) rings and each chloride ion acts as an acceptor of four hydrogen bonds.

Full text of DOI:10.1107/S0108270106022104

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
MeO, and, additionally, Y is ethynyl. These sulfonamides
generally crystallize more readily than the related carbox-
amides, chalcones, or pyridine and other heterocyclic analo-
gues, the structural systematics of which are also under
investigation. The syntheses are usually trivial. In a few cases,
the not unexpected disulfonyl by-product has been isolated.
Adjustment of the reactant quantities and reaction conditions
has allowed the required product to be formed exclusively.
In only one case out of more than 100 samples of this set,
and out of many hundreds of examples in the extended set, has
an unexpected product been encountered. This was during the
synthesis intended to produce compound (II), where X = Br
and Y = H. This compound is dif®cult to crystallize because of
its extreme solubility in most solvents, including hydrocarbons,
and the result of evaporative crystallization is generally a
viscous syrup. During an attempted crystallization of (II) from
toluene, novel crystals were encountered which were initially
thought to be the toluene solvate of the hydrochloride of (II).
This seemed chemically improbable, because of the weak
basicity of sulfonamides, although it is possible for favour-
able crystal structures of salts and adducts to contradict
expectations derived from solution-determined basicities.
Re®nement of the structure led to the elucidation of the
composition as the anilinium chloride adduct, (III), of the
required sulfonamide, (II).
ISSN 0108-2701
The anilinium chloride adduct
of 4-bromo-N-phenylbenzene-
sulfonamide
Thomas Gelbrich,* Terence L. Threlfall and Michael B.
Hursthouse
School of Southampton, Department of Chemistry, Highfield, Southampton
SO17 1BJ, England
Correspondence e-mail: gelbrich@soton.ac.uk
Received 15 May 2006
Accepted 9 June 2006
Online 14 July 2006
The title compound anilinium chloride±4-bromo-N-phenyl-
(1/1),
benzenesulfonamide
C6H8N+ÁCl ÁC12H10BrNO2S,
displays a hydrogen-bonded ladder motif with four indepen-
dent NÐHÁ Á ÁCl bonds in which both the NH group of the
sulfonamide molecule and the NH3 group of the anilinium ion
[NÁ Á ÁCl = 3.135 (3)±3.196 (2) A and NÐHÁ Á ÁCl = 151±167 ]
are involved. This hydrogen-bonded chain contains two
independent R24(8) rings and each chloride ion acts as an
acceptor of four hydrogen bonds.
ꢀ
Ê
Comment
In a project aimed at relating crystal structure to molecular
structure, which we term structural systematics, large numbers
of related molecules are synthesized and their crystal struc-
tures determined. For this purpose, it is essential to choose
compounds that can be synthesized readily, and for well
known reactions it is usually easy to determine whether this is
the case. By contrast, it is not possible to forecast whether the
products will crystallize easily with suf®cient size and quality
for single-crystal diffraction, except in a very general and
imperfect way by experience of crystallizing large numbers of
The bond lengths and angles of the sulfonamide molecule
(Fig. 1) are in accordance with those in previously reported
molecules of the general structure (I) [X = Cl and Y = Br, and
Â
X = Br and Y = H (Rerat, 1969); X = Y = MeO (Pokrywiecki et
al., 1973); X = I and Y = NO2, and X = NO2 and Y = I (Kelly et
al., 2002)]. Our own systematic investigation of crystal struc-
tures formed by molecules (I) has shown that they are
generally dominated by intermolecular NÐHÁ Á ÁO hydrogen-
bond interactions between the amine group and one sulfonyl
O atom, with the exception of only a few cases where X or Y is
CN or NO2. These interactions generate two distinct supra-
molecular synthons, viz. a dimer resulting in the formation of
R22(8) rings (Bernstein et al., 1995) and a chain motif. These
typical NÐHÁ Á ÁO chains also occur in the single-component
structure of sulfonamide (II), to be published elsewhere.
However, the formation of either of the two NÐHÁ Á ÁO bond
motifs is prevented in cocrystal (III) by the presence of the
chloride ion. Instead, sulfonamide molecules are linked by
NÐHÁ Á ÁCl hydrogen bonds to chloride ions. Furthermore, Cl
is at the same time involved in another three NÐHÁ Á ÁCl
related compounds. In this project, over 100 benzenesulfona-
mides of the general structure (I) have been synthesized,
where X and Y are H, CH3, F, Cl, Br, I, CF3, CN, NO2 and
o470 # 2006 International Union of Crystallography
DOI: 10.1107/S0108270106022104
Acta Cryst. (2006). C62, o470±o472

organic compounds
bonding interactions with the ammonium groups of three
different anilinium ions. In turn, each anilinium ion is
connected via its ammonium group to three Cl ions (Fig. 2).
