Crystal Structure of N-(2-Cyano-1-Phenylprop-2-en-1-yl)-4-Methylbenzenesulfonamide

Article abstract of DOI:10.1134/S0022476618050244

New allylsulfonamide is prepared in a four-step synthetic route: the Morita-Baylis-Hillman adduct prepared from benzaldehyde and acrylonitrile is acetylated using acetic anhydride and DMAP. The acetylated product reacts with DABCO displaced by the additio

Full text of DOI:10.1134/S0022476618050244

Journal of Structural Chemistry. Vol. 59, No. 5, pp. 1192-1194, 2018.
Original Russian Text © 2018 R. A. C. Souza, S. Guilardi, M. M. M. Rubinger, L. R. Terra, E. C. Tavares, J. A. Ellena.
CRYSTAL STRUCTURE OF N-(2-CYANO-1-
PHENYLPROP-2-EN-1-YL)-4-METHYLBENZENESULFONAMIDE
1 1
R. A. C. Souza , S. Guilardi *,
2
2
3
M. M. M. Rubinger , L. R. Terra , E. C. Tavares ,
4
and J. A. Ellena
New allylsulfonamide is prepared in a four-step synthetic route: the Morita-Baylis-Hillman adduct prepared
from benzaldehyde and acrylonitrile is acetylated using acetic anhydride and DMAP. The acetylated
product reacts with DABCO displaced by the addition of 4-methylbenzenesulfonamide. The final product is
characterized by high-resolution mass spectrometry, infrared, and NMR spectroscopic techniques. The
X-ray crystallographic method is used to determine the crystal structure and features of the molecular
structure of the compound.
DOI: 10.1134/S0022476618050244
Keywords: synthesis, X-ray crystallographic analysis, allylsulfonamide, Morita-Baylis-Hillman adduct.
INTRODUCTION
Several compounds bearing sulfonamide groups exhibit important biological properties, such as antitumor and
antimicrobial activities [1]. It has recently been discovered that allysulfonamides such as (Z)-N-(2-cyano-3-phenylprop-2-en-
1-yl)-benzenesulfonamide inhibit the growth of plant pathogenic fungi [2]. Here we present the synthesis of novel
allylsulfonamide bearing a terminal C=C double bond, aiming to study the influence of this structural change in the
antifungal activity of this group of substances. Thus, this paper discusses the synthesis, spectroscopic characterization, and
crystal structure determination of N-(2-cyano-1-phenylprop-2-en-1-yl)-4-methylbenzenesulfonamide.
EXPERIMENTAL
Synthesis. Morita-Baylis-Hillman aduct 2-[hydroxy(phenyl)methyl]acrylonitrile (1) was prepared from
benzaldehyde and acrylonitrile under trimethylamine catalysis, as described in the literature [3]. Compound 1 was acetylated
using acetic anhydride and 4-dimethylaminopyridine (DMAP), forming 2-cyano-1-phenylprop-2-en-1-yl acetate (2) [4].
A mixture of 1 mmol of 1,4-diazabicyclo[2.2.2]octane (DABCO) and 1 mmol of 2 in THF:H O 1:1 (6 ml) was stirred at room
2
temperature for 30 min. Then, 2 mmol of 4-methylbenzenesulfonamide and 2 mmol of triethylamine were added and the
mixture was stirred for further 8 h. The title product (3, 37% yield) was isolated upon extractions with CH Cl and purified
2 2
by column chromatography with silica gel (hexane/ethyl acetate 2:1). White crystals of 3 (m.p. 124.5-125.4 °С) suitable for
the X-ray crystallographic analysis were obtained by recrystallization from CHCl and petroleum ether.
3
1
2
Universidade Federal de Uberlândia, Uberlândia, Brazil; *silvana@ufu.br. Universidade Federal de Viçosa,
3
4
Viçosa, Brazil. Universidade Federal de Itajubá, Itajubá, Brazil. Universidade de São Paulo, São Carlos, Brazil. The text
was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 59, No. 5, pp. 1232-1234, June-July, 2018.
Original article submitted March 8, 2017.
1192
0022-4766/18/5905-1192 © 2018 by Pleiades Publishing, Ltd.

