Crystal-to-crystal photodimerization of trans-cinnamamides

Article abstract of DOI:10.1107/S0108768100002329

In the crystals of trans-4-methylcinnamamide, C₁₀H₁₁NO (I), trans-4-chlorocinnamamide, C₉H₈ClNO (II), trans-3-(2-thienyl)acrylamide, C₇H₇NOS (III), and trans-cinnamamide, C₉H₉NO (IV), the shortest intermolecular C...C distances between the C=C double bonds are 3.670 (2), 3.632 (2), 3.762 (3) and 4.120 (2) A, respectively, for the pair of molecules related by a center of symmetry. The structure analysis was also carried out for trans-2-(p-chlorophenyl)-cis-4-(p-chlorophenyl)-1-trans-3-diamidocyclobutane, C₁₈H₁₆Cl₂-N₂O₂ (V), which is the α-type photodimer of (II). The N -H...O hydrogen-bond networks in (I)-(III) are composed of two-dimensional pleated sheets, and those in (IV) and (V) of one-dimensional flat ribbons. The single crystals of (I), (II) and (IV) were photoirradiated with a 250 W ultra-high-pressure mercury lamp through a band-pass filter or a long-pass filter for 2-5 h. The photodimer was produced in each crystal with retention of the single-crystal form. The populations of the dimers were converged to 86.2 (4), 48.4 (6) and 4.5 (2)% in the refinement of the crystals after photoirradiation, (I′), (II′) and (IV′), respectively. Although the intermolecular N-H...O hydrogen-bond network remained in (I′) and (II′), the network was partly broken in (IV′) in the process of photoreaction.

Full text of DOI:10.1107/S0108768100002329

research papers
Acta Crystallographica Section B
Structural
Crystal-to-crystal photodimerization of
Science
trans-cinnamamides
ISSN 0108-7681
a
Received 22 July 1999
Accepted 8 February 2000
Hiroyuki Hosomi, Yoshikatsu
In the crystals of trans-4-methylcinnamamide, C H NO (I),
10 11
b
a
Ito and Shigeru Ohba *
trans-4-chlorocinnamamide, C
nyl)acrylamide, C H NOS (III), and trans-cinnamamide,
H ClNO (II), trans-3-(2-thie-
9 8
7
7
C H NO (IV), the shortest intermolecular CÁ Á ÁC distances
9
9
a
Department of Chemistry, Faculty of Science
between the C C double bonds are 3.670 (2), 3.632 (2),
Ê
.762 (3) and 4.120 (2) A, respectively, for the pair of
and Technology, Keio University, Hiyoshi 3,
Kohoku-ku, Yokohama 223-8522, Japan, and
3
molecules related by a center of symmetry. The structure
b
Department of Synthetic Chemistry and
Biological Chemistry, Faculty of Engineering,
Kyoto University, Kyoto 606-8501, Japan
analysis was also carried out for trans-2-(p-chlorophenyl)-cis-
4
-(p-chlorophenyl)-1-trans-3-diamidocyclobutane, C H Cl -
18 16 2
N O (V), which is the ꢀ-type photodimer of (II). The NÐ
2
2
HÁ Á ÁO hydrogen-bond networks in (I)±(III) are composed of
two-dimensional pleated sheets, and those in (IV) and (V) of
one-dimensional ¯at ribbons. The single crystals of (I), (II)
and (IV) were photoirradiated with a 250 W ultra-high-
pressure mercury lamp through a band-pass ®lter or a long-
pass ®lter for 2±5 h. The photodimer was produced in each
crystal with retention of the single-crystal form. The popula-
tions of the dimers were converged to 86.2 (4), 48.4 (6) and
Correspondence e-mail: ohba@chem.keio.ac.jp
4
tion, (I ), (II ) and (IV ), respectively. Although the inter-
.5 (2)% in the re®nement of the crystals after photoirradia-
0
0
0
molecular NÐHÁ Á ÁO hydrogen-bond network remained in
0 0 0
I ) and (II ), the network was partly broken in (IV ) in the
process of photoreaction.
(
1
. Introduction
Solid-state [2 + 2] photodimerization of trans-cinnamic acids
was extensively investigated by Schmidt and coworkers to
establish the topochemical principles (Cohen & Schmidt, 1964;
Cohen et al., 1964; Schmidt, 1964). The crystal structures and
hydrogen-bond networks of the trans-cinnamamide (IV) and
the 4-chloro derivative (II) were also investigated (Rabino-
vich, 1969; Leiserowitz & Schmidt, 1969) as well as the [2 + 2]
photoreaction of (I)±(III) (Hung et al., 1972). An exposure of
a single-crystal of (IV) to sunlight deformed the X-ray
diffraction peaks, suggesting lattice distortion owing to
photoreaction (Osaki & Schmidt, 1972). The photoreactivities
of (I)±(IV) redetermined in the present study are shown in
Table 1. The yields of ꢀ-type dimers of (I)±(III) were 97±100%
after photoirradiation for 20 h. On the other hand, the yield of
the dimer was only 18% for (IV). The CÁ Á ÁC distance between
Ê
the C C double bonds in (IV) was reported to be 4.109 (4) A
(Iwamoto et al., 1989), which is almost the maximum limit for
the solid-state reaction. Moreover, the intermolecular NÐ
HÁ Á ÁO hydrogen-bond network in (IV) is different from that
in (II). The hydrogen-bond networks in (I) and (III) are
expected to be similar to that of (II) (Leiserowitz & Schmidt,
1969).
