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Abstract
Crystal structures of halogen-substituted benzanilides have been analyzed in terms of weak interactions involving halogens. The four
compounds namely 3-fluoro-N-(3-hydroxyphenyl)benzamide, 3-chloro-N-(3-hydroxyphenyl)benzamide, 3-fluoro-N-(4-methylphenyl)benzamide and 3-chloro-N-(4-methylphenyl)benzamide crystallize in monoclinic symmetry. The packing modes in the crystalline lattice
generate motifs via N H O and O H O hydrogen bonds in structures 1 and 2 and via N H O hydrogen bond, weak C H F and
Cl Cl interactions in structures 3 and 4. These structures when compared with the polymorphs of benzanilide show no orientational disorder
and depict subtle conformational changes, which are directed by both strong hydrogen bonds and weak interactions involving halogens.
q 2004 Elsevier B.V. All rights reserved.
Keywords: Weak interactions; Hydrogen bonds; Polymorphism; Molecular conformation
1. Introduction
Design and synthesis of new materials with desired
physical and chemical properties involve the generation and
study of structural motifs in crystals which is essentially
guided by precise topological control through the manipulation of intermolecular interactions [1]. This necessitates
the understanding of the nature of weak non-covalent
interactions, which dictate conformational and packing
features in crystalline solids. There are a rich variety of such
intermolecular interactions, which serve as tools in
engineering such molecular assemblies [2].
Hydrogen bonds are amongst the most studied of such
intermolecular interactions [3 6]. In recent years molecular
assemblies have been identified involving much weaker
non-covalent interactions to serve as tools in crystal
engineering. Some of these are the halogen halogen
interactions [7,8], charge transfer [9], electrostatic forces
[10 12], and p p stacks [13,14]. Hydrogen bonds [15 19]
are the most important and decisive element in crystal
engineering. The interactions involving hydrogen bond are
of a highly directional nature and the strength depends on
* Corresponding author. Tel.: 91-80-3942796; fax: 91-80-3601310.
E-mail address: ssctng@sscu.iisc.ernet.in (T.N.G. Row).
0022-2860/$ - see front matter q 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2004.03.011
134
2. Experimental
2.1. Synthesis
2.1.1. Compound 1 (3-fluoro-N-(3-hydroxyphenyl)
benzamide)
m-Fluorobenzoyl chloride (0.137 g,0.86 mmol) and
m-amino phenol(0.094 g,0.87 mmol) were taken along
with 10.0 ml of dry dichloromethane and the resulting
mixture stirred for 2 h under ice cold conditions. Compound
1 was isolated by solvent extraction with dichloromethane
and finally subjected to column chromatography packed
with silica and ethyl acetate/hexane was used as the eluant.
Routine M.P, IR, UV VIS and NMR analysis confirmed the
formation of compound 1. Crystals of suitable quality were
grown by solvent evaporation from a solution of the
compound in ethyl acetate/hexane mixture.
2.1.2. Compound 2 (3-chloro-N-(3-hydroxyphenyl)
benzamide)
m-Chloro benzoic acid (0.600 g,3.8 mmol) was taken
along with 10.0 ml of dry dichloromethane. Thionyl
Chloride (5.0 ml) was added and the mixture
was refluxed for 2 h. The product, m-chloro benzoyl
chloride, was distilled under vacuum. 3-Amino Phenol
(0.323 g, 2.9 mmol) was added under ice-cold conditions to
135
Fig. 2. (a) ORTEP diagram of 3-fluoro-N-(3-hydroxyphenyl)benzamide. (b) ORTEP diagram of 3-chloro-N-(3-hydroxyphenyl)benzamide. (c) ORTEP
diagram of 3-fluoro-N-(4-methylphenyl)benzamide. (d) ORTEP diagram of 3-chloro-N-(4-methylphenyl)benzamide.
136
Fig. 3. (a) Region of strong N H O, O H O, CH O interactions in Compound 1. (b) Region of strong NH O, OH O, CH O interactions in
Compound 2. (c) Regions of strong N H O hydrogen bonds and weak C H F interactions in Compound 3. (d) Regions of strong NH O hydrogen
bonds and weak Cl Cl interactions in Compound 4.
