Synthesis and crystal structure of 4-(tert-butyl)-N-(pyridin-3-ylmethyl) benzenesulfonamide

Article abstract of DOI:10.1007/s10870-013-0436-8

Reaction between 4-tert-butylphenyl sulfonyl chloride and 3-picolylamine in presence of triethylamine lead to the formation of 4-(tert-butyl)-N-(pyridin-3- ylmethyl) benzenesulfonamide. This compound crystallized in a triclinic space group, P-1, with cell parameters a = 6.7945 (2), b = 7.1791 (3), c = 17.1267 (7), α = 96.153 (1), β = 100.573 (2), γ = 98.911 (2) and Z = 2, with the whole molecule being the asymmetric unit. The compound has extensive π-π interactions along c-axis between the phenyl ring and the pyridyl ring at a distance of ~3.7 A?. In addition, the crystal also has a nearly linear intermolecular N-H···N hydrogen bond at a relatively short distance of 1.96 A?. Graphical Abstract: The title compound has extensive π-π interactions along c-axis between phenyl ring and the pyridyl ring at a distance of ~3.7 A?. In addition, the crystal also has a nearly linear intermolecular N-H···N hydrogen bond at a relatively short distance of 1.96 A?. Packing diagram of the title compound along c-axis showing π-π stacking.[Figure not available: see fulltext.]

Full text of DOI:10.1007/s10870-013-0436-8

J Chem Crystallogr (2013) 43:409–411
DOI 10.1007/s10870-013-0436-8
ORIGINAL PAPER
Synthesis and Crystal Structure of 4-(tert-butyl)-N-(pyridin-3-
ylmethyl) benzenesulfonamide
•
K. Balu R. Srinivasa Gopalan
Received: 28 February 2013 / Accepted: 10 July 2013 / Published online: 20 July 2013
Ó Springer Science+Business Media New York 2013
Abstract Reaction between 4-tert-butylphenyl sulfonyl
chloride and 3-picolylamine in presence of triethylamine
lead to the formation of 4-(tert-butyl)-N-(pyridin-3-ylme-
thyl) benzenesulfonamide. This compound crystallized in a
triclinic space group, P-1, with cell parameters a = 6.7945
(2), b = 7.1791 (3), c = 17.1267 (7), a = 96.153 (1),
b = 100.573 (2), c = 98.911 (2) and Z = 2, with the
whole molecule being the asymmetric unit. The compound
has extensive p–p interactions along c-axis between the
and the crystal structure of the copper complex. In this
paper, we report the synthesis and crystal structure of the
meta isomer, 4-(tert-butyl)-N-(pyridin-3-ylmethyl) ben-
zenesulfonamide. Similar compounds containing benzyl
sulfonamides have been reported in literature [7].
Materials and Methods
˚
phenyl ring and the pyridyl ring at a distance of *3.7 A. In
addition, the crystal also has a nearly linear intermolecular
Chemicals
N–HÁÁÁN hydrogen bond at a relatively short distance of
n-hexane, ethyl acetate, ethanol, dichloromethane, sodium
sulphate (anhydrous) were procured from Merck, India
with purity [97 %. 3-picolylamine and 4-tert-butyl sulfo-
nyl chloride were purchased from Sigma-Aldrich. Standard
laboratory grade silica gel (230–400 mesh) was obtained
from SRL, India. All reagents were used as received
without further purification.
˚
1.96 A.
Keywords Crystal structure Á p–p interactions Á N–HÁÁÁN
hydrogen bond
Introduction
Synthesis of 4-(tert-butyl)-N-(pyridin-3-ylmethyl)
Several scientists have studied oxidative DNA cleavage by
metal complexes [1–5]. Owing to the fact that all these
complexes show their own selectivity for a cleavage
mechanism, the design of new DNA cleavage agents is of
great interest.
benzenesulfonamide
To an ethanolic solution of 4-tert-butylphenyl sulfonyl
chloride (0.97 g, 4 mmol), triethylamine (0.5 g, 5 mmol),
and then 3-picolylamine (0.54 g, 5 mmol in ethanol, 2 ml)
was added slowly in drops. The solution was stirred at 40 °C
for 3 h (Scheme 1). After completion of the reaction, the
reaction mixture was filtered, concentrated, dissolved in
dichloromethane (25 ml) and washed with distilled water
(10 ml). The solution was dried again with anhydrous
sodium sulfate, filtered and concentrated. The crude material
was purified by column chromatography using hexane–ethyl
acetate. The formed compound was characterized using
proton NMR. [1H NMR (200 MHz,CDCl3): 8.41 (m,
2H, Ar–H),7.73 (d, 2H, J = 8.4 Hz, Ar–H),7.62 (d, 1H,
One of the most interesting aspect on this research is
developing is the influence of the ligands on the nuclease
activity of the complexes. In this context, Macias et al. [6]
have earlier reported the synthesis of sulfonamides from
2-picolylamine and 4-tert-butylbenzene sulfonyl chlorides
K. Balu Á R. S. Gopalan (&)
Unilever R&D Bangalore, 64, Main Road, Whitefield P.O.,
Bangalore 560 066, India
e-mail: srinivasa.gopalan@unilever.com
123