#
2000 International Union of Crystallography
Printed in Great Britain ± all rights reserved
6
82 Hosomi et al. ꢀ trans-Cinnamamides
Acta Cryst. (2000). B56, 682±689

research papers
Table 1
Photoreactivities of trans-cinnamamides in the solid state.
(III): An orientational disorder of the
thiophene ring was treated according to
the convenient method by Pelletier &
Brisse (1994), assuming that the S1 and
C10* atoms (and the S1* and C10 atoms)
share the same positional and displace-
ment parameters. The site occupation
factor of S1 was re®ned to 0.825 (3). The
positional parameters of the H10 and
H10* atoms were calculated and ®xed
with Uiso (H) = 1.2Ueq (parent atom).
Compound
(I)
(II)
(III)
(IV)
Aromatic moiety
Radiation time (h)²
Product yield (%)³
4-Me-Ph
20
100
4-Cl-Ph
20
100
2-Thienyl
20
97
Ph
20
18
²
Powdered crystals were spread between two Pyrex plates and irradiated with a 400 W high-pressure mercury lamp
under an argon stream at room temperature. ³ Only the ꢀ-truxillamides were obtained. The yields were estimated by
NMR spectra.
A single-crystal-to-single-crystal transformation is an
excellent method to observe in situ the reactions in the solid
state (Suzuki, 1996; Tokitoh et al., 1998; Hosomi et al., 1998;
Leibovitch et al., 1998; Harada et al., 1999; Hosomi et al., 2000,
Other H atoms were re®ned isotropically.
0
Structure (I ): A single crystal of (I) was photoirradiated
with the 250 W ultra high-pressure Hg lamp through a band-
pass ®lter BP365 (T = 50% at 365 nm, half-height width
10 nm). The photoreaction was followed by measuring the
lattice constants repeatedly on a four-circle diffractometer.
The ꢁvalue increased continuously and became obtuse from
ꢁ
acute [87.69 (2) ]. The X-ray diffraction ability of the crystal
decreased as the reaction proceeded and the X-ray measure-
ment became impossible after photoirradiation for 10 h. To
ensure suf®cient resolution of the structure analysis, several
crystals were photoirradiated for 5 h and X-ray intensities
were measured on a crystal whose typical peak half-width was
ꢁ
0
8
.45 . The population of the dimer was converged to
6.2 (4)%, and that of the monomer to 13.8 (4)%. The posi-
and references therein). Photoirradiation far into the long
wavelength absorption tail is effective for protecting the single
crystals from degradation by the photoreaction (Enkelmann et
al., 1993; Novak et al., 1993). This technique has been applied
to the [2 + 2] photodimerization of trans-cinnamamides to see
whether the photoreaction proceeds keeping the inter-
molecular hydrogen bonds.
tional and isotropic displacement parameters of the atoms of
the monomer were ®xed to the corresponding values of (I).
For the dimer, the non-H atoms were re®ned anisotropically.
Structure (II ): A single crystal of (II) was photoirradiated
for 6 h with a 250 W ultra-high-pressure Hg lamp through a
0
2. Experimental
trans-4-Chlorocinnamamide (II) and trans-cinnamamide (IV)
were commercially available. trans-4-Methylcinnamamide (I)
and trans-3-(2-thienyl)acrylamide (III) were prepared
according to the method reported (Hung et al., 1972; Mason &
Nord, 1951). The ꢀ-type photodimer (V) was prepared by the
solid-state reaction of (II). The crystals were grown by slow
evaporation from ethanol (I), 2-propanol/ethanol (II),
methylene chloride (III) and chloroform (IV)±(V) solutions.
Crystal data, experimental conditions and re®nement
1
details are listed in Table 2. Absorption corrections were
made by integration from crystal shape (Coppens et al., 1965)
for (II)±(III), and by -scan for (V) (North et al., 1968).
Selected bond distances and angles are listed in Table 3, and
the hydrogen-bonding geometry in Table 4.
Structure (I): There is a rotational disorder of the methyl-H
atoms. Two sets of positions [H12A/H12C and H12*A/H12*C]
were assumed with site occupancy factor 50% each. Structure
Figure 1
(a) The structure of a pair of molecules in (I) related by a center of
symmetry; (b) the disordered structure in (I ) which consists of the
monomer (open bonds) 13.8 (4)% and the dimer (solid bonds) 86.2 (4)%.