As a result, two crystallographically independent hydrogen-
bonded rings are formed, which are both of the R24(8) type.
Each ring has a centre of inversion, and adjacent rings, which
are crystallographically independent, viz. Á Á ÁCl1Á Á ÁH2ÐN2Ð
H4Á Á ÁCl1Á Á Á and Á Á ÁCl1Á Á ÁH3ÐN2ÐH4Á Á ÁCl1Á Á Á, have a
common N2ÐH4Á Á ÁCl1 edge. Thus, a corrugated ladder
structure is obtained. This one-dimensional in®nite structure
propagates parallel to [100]. It consists of two antiparallel
strands of three-connected nodes, composed alternately by
chloride ions and ammonium groups of the anilinium ions.
Additionally, each chloride node has a fourth connection to
one sulfonamide molecule, and neighbouring sulfonamide
molecules attached to the same strand of the ladder are
related by translation symmetry. By contrast, two molecules
connected to chloride nodes located in different strands of the
same ladder are related by inversion symmetry.
For the three H atoms in the ammonium group of the
anilinium ion, the structure of (III) contains one chloride ion
as a potential hydrogen-bond acceptor, and ignoring the
sulfonamide molecule, a net consisting of three-connected
chloride and ammonium nodes is formed as a result. The same
situation was found in the structure of anilinium chloride
Â
Â
(Lopez-Dupla et al., 2003), from which, however, a funda-
mentally different topology arises. Here, a two-dimensional
hydrogen-bonded net with (6,3)-topology (Wells, 1977) is
formed in which the two types of nodes alternate. By contrast,
the ladder motif observed in (III) occurs in other related
bromide and iodide structures, such as 2-methyl-4-nitro-
Figure 1
The asymmetric unit of (III), showing the atomic numbering scheme.
Displacement ellipsoids are drawn at the 30% probability level.
Figure 3
Figure 2
Part of the crystal structure of (III), consisting of two complete NÐ
HÁ Á ÁCl-bonded ladders (lower section) and portions of another two such
units, showing the interplay between different types of intermolecular
interaction. The structure is viewed in the direction of the translation
vector of the NÐHÁ Á ÁCl hydrogen-bonded chains. Only H atoms
involved in contacts listed in Table 1 are shown.
The one-dimensional hydrogen-bonded net (ladder) between sulfon-
amide molecules, anilinium cations and chloride anions in (III).
Hydrogen bonds are indicated by dashed lines. Atoms marked with an
asterisk (*) or hash (#) are at the symmetry positions (x 1, y, z) and
(
x + 1, y, z + 1), respectively.
C6H8N+ÁCl ÁC12H10BrNO2S o471
ꢁ
Acta Cryst. (2006). C62, o470±o472
Gelbrich et al.

organic compounds
Re®nement
anilinium iodide (Lemmerer & Billing, 2006), while the high-
and low-temperature forms of anilinium bromide (Sakai &
Terauchi, 1981; Fecher et al., 1981) and anilinium iodide
(Fecher & Weiss, 1986) produce a disordered derivative of the
same ladder.
Each NÐHÁ Á ÁCl-bonded ladder exhibits additional internal
close C14ÐH14Á Á ÁO1 contacts between anilinium ions and
sulfonamide molecules (Table 1). There is also a set of two
close BrÁ Á Áꢀ contacts between two sulfonamide molecules
which belong to neighbouring ladders related by translation
along the c axis. The separation between Br and the centroid
Re®nement on F2
R[F2 > 2ꢅ(F2)] = 0.034
wR(F2) = 0.088
S = 1.04
3286 re¯ections
248 parameters
H atoms treated by a mixture of
independent and constrained
re®nement
w = 1/[ꢅ2(F2o) + (0.045P)2
+ 0.0802P]
where P = (F2o + 2Fc2)/3
(Á/ꢅ)max = 0.001
3
Ê
Áꢇmax = 0.37 e A
Áꢇmin
3
Ê
0.55 e A
=
Extinction correction: SHELXL97
Extinction coef®cient: 0.0060 (13)
Table 1
Hydrogen-bond geometry (A, ).