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J Chem Crystallogr (2013) 43:409–411
Scheme 1 Synthesis of 4-(tert-
butyl)-N-(pyridin-3-ylmethyl)
benzenesulfonamide
˚
J = 7.9 Hz, Ar–H), 7.45 (d, 2H, J = 8.4 Hz, Ar–H), 7.20
(m, 1H, Ar–H), 5.71 (t, 1H, –NH), 4.12 (d, 2H, J = 6.2 Hz,
–CH2), 1.31 (s, 9H, –CH3)].
monochromator for the Mo-Ka radiation (k = 0.71071 A).
The crystal structure was solved by direct methods using
the SHELXTL program [8] and refined by full matrix least
squares on F2. All non-hydrogen atoms were refined
anisotropically. Hydrogen atoms were fixed using HFIX
and were refined isotropically. Hydrogen bond analysis
was carried out using the PLATON routine [9]. Crystal
structure data of the complex is given in Table 1.
Single crystals were grown by dissolving 100 mg of the
compound in 1 ml of hot isopropyl alcohol and allowing it
to grow at room temperature for 2 weeks. The crystals
obtained were examined under an optical microscope and
high quality crystals suitable for single-crystal diffraction
were separated out. X-ray diffraction intensities were
measured at room temperature (293 K) on a Bruker
AXS kappa apex2 CCD diffractometer using a graphite
CCDC 926757 contains the supplementary crystallo-
graphic data for this complex. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/data_request/cif or
by emailing data_request@ccdc.cam.ac.uk, or by contacting
The Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB2 1EZ, UK; fax: ?44 1223 336033.
Table 1 Crystal data and structure refinement for 4-(tert-butyl)-N-
(pyridin-3-ylmethyl) benzenesulfonamide
Empirical formula
C16H20N2O2S
Formula weight
T (K)
304.40
298 (2)
0.71073
Triclinic
P-1
Results and Discussion
˚
Wavelength (A)
The compound, 4-(tert-butyl)-N-(pyridin-3-ylmethyl) ben-
zenesulfonamide crystallized in a triclinic space group,
P-1, with cell parameters a = 6.7945 (2), b = 7.1791 (3),
c = 17.1267 (7), a = 96.153 (1), b = 100.573 (2),
c = 98.911 (2) and Z = 2, with the whole molecule being
the asymmetric unit (see Fig. 1).
Crystal system
Space group
Unit cell dimensions
˚
a (A)
6.7945 (2)
7.1791 (3)
17.1267 (7)
96.153 (1)
100.573 (2)
98.911 (2)
2
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
Z
3
˚
Volume (A )
803.37 (5)
1.258
qcalc (Mg/m3)
l (mm-1
)
0.207
F(000)
324
Crystal size
0.35 9 0.30 9 0.30 mm3
2.44–25.00
-7 B h B 8
-8 B k B 8
-20 B l B 20
h range for data collection (°)
hkl range
Reflections
Collected
14,217
Unique
2,826
Data/restraints/parameters
R (F) (I [ 2r)
wR (F2) (all data)
S
2826/37/228
0.0406
0.1107
Fig. 1 ORTEP diagram of the title compound with the atom
numbering scheme. Displacement ellipsoids are drawn at 50 %
probability level
1.031
3
˚
Max./min. Dq (e/A )
0.164/-0.273
123

J Chem Crystallogr (2013) 43:409–411
411
phenyl and the pyridyl groups are almost perpendicular to
˚
each other with distance between them being[4.5 A. This
clearly indicates absence of any p–p interactions in the
reported structure.
In addition to this p–p stacking in the molecule under
study, there exists a hydrogen bonding between amidic N–H
and pyridyl nitrogen. This hydrogen bond is nearly linear
˚
(\N–HÁÁÁN = 169°) and has a length of 1.96 A.
Conclusions
The molecule under study shows interesting p–p stacking
and hydrogen bonding pattern in crystal structure. The p–p
stacking is quite extensive and exists within the molecule
as well as between adjacent molecules along c-axis. This
stacking is quite different to that found in a similar com-
pound reported in literature. We presume that it is this kind
of p–p stacking and hydrogen bonding that is responsible
for the structure formed.
Acknowledgments The authors would like to acknowledge the
reviewers for valuable inputs.
Fig. 2 Packing diagram of the title compound along c-axis showing
p–p stacking
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˚
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˚
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123