Displacement ellipsoids are plotted at the 30% probability level. H atoms
are shown as spheres of arbitrary size.
0
1
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: OA0024). Services for accessing these data are described
at the back of the journal.
Acta Cryst. (2000). B56, 682±689
Hosomi et al. ꢀ trans-Cinnamamides 683

research papers
Table 2
Experimental details.
Atomic scattering factors were taken from International Tables for Crystallography (1992, Vol. C). For all compounds, data collection and cell re®nement:
MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); data reduction: TEXSAN (Molecular Structure Corporation, 1999); program
used to solve structure: SIR92 (Altomare et al., 1994); program used to re®ne structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for
publication: TEXSAN and ORTEPII (Johnson, 1976).
0
0
(I)
(I )
(II)
(II )
(III)
Crystal data
Chemical formula
Chemical formula weight
Cell setting
C H NO
11
C H NO
10 11
161.20
Monoclinic
C2=c
22.444 (1)
9.557 (2)
8.632 (1)
94.50 (1)
1845.9 (5)
8
C H ClNO
8
181.62
Monoclinic
C H ClNO
8
181.62
Monoclinic
C H NOS
7
1
0
9
9
7
161.20
Monoclinic
C2=c
23.599 (3)
9.148 (3)
8.208 (3)
87.69 (2)
1770.5 (8)
8
153.20
Orthorhombic
Pbca
20.243 (3)
9.087 (2)
8.137 (2)
90
1496.9 (4)
8
1.359
Mo Kꢀ
0.71073
25
14.3±14.9
0.357
298 (1)
Plate-like
0.7 Â 0.3 Â 0.05
Colorless
Space group
Ê
P2 =c
P2 =c
1
1
a (A)
Ê
11.037 (1)
9.075 (2)
9.042 (2)
108.42 (1)
859.3 (2)
4
11.398 (3)
9.330 (4)
8.698 (3)
108.95 (2)
874.8 (5)
4
b (A)
Ê
c (A)
ꢁ
ꢁ
V (A )
ꢂ †
Ê
3
Z
D (Mg m
�
3
)
Radiation type
1.209
1.160
1.404
1.379
x
Mo Kꢀ
0.71073
25
13.2±15.0
0.079
298 (1)
Plate-like
0.8 Â 0.5 Â 0.2
Colourless
Mo Kꢀ
0.71073
25
12.0±14.6
0.075
298 (1)
Plate-like
0.7 Â 0.4 Â 0.2
Colourless
Mo Kꢀ
0.71073
25
12.2±14.8
0.390
298 (1)
Plate-like
0.6 Â 0.6 Â 0.1
Colourless
Mo Kꢀ
0.71073
25
10.7±14.8
0.383
298 (1)
Plate-like
0.6 Â 0.6 Â 0.1
Colourless
Ê
Wavelength (A)
No. of re¯ections for cell parameters
ꢁ
ꢂrange ( )
�
1
ꢃ(mm
)
Temperature (K)
Crystal form
Crystal size (mm)
Crystal colour
Data collection
Diffractometer
Data collection method
Absorption correction
Tmin
Rigaku AFC-7R
Rigaku AFC-7R
ꢂ±2ꢂscans
None
Rigaku AFC-7R
ꢂ±2ꢂscans
Integration
0.799
0.961
2101
1977
1360
I >2ꢄ(I)
0.015
27.5
� 14 ! h ! 14
0 ! k ! 12
� 12 ! l ! 0
3
Every 150 re¯ec-
tions
Rigaku AFC-7R
!scans
Integration
0.812
0.962
2138
2006
1148
I >2ꢄ(I)
0.026
27.5
� 14 ! h ! 14
0 ! k ! 12
� 12 ! l ! 0
3
Rigaku AFC-7R
ꢂ±2ꢂscans
Integration
0.735
0.975
2476
2188
1074
I >2ꢄ(I)
0.024
30
� 14 ! h ! 28
0 ! k ! 12
0 ! l ! 11
3
Every 150 re¯ec-
tions
ꢂ±2ꢂscans
None
�
�
Tmax
�
�
No. of measured re¯ections
No. of independent re¯ections
No. of observed re¯ections
Criterion for observed re¯ections
Rint
2080
2034
2404
2128
1420
1294
I >2ꢄ(I)
0.030
27.5
I >2ꢄ(I)
0.017
27.5
0 ! h ! 29
� 12 ! k ! 5
� 11 ! l ! 11
3
ꢁ
ꢂmax ( )
Range of h, k, l
0 ! h ! 31
�
�
3
12 ! k ! 0
11 ! l ! 11
No. of standard re¯ections
Frequency of standard re¯ections
Every 150 re¯ec-
tions
Every 150 re¯ec-
tions
Every 150 re¯ec-
tions
Re®nement
Re®nement on
2
2
2
2
2
F
0.038
F
0.062
F
0.038
F
0.049
F
0.049
2
2
