(E)-2-[2-(1-naphthyl)vinyl]-3-tosyl-2,3-dihydro-1,3-benzothiazole

Article abstract of DOI:10.1107/S0108270100006259

The title compound, C₂₆H₂₁NO₂S₂, which consists of a benzothiazole skeleton with α-naphthylvinyl and tosyl groups at positions 2 and 3, respectively, was prepared by palladiumcopper-catalyzed heteroannulation. T

Full text of DOI:10.1107/S0108270100006259

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
dihedral angles between the planar parts of A (atoms N, C8±
C13 and S2), B (atoms C17±C26) and C (atoms C1±C7) are
A/B 82 (1), A/C 112 (1) and B/C 131.5 (4)ꢁ. The maximum
deviation for an in-plane atom (C9) from the corresponding
ISSN 0108-2701
Ê
least-squares plane is 0.04 (8) A. The bond lengths and angles
observed for the heterocyclic ring in (II) are similar to those
reported for related structures (Miler-Srenger, 1973; Yeap et
al., 1991). The C13ÐS2ÐC14 angle of 91.0 (2)ꢁ indicates that
(E)-2-[2-(1-Naphthyl)vinyl]-3-tosyl-
2,3-dihydro-1,3-benzothiazole
Susim Maiti,a Monika Mukherjee,a* Bidisha Nandi,b
Madeleine Helliwellc and Nitya G. Kundub
aDepartment of Solid State Physics, Indian Association for the Cultivation of Science,
Jadavpur, Calcutta 700 032, India, bDepartment of Organic Chemistry, Indian
Association for the Cultivation of Science, Jadavpur, Calcutta 700 032, India, and
cDepartment of Chemistry, University of Manchester, Manchester M13 9PL, England
Correspondence e-mail: sspmm@mahendra.iacs.res.in
Received 21 March 2000
Accepted 25 April 2000
the S2 atom uses only the p orbital to form bonds with the C13
and C14 atoms, of which C13 is part of an aromatic ring and
C14 is sp3 hybridized. Consequently, the SÐC bond distances
in the heterocyclic ring [S2ÐC13 1.751 (4) and S2ÐC14
The title compound, C26H21NO2S2, which consists of a
benzothiazole skeleton with ꢀ-naphthylvinyl and tosyl groups
at positions 2 and 3, respectively, was prepared by palladium±
copper-catalyzed heteroannulation. The E con®guration of the
molecule about the vinyl C C bond is established by the
benzothiazole±naphthyl CÐCÐCÐC torsion angle of
177.5 (4)ꢁ. The ®ve-membered heterocyclic ring adopts an
Ê
1.838 (4) A] differ signi®cantly. The asymmetric nature of the
bonding of the C atoms (C8 and C14) is also re¯ected in the
difference between the two NÐC distances [NÐC8 1.426 (5)
Ê
and NÐC14 1.482 (5) A]. The bond distances and angles for
3
Ê
envelope conformation with the Csp atom 0.380 (6) A from
the tosyl and ꢀ-naphthylvinyl groups are within expected
ranges (Chiaroni et al., 1994; Dobson & Gerkin, 1996). A
comparison of the geometrical parameters of various hetero-
cyclic derivatives (Table 3) reveals that the conformation of
the ®ve-membered C3NS ring has a profound in¯uence on the
molecular dimensions. In compounds with a non-planar C3NS
ring, the SÐC and NÐC bond distances show greater asym-
metry compared with those having a planar C3NS ring.
Ê
the C2NS plane. The two SÐC [1.751 (4) and 1.838 (4) A] and
Ê
two NÐC [1.426 (5) and 1.482 (5) A] bond lengths in the
thiazole ring differ signi®cantly.
Comment
The benzothiazole system, (I), containing a heterocyclic ring
with sulfur and nitrogen as heteroatoms, is often used as an
antihypertensive, an anticoagulant and a calcium agonist
(Yamamoto et al., 1998). Substituted benzothiazolines ®nd
wide-ranging applications as ef®cient anticonvulsants, vaso-
dilators, blood platelet aggregation inhibitors (Ucar et al.,
1998) and antifungal agents (Kanoongo et al., 1990). As part of
our ongoing program on the synthesis and characterization of
new heterocyclic compounds of biological importance (Kundu
et al., 1999; Nandi & Kundu, 2000) and to build up a hierarchy
for such systems, the structure determination of (E)-2-[2-
(1-naphthyl)vinyl]-3-tosyl-2,3-dihydro-1,3-benzothiazole, (II),
was undertaken.
The E con®guration of the molecule of (II), which contains
a benzothiazole moiety (A) with ꢀ-naphthylvinyl (B) and tosyl
(C) substituents at the 2 and 3 positions, respectively, is
established by the torsion angle C14ÐC15ÐC16ÐC17 of
177.5 (4)ꢁ. The ®ve-membered thiazole ring (atoms N, C8,
C13, S2 and C14) displays an envelope conformation, with the
Figure 1
ZORTEP (Zsolnai, 1995) view of (II) with ellipsoids at the 50%
probability level.
Ê
C14 atom 0.380 (6) A from the least-squares plane through
Ê
the remaining endocyclic atoms (r.m.s deviation 0.006 A). The
ꢀ
992 # 2000 International Union of Crystallography
Printed in Great Britain ± all rights reserved
Acta Cryst. (2000). C56, 992±994

