4-[3-(3,4-dimethoxyphenyl)prop-2-enoyl]phenyl methacrylate and 4-[3-(2-bromophenyl)prop-2-enoyl]phenyl methacrylate.

Article abstract of DOI:10.1107/S0108270101018273

Chalcones (alpha,beta-unsaturated ketones) are effective antitumour agents. It has been proved that having halogen or methoxy groups substituted in various positions of the phenyl ring enhances the activity of chalcones many times. The title compounds, C2

Full text of DOI:10.1107/S0108270101018273

organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
The keto group is in the s-cis conformation in compounds
I) and (II), as can be seen from the C7ÐC8ÐC9ÐO1
torsion-angle values of 4.7 (3) for (I) and 7.2 (6) for (II).
The two phenyl rings make dihedral angles with the keto
(
ꢀ
ꢀ
ISSN 0108-2701
ꢀ
ꢀ
group of 8.5 (2) and 11.8 (1) for (I), and 4.8 (2) and 7.6 (2)
for (II). In general, the bond lengths in these conjugated
4
2
4
-[3-(3,4-Dimethoxyphenyl)prop-
-enoyl]phenyl methacrylate and
-[3-(2-bromophenyl)prop-2-enoyl]-
phenyl methacrylate
a
a
b
A. Jeyabharathi, M. N. Ponnuswamy, S. Nanjundan,
c
c
Hoong-Kun Fun, * Suchada Chantrapromma, ² Anwar
c
c
Usman and Ibrahim Abdul Razak
a
Department of Crystallography and Biophysics, University of Madras, Guindy
b
Campus, Chennai 600 025, India, Department of Chemistry, Anna University,
c
Chennai 600 025, India, and X-ray Crystallography Unit, School of Physics,
Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
Correspondence e-mail: hkfun@usm.my
systems are longer than the double bonds and shorter than
the single bonds. In both structures, the bond lengths agree
with reported values (Carpy et al., 1978). From the torsion
Received 18 July 2001
Accepted 30 October 2001
Online 22 December 2001
ꢀ
angle values C5ÐC4ÐC7ÐC8 = � 176.0 (2) , C4ÐC7ÐC8Ð
ꢀ
ꢀ
C9 = 177.5 (2) , C7ÐC8ÐC9ÐC10 = � 173.2 (2) and C8Ð
Chalcones (ꢀ,ꢁ-unsaturated ketones) are effective antitumour
agents. It has been proved that having halogen or methoxy
groups substituted in various positions of the phenyl ring
enhances the activity of chalcones many times. The title
compounds, C H O and C H BrO , respectively, were
ꢀ
C9ÐC10ÐC15 = � 167.2 (2) in (I), and C1ÐC6ÐC7ÐC8 =
ꢀ
ꢀ
1
70.6 (4) , C6ÐC7ÐC8ÐC9 = 178.9 (3) , C7ÐC8ÐC9Ð
ꢀ
ꢀ
C10 = � 173.8 (4) and C8ÐC9ÐC10ÐC11 = 8.1 (6) in (II), it
is clear that the unsaturated ketone system is not strictly
planar. This deviation from planarity affects the ꢂ-electron
conjugation. The H atoms at C7 and C8 are trans. The opening
2
1
20
5
19 15
3
chosen for crystallographic study in order to determine their
structures and conformations. In both compounds, the keto
group is in the s-cis conformation and is almost planar. There
are weak intramolecular interactions in both structures.
ꢀ
of the C4ÐC7ÐC8 angle to 129.5 (2) in (I) and the C6Ð
Comment
Chalcones possess multi-protecting, biochemical, antifungal,
antimalarial and antifertility activities. The carbonyl group is a
characteristic functional group in chalcones. In recent years,
the synthesis of polymers having a photosensitive functional
group has been an active ®eld of research in polymer science.
Monomers having structures similar to the title compounds,
Figure 1
The molecular structure of compound (I) drawn with 30% probability
displacement ellipsoids. H atoms are shown as small spheres of arbitrary
radii.