ꢀ
Ê
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
of the benzene ring is 3.52 A. Furthermore, the anilinium ions
of two neighbouring ladders related by translation along the b
N1ÐH1Á Á ÁCl1
N2ÐH2Á Á ÁCl1
N2ÐH3Á Á ÁCl1i
N2ÐH4Á Á ÁCl1ii
C14ÐH14Á Á ÁO1iii
C17ÐH17Á Á ÁCl1iv
0.878 (14)
0.91
0.91
0.91
0.95
2.332 (18)
2.30
2.25
2.33
2.39
3.157 (3)
3.196 (2)
3.135 (3)
3.152 (2)
3.307 (3)
3.661 (3)
157 (3)
167
163
151
163
Ê
axis are ꢀ±ꢀ stacked (centroid separation = 4.01 A). The same
two units are also linked by two sets of CÐHÁ Á ÁCl contacts
between their anilinium and chloride ions (Table 1). All
described close contacts are shown in the packing diagram
(Fig. 3).
0.95
2.85
144
Symmetry codes: (i)
x ‡ 1; y ‡ 1; z ‡ 1.
x
1; y; z; (ii) x ‡ 1; y; z ‡ 1; (iii) x; y; z ‡ 1; (iv)
The origin of the anilinium chloride resulting from part of
the reactant aniline acting as a proton acceptor is readily
understood. It is surprising that it was not eliminated during
the normal work-up procedure of evaporation to small volume
to remove the pyridine and pyridine hydrochloride, followed
by puddling with water to effect solidi®cation. If this persis-
tence into the ®nal product is due to the particular stability of
the crystal structure, then it is surprising that analogous
compounds have not been frequently encountered during this
project.
All H atoms were located in difference maps. The position of the H
atom attached to N1 was re®ned with the NÐH distance restrained to
Ê
0.900 (15) A. All other H atoms were treated as riding, with CÐH
Ê
Ê
distances of 0.95 A and NÐH distances of 0.91 A. All Uiso(H) values
were re®ned freely.
Data collection: COLLECT (Hooft, 1998); cell re®nement:
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduc-
tion: DENZO and COLLECT; program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure:
SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker,
1998) and MERCURY (Macrae et al., 2006).
Experimental
4-Bromobenzenesulfonyl chloride (0.255 g, 1 mmol) was added to a
solution of aniline (0.093 g, 1 mmol) in pyridine (3 ml). The orange±
red colour that formed was discharged on boiling. After boiling for
30 min, the solution was evaporated to a small bulk under nitrogen
until white fumes of pyridine hydrochloride began to appear. The
cooled residue was treated with water and scratched with a rod until it
solidi®ed. The product was ®ltered off, dissolved in ethanol (5 ml)
and allowed to evaporate to a syrup. The product was taken up in
toluene (4 ml) and allowed to evaporate until crystals appeared. The
elongated prisms were identi®ed as the anilinium chloride adduct of
4-bromo-N-phenylbenzenesulfonamide, and the smaller plates as
4-bromo-N-phenylbenzenesulfonamide itself.
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: JZ3025). Services for accessing these data are
described at the back of the journal.
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Crystal data
C6H8N+ÁCl ÁC12H10BrNO2S
Lemmerer, A. & Billing, D. G. (2006). Acta Cryst. C62, o271±o273.
Â
3
Ê
V = 943.31 (11) A
Z = 2
Â
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a = 5.6705 (4) A
3
Dx = 1.555 Mg m
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Ê
1
Ê
b = 9.9954 (7) A
ꢄ = 2.44 mm
T = 120 (2) K
Ê
c = 17.3234 (12) A
ꢁ = 83.137 (4)ꢀ
ꢂ = 81.655 (4)ꢀ
ꢃ = 77.163 (3)ꢀ
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Bruker±Nonius KappaCCD
diffractometer
' and ! scans
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
Tmin = 0.359, Tmax = 0.615
8226 measured re¯ections
3286 independent re¯ections
2646 re¯ections with I > 2ꢅ(I)
Rint = 0.039
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È
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ꢆmax = 25.1ꢀ
o472 Gelbrich et al. C6H8N+ÁCl ÁC12H10BrNO2S
Acta Cryst. (2006). C62, o470±o472
ꢁ