organic compounds
Table 2
Hydrogen-bonding and short-contact geometry (A, ).
Both sulfonyl-O atoms are involved in weak (CÐHÁ Á ÁO)
intermolecular hydrogen bonds with benzothiazole and
naphthyl C atoms (Table 2). In the solid state, the crystal
packing is stabilized by van der Waals interactions and a weak
intermolecular hydrogen bond.
ꢁ
Ê
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C10ÐH10Á Á ÁO1i
C12ÐH12Á Á ÁO1ii
C20ÐH20Á Á ÁO2iii
0.93
0.93
0.93
2.53
2.69
2.71
3.411 (6)
3.346 (6)
3.399 (6)
159
128
132
1
2
1 1
Symmetry codes: (i) 1 x; y; z; (ii) x; y 1; z; (iii)
x; y
;
2 2
z.
Experimental
A mixture of 3-(2-aminophenylthio)prop-1-yne (3.67 mmol) and
1-iodonaphthalene (4.4 mmol) in acetonitrile (5 ml) was stirred at
room temperature for 24 h under a nitrogen atmosphere in the
presence of (PPh3)2PdCl2 (0.11 mmol), CuI (0.22 mmol) and
triethylamine (14.68 mmol). The resultant product after tosylation
with p-TsCl (1.2 equivalents) in the presence of pyridine (2.0
equivalents) in dichloromethane was cyclized with CuI (40 mole%) in
triethylamine (4.0 equivalents) by re¯uxing in tetrahydrofuran
(10 ml) for 36 h under an argon atmosphere to afford (II), which was
puri®ed by column chromatography on silica gel (60±120 mesh) using
5% ethyl acetate as eluant in light petroleum (333±353 K) (yield 63%,
m.p. 452±453 K). Single crystals suitable for X-ray analysis were
obtained by slow crystallization from a solution of (II) in a mixture of
light petroleum (333±353 K) and ether (3:1).
Table 3
Geometric parameters (A) of heterocyclic compounds containing the
C3NS ring.
Ê
Compound
C3NS ring
conformation
D²
SÐC
NÐC
a
C15H9Cl2NS2
planar
1.739 (4)
1.760 (4)
1.732 (2)
1.747 (2)
1.739 (3)
1.754 (3)
1.751 (8)
1.861 (9)
1.751 (8)
1.861 (9)
1.748 (2)
1.846 (2)
1.751 (4)
1.838 (4)
1.297 (5)
1.384 (5)
1.397 (2)
1.297 (2)
1.398 (3)
1.299 (3)
1.370 (9)
1.490 (9)
1.370 (3)
1.464 (4)
1.388 (3)
1.463 (3)
1.426 (5)
1.482 (5)
C
13H9NOSb
planar
C11H8N2Sc
planar
d
e
C
C
18H18N2S2
envelope
envelope
envelope
envelope
0.409 (12)
0.288 (1)
0.322 (2)
0.380 (6)
18H20N2S2
C11H13NOSf
Crystal data
g
3
C
26H21NO2S2
C26H21NO2S2
Mr = 443.56
Monoclinic, P21=n
Ê
a = 10.006 (4) A
Dx = 1.336 Mg m
Cu Kꢀ radiation
Cell parameters from 20
re¯ections
² Deviation of C atom bonded to S and N atoms from C2NS plane. References: (a) Yang
Â
et al. (1995); (b) Teo et al. (1995); (c) Davidovic et al. (1999); (d) Miler-Srenger (1969);
(e) Miler-Srenger (1973); (f) Yeap et al. (1991); (g) present work.