137
Table 1
Crystal data
Data
Compound 1
Compound 2
Compound 3
Compound 4
CCDC number
Formula
Formula weight
Temperature (K)
Radiation
)
Wavelength (A
Crystal system
Space group
)
a (A
)
b (A
)
c (A
a (8)
b (8)
g (8)
3)
Volume (A
Z
Density (g/ml)
m (1/mm)
F (000)
u (min, max)
h; k; l (min, max)
No. refln. measured
No. unique refln
No of parameters
Refinement method
R_all
R_obs
wR2_all
wR2_obs
23)
Drmax (eA
23)
Drmin (eA
GooF
211783
C13H10N1O2 F1
231.2
293(2)
Mo Ka
0.71073
Monoclinic
P21 =n
11.491(3)
5.061(1)
18.633(4)
90.00
106.514(4)
90.00
1038.90(13)
4
1.48
0.112
479.9
(1.9, 27.5)
(214,14) (26,6)(223,24)
7947
2271
194
Full matrix least Squares on F 2
0.049
0.043
0.117
0.111
0.17
20.22
1.057
211780
C13H10Cl1N1O2
247.67
293(2)
Mo Ka
0.71073
Monoclinic
P21 =n
12.069(3)
4.969(1)
18.831(4)
90.00
102.295(4)
90.00
1103.5(4)
4
1.491
0.333
512
(1.8, 26.4)
(215,15) (26,6)(222,23)
8329
2246
194
Full matrix least squares on F 2
0.047
0.036
0.103
0.094
0.23
20.20
1.025
211782
C14H12N1O1F1
229.3
293(2)
Mo Ka
0.71073
Monoclinic
P21 =c
27.388(4)
5.337(7)
7.976(1)
90.00
96.231(2)
90.00
1158.91(4)
4
1.31
0.094
479.9
(1.5, 26.4)
(234,31) (26,6) (29,9)
8400
2313
202
Full matrix least squares on F 2
0.083
0.065
0.152
0.143
0.29
20.14
1.188
211781
C14H12Cl1N1O1
245.71
293(2)
Mo Ka
0.71073
Monoclinic
C2=c
28.578(1)
5.518(2)
15.437(6)
90.00
102.830(6)
90.00
2373.37(37)
8
1.38
0.303
1024
(1.5, 26.4)
(235,32) (26,6) (219,19)
8973
2414
202
Full matrix least squares on F 2
0.077
0.063
0.141
0.137
0.41
20.16
1.180
3. Results
3.1. Structure of (3-fluoro-N-(3-hydroxyphenyl)benzamide)
Compound 1 crystallizes in the space group P21 =n with
Z 4. The crystals are plate-like and show no evidence
for concomitant polymorphism or orientational disorder in
the crystal packing as was found in the parent compound
[30,31]. The dihedral angle between the least squares plane
through the two-phenyl rings and the dihedral angle
between the planes passing through the amido group and
each of the phenyl rings are listed in Table 2. Two strong
and well defined hydrogen bonds hold the molecules
Table 2
Selected dihedral angles between least squares planes
Plane 1 and 3
Plane 2 and 3
Plane 1 and 2
Compound 1 (8)
Compound 2 (8)
Compound 3 (8)
Compound 4 (8)
Polymorph 1 [30]
2.78(4)
22.02(6)
23.45(6)
3.76(5)
27.67(8)
29.40(8)
62.43(7)
32.40(11)
28.37(12)
56.01(8)
29.97(12)
27.91(12)
62.6*
31.3*
31.6*
Plane 1, the phenyl ring C2/C7, Plane 2, the amido group N1C1O2, Plane 3, the phenyl ring C8/C13.
138
Table 3
Intermolecular interactions
Compound 1
Compound 2
Compound 3
Compound 4
Benzanilide polymorph 1a
Benzanilide polymorph 2b
a
b
D X A
)
r(D X) (A
)
r(X A) (A
)
r(D A) (A
/DX A (8)
N1H1N O10
O2H2O O10
C7 H7 O20
N1H1N O10
O2H2O O10
C7 H7 O20
N1H1N O10
C5 H5 F10
N1H1N O10
C4 Cl1 Cl10
N H O0
N H O0
0.88(2)
0.86(2)
0.97(2)
0.79(2)
0.85(3)
0.93(2)
0.85(2)
0.96(3)
0.81(3)
1.739(3)
1.15a
0.88b
2.32(2)
1.95(2)
2.47(2)
2.29(2)
1.95(3)
2.46(2)
2.36(2)
2.68(3)
2.58(3)
3.29(1)
2.03a
2.31
3.087(2)
2.784(1)
3.403(2)
2.987(2)
2.774(2)
3.361(2)
3.203(2)
3.525(3)
3.349(3)
4.977(3)
3.112(6)
3.141(4)
146.03(2)
162.83(2)
162.75(2)
149.07(2)
167.09(3)
164.96(2)
169.32(2)
147.96(2)
160.73(2)
162.59(4)
157a
157
4. Discussion
The four crystal structures indicate that in substituted
benzanilides intermolecular hydrogen bonds play a crucial
role in the packing of the molecules. Also these interactions
ensure the absence of orientational disorder and formation
of concomitant polymorphism unlike in the case of the
parent compound [30,31]. The presence of O H O
{Etters symbol [39]: R22 16} and N H O {C(4)}
hydrogen bonds in the structures of 1 and 2 lead to motifs
(Fig. 3a and b), which completely avoid orientational
disorder in the molecular structure. In structures 1 and 2 an
additional C H O {R22 18} provides additional stability
to the dimer formed by O H O hydrogen bond. Also in
the solvent system (ethyl acetate/hexane) the crystals are
well grown as plates and do not indicate any concomitance.
The formation of dimeric units across the center of
symmetry involving O H O hydrogen bonds in compounds 1 and 2 appear to rule out any short interactions
involving halogens. The halogen interactions C H F
{C(4)} in compound 3 and Cl Cl in compound 4 appear to
render the conformation in these two structures to be similar
to those of the parent compound (Table 3). However, it is of
interest to note that the interactions involving halogens do
remove orientational disorder and form clear plate like
139
Fig. 4. (a) Packing diagram of Compound 1 showing O H O, C H O dimers and NH O chains in the crystal lattice. (b) Packing diagram of Compound
2 showing O H O, C H O dimers and N H O chains in the crystal lattice. (c) Packing diagram of Compound 3 showing the N H O chains running
parallel to crystallographic b axis and weak C H F interactions. (d) Packing diagram of Compound 4 showing NH O chains running parallel to
crystallographic b axis as well as Cl Cl interaction across the center of symmetry.
140
Fig. 4 (continued )
6. Supplementary material
Crystallographic details (excluding structure factors) on
the structure analysis of the Compounds 1 4 reported in this
paper have been deposited with the Cambridge Crystallographic Data Center,12 Union Road,Cambridge,CB2,1EZ,UK; (Fax: 44-1223-336-033; e-mail:deposit@ccdc.
sam.ac.uk).The depository numbers are given in the tables.
Acknowledgements
We thank Mr Kabirul Islam for assistance during the
synthesis and Prof G. Mehta for kindly allowing use of
laboratory facilities. We also thank IRHPA-DST for
providing the CCD facility at IISc, Bangalore.
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141