N-Benzyl-2′-iodocinnamanilide and N-benzyl-2′-iodo-4′-methyl-2-phenyl-cinnamanilide

Article abstract of DOI:10.1107/S0108270199015243

The aromatic ring of the cinnamic moiety in N-benzyl-2′-iodocinnamanilide, C₂₂H₁₈INO, (I), and N-benzyl-2′-iodo-4′-methyl-2-phenylcinnamanilide, C₂₉H₂₄INO, (II), makes a dihedral angle with the iodophenyl ring o

Full text of DOI:10.1107/S0108270199015243

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
ISSN 0108-2701
N-Benzyl-20-iodocinnamanilide and
N-benzyl-20-iodo-40-methyl-2-phenyl-
cinnamanilide
S. Renganayaki,a E. Subramanian,a S. Shanmuga Sundara
Rajb and Hoong-Kun Funb*
Figure 1
aDepartment of Crystallography and Biophysics, University of Madras, Guindy
Campus, Chennai 600 025, India, and bX-ray Crystallography Unit, School of
Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
Correspondence e-mail: hkfun@usm.my
The structure of (I) showing 30% probability displacement ellipsoids and
the atom-numbering scheme. H atoms are drawn as small spheres of
arbitrary radii.
comparable with those reported in the literature (Elmali &
Elerman, 1997; Banerjee et al., 1994). Views of molecules (I)
and (II) can be seen in Figs. 1 and 2, respectively.
Received 4 November 1999
Accepted 24 November 1999
The widening of the C1ÐC7ÐC8 angle [128.1 (4)ꢀ] in (I) is
The aromatic ring of the cinnamic moiety in N-benzyl-20-
iodocinnamanilide, C22H18INO, (I), and N-benzyl-20-iodo-40-
methyl-2-phenylcinnamanilide, C29H24INO, (II), makes a
dihedral angle with the iodophenyl ring of 72.1 (2) and
81.0 (2)ꢀ in (I) and (II), respectively. In (I), molecules exist as
discrete components, while in (II), they form in®nite chains
along the b axis, through IÁ Á ÁO non-bonded interactions.
attributable to steric factors involving C2 and C8 [C2Á Á ÁC8 =
Ê
3.040 (6) A]. Steric repulsion between phenyl rings A and D in
(II) might contribute to further widening of this angle
[130.8 (4)ꢀ].
In both compounds, the phenylmethyl ring B and the
carbonyl group are synperiplanar (cis) to each other [O10Ð
C9ÐN11ÐC12 = 4.4 (6)ꢀ in (I) and 3.9 (6)ꢀ in (II)] and the
phenyl ring C is antiperiplanar (trans) to the carbonyl group,
with the O10ÐC9ÐN11ÐC19 torsion angle = 178.7 (4) in
(I) and 177.7 (4)ꢀ in (II). As seen from the torsion angle, the
ꢀ,ꢁ-unsaturated carbonyl unit has the s-cis conformation. The
dihedral angles between rings are A/B 62.0 (3), A/C 72.1 (2)
and B/C 60.7 (2) for (I), and 51.9 (3), 81.0 (2) and 48.0 (3)ꢀ,
respectively, for (II). In (II), rings C and D are in a syn
orientation, with an interplanar angle of 21.6 (2)ꢀ.
Comment
Cinnamoyl anilides are substrates for cyclization to biologi-
cally active ®ve-membered 2-oxindole derivatives and six-
membered 2-oxyquinolines by photochemical methods. ortho-
Iodinated anilides are used for the same reaction by electro-
chemical methods. The interest lies in the synthetic potential
of these iodinated compounds and those of other acyclamides,
which react with a wide range of nucleophilic compounds and
which therefore present new possibilities in the synthesis of
heterocyclic compounds (Augustin et al., 1980). We have
undertaken X-ray structure analysis of N-benzyl-20-iodo-
cinnamanilide (I) and N-benzyl-20-iodo-40-methyl-2-phenyl-
cinnamanilide (II) to identify conformational features that
favour cyclization.
In (I), the packing of the molecules is stabilized by CÐ
HÁ Á ÁO and van der Waals interactions, while in (II) the
The molecular geometry of the cinnamamide part of the
title compounds agrees well with their analogues, N-methyl-20-
nitrocinnamanilide (Subramanian et al., 1999) and N-(4-
chloro-2-iodophenyl)-N-methylcinnamamide (Renganayaki et
al., 1999), reported by our group, and with other reported
values (Iwamoto & Kashino, 1990; Iwamoto et al., 1989). The
Figure 2
The structure of (II) showing 30% probability displacement ellipsoids
and the atom-numbering scheme. H atoms are drawn as small spheres of
arbitrary radii.
Ê
CÐI distance [2.094 (4) in (I) and 2.101 (4) A in (II)] is
ꢁ
Acta Cryst. (2000). C56, 349±350
# 2000 International Union of Crystallography
Printed in Great Britain ± all rights reserved 349