R‰F >2ꢄꢂF †Š
2
wRꢂF †
0.116
1.03
0.212
1.19
0.115
1.02
0.145
1.11
0.142
0.99
S
No. of re¯ections used in re®nement
No. of parameters used
H-atom treatment
2034
165
All H-atom para-
meters re®ned
2128
110
1977
141
All H-atom para-
meters re®ned
w = 1/[ꢄ(Fo
+ (0.0518P)
+ 0.3386P], where
2006
218
2188
116
H atoms: see text
H-atom parameters
not re®ned
w = 1/[ꢄ(Fo
+ (0.0648P)
+ 2.4674P], where
P = (Fo + 2F )/3
c
H-atom parameters
not re®ned
w = 1/[ꢄ(Fo
+ (0.0526P)
+ 0.2095P], where
P = (Fo + 2F )/3
c
2
2
2
2
2
2
2
2
2
2
Weighting scheme
w = 1/[ꢄ(Fo
)
)
2
)
2
)
2
w = 1/[ꢄ(F )
o
+ (0.0521P)
+ 0.5253P], where
2
2
+
+
(0.052P)
0.6818P], where
2
2
2
2
2
2
2
2
2
2
P = (Fo + 2F )/3
c
P = (Fo + 2F )/3
c
P = (Fo + 2F )/3
c
ꢂÁ=ꢄ†
0.0001
0.16
0.0001
0.30
0.0001
0.27
0.0001
0.15
0.0001
0.21
max
Ê
� 3
� 3
Áꢅ (e A
)
max
Ê
Áꢅmin (eA )
Extinction method
� 0.16
� 0.22
� 0.21
� 0.14
� 0.17
None
None
None
None
None
band-pass ®lter BP365. A peak half-width of X-ray diffrac-
ꢁ
non-H atoms of the dimer and monomer were re®ned
anisotropically.
Structure (IV ): Photoirradiation for several hours through
BP365 or UV36 (T = 15% at 350 nm) did not cause a signi®-
tion increased gradually from 0.47 to 0.70 . The populations
of the dimer and monomer were re®ned to 48.4 (6) and
0
5
1.6 (6)%, respectively. The positional parameters of all the
6
84 Hosomi et al. ꢀ trans-Cinnamamides
Acta Cryst. (2000). B56, 682±689

research papers
Table 2 (continued)
0
(IV)
(IV )
(V)
Crystal data
Chemical formula
Chemical formula weight
Cell setting
C H NO
9
147.18
Monoclinic
C H NO
9
147.18
Monoclinic
C H Cl N O
2
363.24
9
9
18 16
2
2
Triclinic
P1
8.733 (3)
18.578 (9)
5.210 (3)
91.86 (4)
93.04 (4)
93.21 (3)
842.2 (7)
2
Space group
Ê
P2 =a
P2 =a
1
1
a (A)
Ê
16.047 (2)
5.084 (2)
9.584 (2)
90
94.06 (1)
90
779.9 (3)
4
1.253
Mo Kꢀ
0.71073
25
16.191 (2)
5.079 (2)
9.509 (2)
90
93.37 (2)
90
780.7 (4)
4
1.252
Mo Kꢀ
0.71073
25
b (A)
Ê
c (A)
ꢁ
ꢀ
ꢁ
ꢂ †
ꢁ
ꢂ †
ꢁ
ꢆꢂ †
Ê
V (A )
3
Z
D (Mg m
�
3
)
Radiation type
1.432
x
Mo Kꢀ
0.71073
25
10.8±14.4
0.398
Ê
Wavelength (A)
No. of re¯ections for cell parameters
ꢁ
ꢂrange ( )
12.2±14.8
0.083
12.2±14.6
0.083
�
1
ꢃ(mm
)
Temperature (K)
Crystal form
298 (1)
Prism
298 (1)
Prism
298 (1)
Needle
Crystal size (mm)
Crystal colour
0.8 Â 0.3 Â 0.2
0.8 Â 0.3 Â 0.2
0.4 Â 0.1 Â 0.05
Colourless
Colourless
Colourless
Data collection
Diffractometer
Data collection method
Absorption correction
Tmin
Rigaku AFC-7R
Rigaku AFC-7R
ꢂ±2ꢂscans
None
Rigaku AFC-7R
ꢂ±2ꢂscans
scan
0.868
0.980
3320
2961
1393
I >2ꢄ(I)
0.029
25.0
0 ! h ! 10
� 22 ! k ! 22
� 6 ! l ! 6
3
ꢂ±2ꢂscans
None
�
�
Tmax
�
�
No. of measured re¯ections
No. of independent re¯ections
No. of observed re¯ections
Criterion for observed re¯ections
Rint
1857
1790
1859
1793
1259
1163
I >2ꢄ(I)
0.007
27.5
I >2ꢄ(I)
0.008
27.5
0 ! h ! 21
� 7 ! k ! 0
� 12 ! l ! 12
3
ꢁ
ꢂmax ( )
Range of h, k, l
0 ! h ! 21
�
�
3
7 ! k ! 0
12 ! l ! 12
No. of standard re¯ections
Frequency of standard
re¯ections
Every 150 re¯ections
Every 150 re¯ections
Every 150 re¯ections
Intensity decay (%)
0.8
1.3
0
Re®nement
Re®nement on
2
2
2
F
F
F
2
2
R‰F >2ꢄꢂF †Š
0.040
0.121
1.02
0.051
0.160