Ê
b = 8.543 (3) A
ꢂ = 14.4±16.4ꢁ
ꢃ = 2.371 mm
T = 296.2 K
1
Ê
c = 26.09 (1) A
ꢁ = 98.52 (4)ꢁ
V = 2205 (1) A
Z = 4
3
Ê
Prismatic, colourless
0.30 Â 0.30 Â 0.20 mm
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.069
wR(F2) = 0.225
S = 1.012
4476 re¯ections
w = 1/[ꢄ2(Fo2) + (0.1300P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max = 0.021
Data collection
Rigaku AFC-5R diffractometer
!±2ꢂ scans
Absorption correction: empirical
(North et al., 1968)
Tmin = 0.5365, Tmax = 0.6485
4742 measured re¯ections
4476 independent re¯ections
2609 re¯ections with I > 2ꢄ(I)
Rint = 0.039
max = 78.26ꢁ
ꢂ
3
Ê
Áꢅmax = 0.44 e A
h = 12 ! 11
3
Ê
0.70 e A
Áꢅmin
=
k = 8 ! 10
282 parameters
H-atom parameters constrained
l = 33 ! 32
3 standard re¯ections
every 150 re¯ections
intensity decay: 4.20%
The H atoms were re®ned using a riding model and their isotropic
displacement parameters were set to 1.2 times (1.5 times for CH3
groups) the equivalent displacement parameters of their parent
atoms.
Table 1
Selected geometric parameters (A, ).
ꢁ
Ê
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1994); cell re®nement: MSC/AFC
Diffractometer Control Software; data reduction: TEXSAN (Mole-
cular Structure Corporation, 1995); program(s) used to solve struc-
ture: MULTAN88 (Debaerdemaeker et al., 1988); program(s) used to
re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ZORTEP (Zsolnai, 1995); software used to prepare material for
publication: SHELXL97.
S1ÐO2
S1ÐO1
S1ÐN
S1ÐC7
S2ÐC13
S2ÐC14
1.423 (3)
1.426 (3)
1.649 (4)
1.750 (5)
1.751 (4)
1.838 (4)
NÐC8
NÐC14
C14ÐC15
C15ÐC16
C16ÐC17
1.426 (5)
1.482 (5)
1.492 (6)
1.297 (6)
1.465 (6)
O2ÐS1ÐO1
O2ÐS1ÐN
O1ÐS1ÐN
O2ÐS1ÐC7
O1ÐS1ÐC7
NÐS1ÐC7
119.7 (2)
106.2 (2)
106.1 (2)
109.4 (2)
107.1 (2)
107.9 (2)
91.0 (2)
C13ÐC8ÐN
113.4 (3)
113.0 (3)
110.5 (4)
105.5 (3)
112.2 (3)
123.6 (4)
128.6 (4)
C8ÐC13ÐS2
NÐC14ÐC15
NÐC14ÐS2
C15ÐC14ÐS2
C16ÐC15ÐC14
C15ÐC16ÐC17
C13ÐS2ÐC14
C8ÐNÐC14
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1385). Services for accessing these data are
described at the back of the journal.
111.8 (3)
C14ÐC15ÐC16ÐC17
177.5 (4)
ꢀ
Acta Cryst. (2000). C56, 992±994
Susim Maiti et al. C26H21NO2S2 993

organic compounds
Molecular Structure Corporation (1995). TEXSAN. Version 1.7. MSC, 3200
Research Forest Drive, The Woodlands, TX 77381, USA.
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ꢀ
994 Susim Maiti et al. C26H21NO2S2
Acta Cryst. (2000). C56, 992±994