–1
Spectroscopic data. IR (ATR; ν , cm ): 3228, 2927, 2872, 2235, 1597, 1493, 1453, 1338, 1163, 1091, 1068, 968,
max
1
957, 945, 913, 857, 844, 818, 789, 745, 732, 703, 677, 582, 549. H NMR (300 MHz, CDCl ): δ 2.43 (s, 3H, CH ), 5.02-5.08
3
3
2 2
(m, 2H, NH and H-1), 6.00 (d, 1H, J = 1.0 Hz, H-9a), 6.07 (d, 1H, J = 1.0 Hz, H-9b), 7.07-7.15 (m, 1H, H-5), 7.26-
HH
HH
3 13
7.30 (m, 4H, H-3, H-4, H-6 and H-7), 7.30-7.33 (m, 2H, H-3′ and H-5′), 7.69-7.73 (d, 2H, J = 9.0 Hz, H-2′ and H-6′). C
HH
NMR (75 MHz, CDCl ): δ 21.6 (C-7′), 59.8 (C-1), 116.5 (C-8), 123.3 (CN), 126.8 (C-2′ and C-6′), 127.3 (C-4 and C-6),
3
129.1 (C-5), 129.3 (C-3′ and C-5′), 129.8 (C-3 and C-7), 131.8 (C-9), 136.1 (C-2), 136.7 (C-4′), 144.1 (C-1′). HR-ESI-MS
–
(anionic mode): Anal. Calcd. for C H N O S : 311.0854, Found: 311.0863.
17 15
2
2
X-ray crystallography. The X-ray diffraction data were collected on a Bruker APEX II-DUO diffractometer
equipped with a CCD area detector and a graphite monochromator with CuK radiation (λ = 0.54178 Å) at 273 K. APEX II
α
and SAINT software packages [5] were used for the unit cell determination, data collection and integration. The structure was
2
solved using direct methods and refined successfully using full-matrix least-squares on F with SHELXL-2014 [6] with
anisotropic atomic displacement parameters for non-hydrogen atoms. All hydrogen atoms were stereochemically positioned and
refined with the riding model. Absorption correction (GAUSSIAN) was applied for the compound using the SORTAV program [7].
The crystallographic data are as follows: chemical formula, M = 312.38, dimensions 0.344×0.262×0.262 mm,
3
monoclinic, P2 /n, а = 10.7646(3) Å, b = 11.1715(3) Å, с = 14.7311(4) Å, β = 109.7(1)°, V = 1667.5(1) Å , Z = 4,
1
3
–1
d
= 1.244 g/cm , μ = 1.790 mm , T /T = 0.578/0.651. The resulting values are: S = 1.072, R1 = 0.0681 for all 3423
min max
cal
reflections and R1 = 0.0569 for 2808 reflections with I > 2σ(I) and 212 refined parameters. The complete data of the X-ray
crystallographic analysis containing atomic coordinates, bond lengths, and bond angles have been deposited at the Cambridge
Crystallographic Data Centre (CCDC No. 1531585).
RESULTS AND DISCUSSION
–1 –1
Spectroscopic studies. The characteristic sulfonamide bands were observed at 3228 cm (νNH), 1338 cm , and
–1
1163 cm (νSO asymmetric and symmetric, respectively) in the IR spectrum of compound 3. The νCN band at 2235 cm
–1
2
–1 –1
was shifted to higher wavenumbers with respect to precursors 1 and 2 (2229 cm and 2228 cm , respectively). The expected
–1 1
disubstituted CH band was observed at 857 cm . In the H NMR spectrum of compound 3, the region between δ 7.07 and
2
7.73 showed four multiplets integrating an area of nine hydrogen atoms due to the aromatic rings. The most important
diagnostic signals were the singlet at δ 2.43 due to the methyl group and two coupled doublets (J = 1 Hz) of the methylidene
13
group at δ 6.00 and 6.07. The H1 and NH signals superimposed at ca. δ 5.05. The C NMR spectrum of compound 3 showed
all the expected signals. The C=CH signals were observed at δ 116.5 (C8) and 131.8 (C9), and the C1 signal at δ 129.8. The
2
methyl and nitrile signals appeared at δ 21.6 and 123.3, respectively. The remaining signals were assigned to the aromatic
carbon atoms.
X-ray structural description. Fig. 1a shows the ORTEP [8] drawing of the asymmetric unit of compound 3,
including the numbering scheme.
The C–C bond lengths in phenyl ring 1 (C1′ to C6′) range from 1.363(5) to 1.390(4) Å. The C4′–C7′ (1.571(4) Å)
distance is longer than the other observed values in correlated compounds [9, 10]. The sulfur atom exhibits a distorted
tetrahedral geometry (angles ranging from 105.3(1)° to 120.6(2)°), probably due to non-bonded intramolecular distances
O1–O2, O1–N1, O2–N1, O1–C1′, and O2–C1′, resulting in structures with less steric interferences. The S–C, S=O, S–N, and
N–C bond lengths present values similar to the other reported structures of sulfonamides [2, 10].
3
The C1–N1–S [121.9(2)°] angle is larger than the value expected for the sp hybrid character of the N1 atom. The
C1–C8 (1.518(3) Å) distance is consistent with the expected value for a single bond [11]. The C8–C10, C8=C9, and C10≡N2
distances are consistent with the values reported by the other authors [12]. The C–C in phenyl ring 2 (C2 to C7) and C1–C2
bond lengths are similar to the observed values in 2-chloro-2,3-diphenyl-3-(tosylamino)propionitrile [10].
The phenyl rings are essentially planar, with r.m.s.d. of 0.0042 Å (ring 1) and 0.0011 Å (ring 2) from the least-
squares plane defined by the atoms. The dihedral angles between these planes is 86.8(1)°. The deviation of the C1 atom to
1193

Fig. 1. ORTEP view of the compound with atom numbering scheme and displacement ellipsoids drawn at
a 30% probability level (a); structural packing in the b axis direction (b). Dashed lines indicate C–H⋯O,
N–H⋯N hydrogen bond and C–H⋯π interactions.
ring 1 is 0.0942(4) Å, the deviation of the C7′ and S atoms to ring 2 is 0.0027(6) Å and 0.0925(4) Å, respectively. The C1,
C8, C9, C10, N2 fragment is planar with r.m.s.d. of 0.0047 Å. The dihedral angles between this plane and rings 1 and 2 are
80.1(1)° and 30.1(1)°, respectively.
The crystal packing is stabilized by two C–H⋯O and one C–H⋯N intramolecular interactions. Furthermore, pairs
2
of N–H⋯N intermolecular interactions linking inversion dimers generate R (12) ring motifs [13] and C–H⋯O
2
intermolecular interactions connect these dimers forming chains in the b axis direction. The C–H⋯π interactions link these
chains along the a axis, forming a three-dimensional supramolecular network (Fig. 1b).
To summarize, a novel allylsulfonamide has been synthesized and its structure was investigated in this study. The
X-ray and the spectroscopic data proved that the position of the allylic double bond differs from the previously published
analogues [2], being external to the main carbon chain. Thus, it might be interesting to compare the biological activities of
these two different groups of allylsulfonamides.
This work was supported by the Brazilian agencies CAPES, FAPEMIG and CNPq.
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