1.05
0.091
0.221
1.60
2
wRꢂF †
S
No. of re¯ections used in
re®nement
1790
1793
2961
No. of parameters used
H-atom treatment
Weighting scheme
137
All H-atom parameters re®ned
137
H atoms: see text
217
H-atom parameters not re®ned
2
2
2
2
2
2
2
2
2
w = 1/[ꢄ(Fo ) + (0.0639P)
0.0958P] where
w = 1/[ꢄ(Fo ) + (0.0927P)
+ 0.0444P] where
w = 1/[ꢄ(Fo ) + (0.05P) ]
where P = (Fo + 2F )/3
2
2
+
P = (Fo + 2F )/3
c
2
2
2
2
P = (Fo + 2F )/3
c
c
ꢂÁ=ꢄ†
0.0001
0.12
0.0001
0.0001
max
Ê
Ê
� 3
)
Áꢅ (e A
0.20
� 0.18
None
±
0.85
� 0.39
None
±
max
� 3
)
Áꢅmin (e A
Extinction method
Extinction coef®cient
� 0.15
SHELXL97 (Sheldrick, 1997)
0.066 (8)
ꢁ
cant change in lattice constants of (IV). The irradiation
through a long-pass ®lter UV34 (T = 10% at 330 nm) caused
the reaction, although the crystal easily decomposed. After
several trials, the X-ray intensities were measured using the
crystal irradiated through the UV34 for 2 h. The typical peak
half-width increased from 0.38 to 0.45 without splitting. At
®rst, the non-H atoms of the monomer constituent were
re®ned anisotropically and the H atoms were re®ned isotro-
pically. Then, the C4* and C5* atoms of the photodimer were
located on a difference synthesis. The C4*ÐC5* and C4*Ð
Acta Cryst. (2000). B56, 682±689
Hosomi et al. ꢀ trans-Cinnamamides 685

research papers
iv
C5* bond lengths were reasonable for a cyclobutane ring.
0
Fig. 2(b) shows the disordered structure of (II ) after photo-
irradiation for 6 h. The population of the dimer is 48.4 (6)%.
Positional parameters of the O1*, N2*, C3*, C6*, C7* and
C11* atoms were derived by the method of trial and error
based on difference syntheses, adjustment of bond lengths,
and re®nements with restraint on bond distances. The posi-
tional parameters of the C8*, C9*, C10* and H atoms were
calculated geometrically. All the positional parameters of the
dimer were ®nally ®xed using the isotropic displacement
parameters of the corresponding atoms of the monomer. By
the introduction of the dimer of 4.5 (2)% population, the R
value reduced from 0.062 to 0.051.
Fig. 3 shows a pair of monomers of trans-3-(2-thienyl)acryl-
0
Ê
amide (III). The C5Á Á ÁC6 distance is 3.762 (3) A. trans-
Cinnamamide (IV) is less photoreactive than (I)±(III) and the
0
Ê
C4Á Á ÁC5 distance in Fig. 4(a) is 4.120 (2) A, which is longer
than the corresponding distances in (I)±(III) by 0.358 (4)±
Ê
0
0.488 (3) A. Fig. 4(b) shows the structure of (IV ) after
photoirradiation for 2 h. The population of the dimer is
4.5 (2)%
In (I ) and (II ), the ethene C atoms are moved nearly
perpendicular to the molecular plane to form a cyclobutane
ring. The length of the movement of the ethene C atom is
0
0
Crystals of (I)±(IV) changed instantly into opaque by
photoirradiation without a ®lter. Plate-like crystals of (III)
were deformed and curled soon after photoirradiation even
through the band pass ®lter BP365. The lowest-energy
0
longer in the phenyl side than in the amido side. In (I ) the
Ê
C5ÐC5* and C4ÐC4* distances are 1.20 (1) and 0.91 (1) A,
absorption maxima of the CH CN solutions are (I) 278, (II)
3
2
73, (III) 302 and (IV) 269 nm.