4
-[3-(3,4-dimethoxyphenyl)prop-2-enoyl]phenyl methacryl-
ate, (I), and 4-[3-(2-bromophenyl)prop-2-enoyl]phenyl meth-
acrylate, (II), have been polymerized in solution using free-
radical initiators (Balaji et al., 2000; Subramanian et al., 2001).
These polymers, containing an ꢀ,ꢁ-unsaturated carbonyl
group, undergo crosslinking upon irradiation with UV light or
an electron beam and are being used as photoresistors (Hyder
Ali & Srinivasan, 1997; Rehab & Salahuddin, 1999). These
photosensitive polymers ®nd application in the ®elds of inte-
grated circuit technology, printing technology and photocur-
able coatings (Nagamatzu & Inui, 1977).
Figure 2
The molecular structure of compound (II) drawn with 30% probability
displacement ellipsoids. H atoms are shown as small spheres of arbitrary
radii.
² Permanent address: Department of Chemistry, Faculty of Science, Prince of
Songkla University, Hat-Yai, Songkhla 90112, Thailand.
o26 # 2002 International Union of Crystallography
DOI: 10.1107/S0108270101018273
Acta Cryst. (2002). C58, o26±o28

organic compounds
ꢀ
Ê
separated by a distance of 2.211 (1) A (Tokuno et al., 1986).
C7ÐC8 angle to 127.3 (4) in (II) can be ascribed to the short
interatomic non-bonded interaction between atoms H8 and
This non-bonded interaction also produces an appreciable
twist about the C4ÐC7 bond for (I) and the C6ÐC7 bond for
(II), at the expense of the conjugation energy of the system.
The exocyclic angles about C10 reveal deviations from normal
Ê
H3 in (I), which are separated by a distance of 2.309 (2) A, and
the interaction between atoms H5 and H8 in (II), which are
ꢀ
trigonal values, with a larger C9ÐC10ÐC11 angle [124.1 (2)
ꢀ
for (I) and 123.5 (3) for (II)] and a smaller C9ÐC10ÐC15
ꢀ
ꢀ
angle [117.6 (2) for (I) and 118.1 (3) for (II)]. There are two
weak CÐHÁ Á ÁO intramolecular interactions in (I) and (II),
and one weak CÐHÁ Á ÁBr interaction in (II) (Tables 2 and 4).
Displacement-ellipsoid plots of the molecules of (I) and (II)
are shown in Figs. 1 and 2, respectively. Figs. 3 and 4 show the
packing of molecules of (I) and (II), viewed down the a axis in
each case.
Experimental
The syntheses of compounds (I) and (II) consist of two steps. 3,4-
Dimethoxystyryl 4-hydroxyphenyl ketone and 1-bromostyryl 4-hy-
droxyphenyl ketone were prepared by the Claissen±Schmidt
condensation of 3,4-dimethoxybenzaldehyde or 1-bromobenz-
aldehyde with 4-hydroxyacetophenone in aqueous alcohol.
Compounds (I) and (II) were then prepared by reacting 3,4-di-
0
0
methoxystyryl 4 -hydroxyphenyl ketone or 1-bromostyryl 4 -hy-
droxyphenyl ketone in methyl ethyl ketone with methacryloyl
chloride in the presence of triethylamine.
Compound (I)
Crystal data
Figure 3
Packing diagram of (I) viewed down the a axis.