organic compounds
Data collection
packing is also stabilized by additional IÁ Á ÁO interactions
1
2
1
2
Ê
[I1Á Á ÁO10( x + 1, y + , z + ) = 3.082 (3) A].
Siemens SMART CCD area-
detector diffractometer
! scans
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
Tmin = 0.674, Tmax = 0.897
19 536 measured re¯ections
6131 independent re¯ections
2831 re¯ections with I > 2ꢄ(I)
Rint = 0.093
ꢂmax = 28.53ꢀ
Experimental
h = 10 ! 14
k = 15 ! 14
For the preparation of (I) the following procedure was employed. To
a solution of o-iodoaniline (0.2 mol) and pyridine (0.2 mol) in dry
benzene (50 ml), cinnamoyl bromide (0.2 mol in hexane) was added
dropwise. The mixture was heated in a water bath at 333±343 K for
5 h and then poured into 80±100 ml of water. The benzene layer was
separated and washed repeatedly with water (3±4 times). The
benzene was dried with magnesium sulfate and then evaporated to
obtain the anilide. For the benzylation of the anilide, NaH (0.2 mol)
was taken in a round-bottomed ¯ask. A solution of anilide (0.2 mol)
in dry dimethylformamide (DMF; 50 ml) was added to the NaH. The
reaction mixture was stirred for 15 min, and then benzyl bromide was
added and stirred for 3 h. The reaction mixture was poured into
water, extracted with ethyl acetate and washed with water repeatedly
to remove the DMF, and the compound was recrystallized from di-
chloromethane. For the preparation of (II), the synthesis procedure
was the same as for (I), with ꢀ-phenylcinnamoyl bromide as the
starting material.
l = 26 ! 21
Intensity decay: none
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.057
wR(F2) = 0.102
S = 0.958
6131 re¯ections
289 parameters
H-atom parameters constrained
w = 1/[ꢄ2(Fo2) + (0.028P)2]
where P = (Fo2 + 2Fc2)/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.45 e A
3
Ê
0.79 e A
Áꢅmin
=
Table 1
Selected geometric parameters (A) for (I).
Ê
I1ÐC24
C9ÐN11
2.094 (4)
1.360 (5)
N11ÐC19
N11ÐC12
1.434 (4)
1.479 (5)
Table 2
Selected geometric parameters (A, ) for (II).
ꢀ
Ê
Compound (I)
I1ÐC24
C9ÐN11
2.101 (4)
1.370 (5)
N11ÐC19
N11ÐC12
1.426 (5)
1.478 (5)
Crystal data
C22H18INO
Mr = 439.27
Mo Kꢀ radiation
Cell parameters from 8192
re¯ections
C8ÐC7ÐC1
130.8 (4)
C7ÐC8ÐC26
125.8 (4)
Orthorhombic, Pbca
Ê
a = 17.7759 (3) A
ꢂ = 1.73±28.37ꢀ
1
Ê
b = 9.0661 (2) A
ꢃ = 1.693 mm
T = 293 (2) K
For both compounds, data collection: SMART (Siemens, 1996);
cell re®nement: SAINT (Siemens, 1996); data reduction: SAINT;
program(s) used to solve structure: SHELXTL (Sheldrick, 1997);
program(s) used to re®ne structure: SHELXTL; molecular graphics:
SHELXTL; software used to prepare material for publication:
SHELXTL and PLATON (Spek, 1990).
Ê
c = 23.5939 (3) A
3
Ê
V = 3802.35 (12) A
Plate, colourless
0.28 Â 0.14 Â 0.06 mm
Z = 8
Dx = 1.535 Mg m
3
Data collection
Siemens SMART CCD area-
detector diffractometer
! scans
Absorption correction: empirical
(SADABS; Sheldrick, 1996)
Tmin = 0.721, Tmax = 0.901
27 608 measured re¯ections
4666 independent re¯ections
2674 re¯ections with I > 2ꢄ(I)
Rint = 0.06
The authors thank M. Raja, Scientist, SPIC Science Foun-
dation, Chennai India, and Professor K. K. Balasubramanian,
Indian Institute of Technology, Madras, for the synthesis and
supply of the compounds. HKF thanks the Malaysian
Government and Universiti Sains Malaysia for research grant
R&D No. 305/p®zik/622004. SSSR thanks the Universiti Sains
Malaysia for a Visiting Postdoctoral Fellowship.
ꢂ
max = 28.31ꢀ
h = 23 ! 13
k = 11 ! 12
l = 31 ! 30
Intensity decay: none
Re®nement
Re®nement on F2
R[F2 > 2ꢄ(F2)] = 0.059
wR(F2) = 0.095
S = 1.091
4666 re¯ections
226 parameters
H-atom parameters constrained
w = 1/[ꢄ2(Fo2) + (0.023P)2 +
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: SK1348). Services for accessing these data are
described at the back of the journal.
2
2.0205P] where P = (Fo2 + 2Fc )/3
(Á/ꢄ)max = 0.001
3
Ê
Áꢅmax = 0.51 e A
3
Ê
1.21 e A
Áꢅmin
=
References
Augustin, M., Richter, M. & Sala, S. (1980). J. Prakt. Chem. 332, 55±68.
Banerjee, R., Das, K., Ganesh, V., Banerjee, P., Surolia, A. & Vijayan, M.
(1994). Acta Cryst. C50, 1726±1728.
Elmali, A. & Elerman, Y. (1997). Acta Cryst. C53, 791±793.
Iwamoto, T. & Kashino, S. (1990). Acta Cryst. C46, 686±688.
Iwamoto, T., Kashino, S. & Haisa, M. (1989). Acta Cryst. C45, 1110±1112.
Renganayaki, S., Subramanian, E., Shanmuga Sundara Raj, S. & Fun, H.-K.
(1999). Acta Cryst. C55, 1672±1673.
Sheldrick, G. M. (1996). SADABS. University of GoÈttingen, Germany.
Sheldrick, G. M. (1997). SHELXTL. Version 5.1. Bruker AXS Inc., Madison,
Wisconsin, USA.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments,
Inc., Madison, Wisconsin, USA.
Spek, A. L. (1990). Acta Cryst. A46, C-34.
Subramanian, E., Renganayaki, S., Shanmuga Sundara Raj, S. & Fun, H.-K.
(1999). Acta Cryst. C55, 764±766.
Compound (II)
Crystal data
3
C29H24INO
Mr = 529.39
Dx = 1.414 Mg m
Mo Kꢀ radiation
Monoclinic, P21=c
Cell parameters from 6014
re¯ections
Ê
Ê
a = 10.8150 (2) A
b = 11.3607 (2) A
ꢂ = 1.88±28.32ꢀ
1
Ê
c = 20.2477 (5) A
ꢃ = 1.308 mm
T = 293 (2) K
ꢁ = 91.271 (1)ꢀ
V = 2487.14 (9) A
Z = 4
3
Ê
Block, colourless
0.32 Â 0.18 Â 0.10 mm
ꢁ
350 S. Renganayaki et al. C22H18INO and C29H24INO
Acta Cryst. (2000). C56, 349±350