3. Discussion
3
.1. Molecular structure
Fig. 1a shows a pair of monomers in trans-4-methylcinna-
mamide (I) related by a center of symmetry. The distance
0
Ê
between the C C double bonds, C4Á Á ÁC5 , is 3.670 (2) A. Fig.
0
1
(b) is a disordered structure of (I ) after photoirradiation for
5
of the dimer correspond to those of the monomer with an
h. The population of the dimer is 86.2 (4)%. The atom labels
Figure 3
The structure of a pair of molecules in (III) related by a center of
symmetry. The positional and anisotropic displacement parameters of
C10* and S1* were assumed to be the same as those of S1 and C10,
respectively. The site occupation factors of S1 and C10 are 0.808 (4), and
those of S1* and C10* are 0.192. Displacement ellipsoids are plotted at
the 30% probability level. H atoms are shown as spheres of arbitrary size.
asterisk. Fig. 2(a) shows a pair of monomers in trans-4-
0
Ê
chlorocinnamamide (II). The C5Á Á ÁC6 distance is 3.632 (2) A.
Figure 2
Figure 4
(a) The structure of a pair of molecules in (IV) related by a center of
symmetry; (b) the disordered structure in (IV ) which consists of the
monomer (open bonds) 95.5 (2)% and the dimer (solid bonds) 4.5 (2)%.
Displacement ellipsoids are plotted at the 30% probability level. H atoms
are shown as spheres of arbitrary size.
(
a) The structure of a pair of molecules in (II) related by a center of
0
0
symmetry; (b) the disordered structure in (II ) which consists of the
monomer (open bonds) 51.6 (6)% and the dimer (solid bonds) 48.4 (6)%.
Displacement ellipsoids are plotted at the 30% probability level. H atoms
are shown as spheres of arbitrary size.
6
86 Hosomi et al. ꢀ trans-Cinnamamides
Acta Cryst. (2000). B56, 682±689

research papers
0
respectively. In (II ) the C6ÐC6* and C5ÐC5* distances are
group are involved in the intermolecular NÐHÁ Á ÁO hydrogen
bonds to form a two-dimensional pleated sheet, and photo-
dimerization occurs within the sheet. According to the nota-
tion proposed by Leiserowitz & Schmidt (1969), the crystal
structures of (I)±(III) belong to a screw-axis related packing.
A twofold screw axis parallel to b lies on the two-dimensional
Ê
.26 (1) and 0.86 (1) A, respectively. Although the orientation
1
of the amido plane altered by 17±25 in (I ) and (II ), the NÐ
ꢁ
0
0
HÁ Á ÁO intermolecular hydrogen bonds were kept after the
0
reaction (Table 4). In (IV ), the ethene C atoms moved for
dimerization not only perpendicular to the molecular plane,
but also along the C C bond direction. The C4ÐC4* and
Ê
C5ÐC5* distances are ca 1.3 A. As can be seen from Table 4
and Fig. 6(b), the cyclic NÐHÁ Á ÁO hydrogen bonds were
broken between the monomer and dimer, and between the
dimers.
3
.2. Crystal structure
Structures of the hydrogen-bond networks in (I)±(III) are
similar to each other. Projections of the crystal structures of
0
(
II) and (II ) are shown in Fig. 5. Both H atoms of the NH
2
Figure 5
Projection of the crystal structure of (a) (II) and (b) (II ) along a. Dashed
lines represent hydrogen bonds. The monomer component in (II ) is
omitted for clarity.
0
Figure 6
Projection of crystal structure of (a) (IV) and (b) (IV ) along b. Dashed
lines represent hydrogen bonds.
0
0
Acta Cryst. (2000). B56, 682±689
Hosomi et al. ꢀ trans-Cinnamamides 687

research papers
Table 3
Selected geometric parameters (A, ).
hydrogen-bond sheet with b = 9.148 (3),
Ê
.075 (2) and 9.087 (2) A for (I), (II) and
Ê
ꢁ
9
(III), respectively.
0
(
C4 C5
I)
(I )
C4*ÐC5*
C4*ÐC5*
1.325 (2)
3.670 (2)
108.9 (1)
80.2 (1)
1.540 (4)
1.595 (4)
90.9 (2)
112.0 (2)
14.6 (4)
On the other hand, the hydrogen-bond
network in (IV) is a one-dimensional ¯at
ribbon, where the cyclic hydrogen-
bonded dimers of the amido moieties are
linked side by side along the b axis (Fig.
i
i
C4Á Á ÁC5
i
i
i
C5 C4Á Á ÁC5
C5*ÐC4*ÐC5*
C3*ÐC4*ÐC5*
O1* C3*ÐC4*ÐC5*
N2*ÐC3*ÐC4*ÐC5*
C3*ÐC4*ÐC5*ÐC6*
i
C3ÐC4Á Á ÁC5
O1 C3ÐC4 C5
N2ÐC3ÐC4 C5
C3ÐC4 C5ÐC6
� 1.7 (2)
179.5 (1)
177.5 (1)
� 168.0 (3)
123.9 (3)
6
a). According to the notation of
0
(II)
C5 C6
(II )
C5*ÐC6*
Leiserowitz & Schmidt (1969), the crystal
structure of (IV) belongs to translation
packing. On photodimerization, the
cyclic hydrogen bonds were broken not
only between the photodimers, but also
between the monomer and the photo-
dimer (Fig. 6b and Table 4).