�
3
C
21
H O
20 5
D
x
= 1.286 Mg m
r
M = 352.37
Cu Kꢀ radiation
Monoclinic, C2/c
Ê
Cell parameters from 25
re¯ections
a = 13.381 (2) A
Ê
ꢀ
b = 20.813 (2) A
Ê
c = 13.881 (2) A
ꢃ = 4.1±25.0
ꢄ = 0.75 mm
T = 293 (2) K
� 1
ꢀ
ꢁ
= 109.68 (1)
Ê
3
V = 3640.0 (8) A
Z = 8
Needle, colourless
0.3 Â 0.2 Â 0.2 mm
Data collection
Enraf±Nonius CAD-4
diffractometer
h = � 2 ! 16
k = 0 ! 25
!/2ꢃ scans
l = � 17 ! 16
3
3
2
812 measured re¯ections
549 independent re¯ections
444 re¯ections with I > 2ꢅ(I)
3 standard re¯ections
every 200 re¯ections
frequency: 120 min
intensity decay: <0.1%
R
int = 0.050
ꢀ
ꢃ
max = 72.0
Table 1
Selected geometric parameters (A, ) for (I).
Ê
ꢀ
C1ÐO4
O5ÐC2
O5ÐC20
O4ÐC21
C9ÐO1
1.362 (3)
1.363 (2)
1.413 (2)
1.426 (3)
1.231 (2)
C9ÐC8
1.475 (3)
1.344 (3)
1.408 (3)
1.197 (2)
O2ÐC16
O2ÐC13
C16ÐO3
O4ÐC1ÐC6
O4ÐC1ÐC2
C11ÐC10ÐC9
C15ÐC10ÐC9
124.93 (18)
115.32 (18)
124.07 (18)
117.59 (19)
O5ÐC2ÐC3
O5ÐC2ÐC1
C8ÐC7ÐC4
125.13 (17)
114.99 (17)
129.5 (2)
C15ÐC10ÐC9ÐC8
O1ÐC9ÐC8ÐC7
C10ÐC9ÐC8ÐC7
167.17 (19)
4.7 (3)
� 173.18 (19)
C9ÐC8ÐC7ÐC4
C5ÐC4ÐC7ÐC8
177.5 (2)
� 176.0 (2)
Figure 4
Packing diagram of (II) viewed down the a axis.
ꢁ
Acta Cryst. (2002). C58, o26±o28
A. Jeyabharathi et al.
21 20
C H O
5
and C19H15BrO
3
o27

organic compounds
Table 2
Short-contact geometry (A, ) for (I).
Table 4
Hydrogen-bonding geometry (A, ) for (II).
Ê
ꢀ
Ê
ꢀ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C7ÐH7Á Á ÁO1
0.93
0.93
2.42
2.34
2.784 (3)
2.685 (3)
103
101
C7ÐH7AÁ Á ÁBr1
C7ÐH7AÁ Á ÁO1
C18ÐH18CÁ Á ÁO2
0.93
0.93
0.93
2.71
2.44
2.37
3.175 (4)
2.781 (5)
2.700 (6)
112
101
100
C18ÐH18BÁ Á ÁO2
Re®nement
After checking their presence in a difference map, all H atoms
were ®xed geometrically and allowed to ride on their attached atoms
Ê
(CÐH = 0.93 and 0.96 A).
2
2
2
2
Re®nement on F
2
w = 1/[ꢅ (F
o
) + (0.0922P)
2
R[F > 2ꢅ(F )] = 0.054
wR(F ) = 0.163
S = 1.04
+ 0.6924P]
where P = (F + 2F )/3
o c
(Á/ꢅ)max < 0.001
Áꢆmax = 0.27 e A
Áꢆmin = � 0.22 e AÊ
2
2
2
For compound (I), data collection: CAD-4 Software (Enraf±
Nonius, 1989); cell re®nement: CAD-4 Software; data reduction: SDP
(Frenz, 1978); program(s) used to solve structure: SHELXTL
(Sheldrick, 1997); program(s) used to re®ne structure: SHELXTL;
molecular graphics: ZORTEP (Zsolnai, 1997); software used to
prepare material for publication: PARST (Nardelli, 1995) and
PLATON (Spek, 1990).
Ê
� 3
3
2
549 re¯ections
38 parameters
� 3
H-atom parameters constrained
Compound (II)
For compound (II), 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, PARST (Nardelli, 1995) and PLATON (Spek, 1990).