Figs. 7 and 8 show the molecular and
crystal structure of (V), which was
prepared by a photodimerization of (II)
and was recrystallized from a chloroform
solution. There are two independent
molecules and the hydrogen-bond
network is composed of a one-dimen-
sional ¯at ribbon along c. The crystal
structure of (V) was different from that
1.326 (3)
3.632 (2)
107.3 (1)
96.0 (1)
� 6.6 (3)
172.7 (2)
� 179.0 (2)
1.548 (9)
1.582 (8)
90.2 (4)
ii
ii
C5Á Á ÁC6
C5*ÐC6*
C6*ÐC5*ÐC6*
C4*ÐC5*ÐC6*
O2* C4*ÐC5*ÐC6*
N3*ÐC4*ÐC5*ÐC6*
C4*ÐC5*ÐC6*ÐC7*
ii
ii
C6 C5Á Á ÁC6
ii
ii
C4ÐC5Á Á ÁC6
117.7 (8)
� 10 (2)
O2 C4ÐC5 C6
N3ÐC4ÐC5 C6
C4ÐC5 C6ÐC7
� 177.1 (7)
� 118.3 (8)
(
III)
C5 C6
(IV)
C4 C5
1.321 (3)
3.762 (3)
117.4 (1)
81.2 (1)
1.316 (2)
4.120 (2)
65.7 (1)
101.6 (1)
14.2 (2)
iii
iv
C5Á Á ÁC6
C4Á Á ÁC5
iii
iv
C6 C5Á Á ÁC6
C5 C4Á Á ÁC5
iii
iv
C4ÐC5Á Á ÁC6
C3ÐC4Á Á ÁC5
O2 C4ÐC5 C6
N3ÐC4ÐC5 C6
C4ÐC5 C6ÐC7
2.5 (3)
� 177.1 (2)
O1 C3ÐC4 C5
N2ÐC3ÐC4 C5
C3ÐC4 C5ÐC6
� 166.5 (1)
178.6 (2)
� 178.8 (1)
0
(
IV )
(V)
C5ÐC6
C5ÐC6
C6ÐC5ÐC6
C55ÐC56
C4*ÐC5*
C4*ÐC5*
C5*ÐC4*ÐC5*
1.519
1.582
86.6
1.57 (1)
1.56 (1)
89.0 (5)
1.54 (1)
1.59 (1)
89.5 (5)
iv
v
iv
v
0
of (II ), which was derived from the
crystal-to-crystal transformation. The cell
volumes of (I ) and (II ) became greater
than those of (I) and (II), indicating the
decrease in packing ef®ciency on photo-
dimerization.
vi
C55ÐC56
C56ÐC55ÐC56
vi
0
0
1
2
3
Symmetry codes: (i) � x;2 � y;1 � z; (ii) 1 � x;� y;1 � z; (iii) � x;1 � y;1 � z; (iv) 2 � x;1 � y;2 � z; (v)
1
� x;1 � y;1 � z; (vi) 1 � x;� y;1 � z.
Figure 7
The structure of two independent molecules in (V). Displacement
ellipsoids are plotted at the 30% probability level. H atoms are shown as
spheres of arbitrary size.
Figure 8
Projection of crystal structure of (V) along c. Dashed lines represent
hydrogen bonds.
6
88 Hosomi et al. ꢀ trans-Cinnamamides
Acta Cryst. (2000). B56, 682±689

research papers
Table 4
Hydrogen-bonding geometry (A, ).
This work was supported in part by a Grant-in-Aid for
Scienti®c Research (No. 10640496) from the Ministry of
Education, Science, Sports and Culture.
Ê
ꢁ
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
i
(
I) N2ÐH2AÁ Á ÁO1
0
0.95 (2)
0.92 (2)
0.96
1.99 (2)
2.04 (2)
2.03
2.19
2.01
2.932 (2)
2.956 (2)
2.961
169 (2)
170 (2)
162
161
166
ii
i
N2ÐH2BÁ Á ÁO1
References
(
I ) N2ÐH2AÁ Á ÁO1
ii
N2ÐH2BÁ Á ÁO1
0.96
3.117
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla,
M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435.
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i
N2*ÐH2*AÁ Á ÁO1* 0.95
2.946 (3)
3.049 (3)
2.941 (3)
3.050 (2)
2.98 (2)
3.06 (1)
2.94 (2)
3.00 (2)
2.916 (3)
2.970 (3)
2.960 (2)
2.943 (2)
2.943 (2)
3.404 ²
2.939 (2)
3.122
3.257²
3.809²
3.025
3.049
2.925 (7)
3.007 (8)
3.005 (7)
3.163 (9)
ii
N2*ÐH2*BÁ Á ÁO1* 0.95
2.12
166
iii
(
(
II) N3ÐH3AÁ Á ÁO2
0.88 (3)
2.09 (2)
2.18 (2)
2.10
2.30
2.04
163 (2)
178 (2)
153
135
157
iv
N3ÐH3BÁ Á ÁO2
0.87 (2)
0.96
0.96
0
iii
II ) N3ÐH3AÁ Á ÁO2
iv
N3ÐH3BÁ Á ÁO2
iii
N3*ÐH3*AÁ Á ÁO2* 0.96
iv
N3*ÐH3*BÁ Á ÁO2* 0.96
2.05
171
v
(
(
(
III) N3ÐH3AÁ Á ÁO2
0.91 (3)
2.01 (3)
2.02 (3)
2.07 (2)
2.14 (2)
2.02 (2)
2.48
2.15 (2)
2.31
2.46
2.94
2.13
2.10
1.94
169 (2)
173 (2)
176 (2)
151 (1)
172 (2)
171
149 (1)
153
141
151
155
168
173
vi
N3ÐH3BÁ Á ÁO2
0.96 (3)
0.90 (2)
0.89 (2)
0.93 (2)
0.93 (2)
0.88 (2)
0.88 (2)
0.96
vii
IV) N2ÐH2AÁ Á ÁO1
5809±5810.
viii
N2ÐH2BÁ Á ÁO1
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Iwamoto, T. & Kashino, S. (1992). Bull. Chem. Soc. Jpn, 65, 2151±
2153.
0
vii
IV ) N2ÐH2AÁ Á ÁO1
vii
N2ÐH2AÁ Á ÁO1*
viii
N2ÐH2BÁ Á ÁO1
N2ÐH2BÁ Á ÁO1*
viii
vii
N2*ÐH2*AÁ Á ÁO1
vii
N2*ÐH2*AÁ Á ÁO1* 0.96
viii
viii
N2*ÐH2*BÁ Á ÁO1
0.96
N2*ÐH2*BÁ Á ÁO1* 0.96
ix
(
V) N3ÐH3AÁ Á ÁO2
0.99
0.96
Iwamoto, T., Kashino, S. & Haisa, M. (1989). Acta Cryst. C45, 1110±
x
N3ÐH3BÁ Á ÁO2
2.11
2.06
2.32
156
164
146
1112.
xi
N53ÐH53AÁ Á ÁO52 0.97
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge
National Laboratory, Oak Ridge, Tennessee, USA.
x
N53ÐH53BÁ Á ÁO52 0.97
1
2
3
2
1
2
1
2
1
2
Leibovitch, M., Olovsson, G., Scheffer, J. R. & Trotter, J. (1998). J.
Am. Chem. Soc. 120, 12755±12769.
Leiserowitz, L. & Schmidt, G. M. J. (1969). J. Chem. Soc. A, pp. 2372±
Symmetry codes: (i) � x; � y;� z; (ii) � x; ‡ y; � z; (iii) 1 � x;� y;2 � z; (iv)
1
2
3
2
1 3
2 2
1
� x; ‡ y; � z; (v) � x;1 � y;2 � z; (vi) � x;y �
;
� z; (vii) 2 � x;1 � y;3 � z;
(
data indicate a breaking of the hydrogen bond involving the photodimer.
viii) x;y � 1;z; (ix) 2 � x;1 � y;1 � z; (x) x;y;z � 1; (xi) � x;� y;1 � z: ² These
2382.
Mason, C. D. & Nord, F. F. (1951). J. Org. Chem. 16, 1869±1872.
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Crystal structures of the photodimer of (IV) have been
reported for monohydrate (Iwamoto & Kashino, 1990),
anhydrate monoclinic (Vaida et al., 1989) and anhydrate
triclinic forms (Iwamoto & Kashino, 1992). The mode of
hydrogen bonding in the latter crystal is similar to that in (V)
0
:
0
:
with the relationship of lattice constants a ˆ: b=2, b ˆ: 2a
0
:
and c ˆ: c.
4. Concluding remarks
Photodimerization in crystals of trans-4-methylcinnamamide,
trans-4-chlorocinnamamide and trans-cinnamamide was
observed by crystal-to-crystal transformations. The lower
photoreactivity of trans-cinnamamide is not only due to longer
CÁ Á ÁC distances between the nearest neighbor C C double
bonds, but also due to partial breakdown of the NÐHÁ Á ÁO
hydrogen-bond network by the photodimerization.
Acta Cryst. (2000). B56, 682±689
Hosomi et al. ꢀ trans-Cinnamamides 689