Crystal data
C
M
19
H
15BrO
= 371.22
Triclinic, P1
a = 7.5272 (3) A
3
Z = 2
�
3
r
D
x
= 1.502 Mg m
Mo Kꢀ radiation
Cell parameters from 4174
re¯ections
ꢃ = 1.8±29.5
ꢄ = 2.52 mm
T = 293 (2) K
Block, light yellow
0.44 Â 0.32 Â 0.12 mm
Ê
Ê
b = 10.1940 (4) A
Ê
c = 11.5780 (4) A
ꢀ
AJ thanks the University Grants Commission for the award
of a teacher fellowship under FIP. The authors would like to
thank the Malaysian Government and Universiti Sains
Malaysia for research grant R&D No. 305/PFIZIK/610942.
ꢀ
ꢀ
� 1
ꢀ
ꢁ
= 96.227 (1)
= 98.428 (1)
ꢀ
Ê
ꢇ = 108.763 (1)
V = 820.54 (5) A
3
Data collection
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: DA1204). Services for accessing these data are
described at the back of the journal.
Siemens SMART CCD area-
detector diffractometer
2840 independent re¯ections
2355 re¯ections with I > 2ꢅ(I)
!
scans
Absorption correction: empirical
SADABS; Sheldrick, 1996)
min = 0.404, Tmax = 0.752
721 measured re¯ections
Rint = 0.052
ꢀ
ꢃ
max = 25.0
(
T
h = � 8 ! 8
k = � 12 ! 8
l = � 13 ! 13
References
4
Balaji, R., Subramanian, K., Nanjundan, S. & Rami Reddy, A. V. (2000). J.
Appl. Polym. Sci. 72, 1412±1418.
Carpy, A., Leger, J. M. & Nuhrich, A. (1978). Cryst. Struct. Commun. 7, 361±
Re®nement
2
364.
Re®nement on F
2
H-atom parameters constrained
2
2
2
2
R[F > 2ꢅ(F )] = 0.056
wR(F ) = 0.146
S = 0.99
w = 1/[ꢅ (F
where P = (F
(Á/ꢅ)max < 0.001
o
) + (0.0895P) ]
Enraf±Nonius (1989). CAD-4 Software. Version 5.0. Enraf±Nonius, Delft, The
Netherlands.
2
2
2
o c
+ 2F )/3
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Japan.
Ê
� 3
2
2
840 re¯ections
09 parameters
Áꢆmax = 0.58 e A
Áꢆmin = � 1.08 e AÊ
� 3
Table 3
Selected geometric parameters (A, ) for (II).
Ê
ꢀ
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
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Wisconsin, USA.
Br1ÐC1
O1ÐC9
O2ÐC16
1.903 (4)
1.207 (5)
1.359 (5)
O2ÐC13
O3ÐC16
C7ÐC8
1.410 (5)
1.199 (5)
1.320 (5)
Siemens (1996). SAINT and SMART. Siemens Analytical X-ray Instruments
Inc., Madison, Wisconsin, USA.
Spek, A. L. (1990). Acta Cryst. A46, C-34.
C11ÐC10ÐC9
123.6 (3)
C15ÐC10ÐC9
118.2 (4)
Subramanian, K., Nanjundan, S. & Rami Reddy, A. V. (2001). Eur. Polym. J.
3
7, 691±698.
C1ÐC6ÐC7ÐC8
C6ÐC7ÐC8ÐC9
C7ÐC8ÐC9ÐO1
170.6 (4)
178.9 (3)
7.2 (6)
C7ÐC8ÐC9ÐC10
C8ÐC9ÐC10ÐC11
� 173.8 (4)
Tokuno, K., Mutsui, M., Miyoshi, F., Asao, Y. & Ohashi, T. (1986). Acta Cryst.
C42, 85±88.
Zsolnai, L. (1997). ZORTEP. University of Heidelberg, Germany.
8.1 (6)
ꢁ
o28 A. Jeyabharathi et al.
21 20
C H O
5
and C19H15BrO
3
Acta Cryst. (2002). C58, o26±o28