Synthesis and crystal structure of [5-chloro-2-(4-nitrobenzyloxy)-phenyl]- (4-chloro-phenyl) methanone

Article abstract of DOI:10.1080/15421400902841551

The title compound, C₂₀H₁₃Cl₂NO ₄, crystallizes in the monoclinic crystal system and space group P2₁/n with cell parameters a = 9.434(2) A, b = 13.167(3) A, c = 15.087(4) A, β = 105.289(8)°, V = 1807.

Full text of DOI:10.1080/15421400902841551

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Synthesis and Crystal Structure
of [5-Chloro-2-(4-nitro-
benzyloxy)-phenyl]-(4-chloro-
phenyl) Methanone
S. Neetha a , T. D. Venu b , M. A. Sridhar a , J.
Shashidhara Prasad a & S. Shashikanth b
a Department of Studies in Physics , University of
Mysore , Mysore, India
b Department of Studies in Chemistry , University of
Mysore , Mysore, India
Published online: 03 Jun 2009.
To cite this article: S. Neetha , T. D. Venu , M. A. Sridhar , J. Shashidhara Prasad & S.
Shashikanth (2009) Synthesis and Crystal Structure of [5-Chloro-2-(4-nitro-benzyloxy)-
phenyl]-(4-chloro-phenyl) Methanone, Molecular Crystals and Liquid Crystals, 503:1,
143-150, DOI: 10.1080/15421400902841551
To link to this article: http://dx.doi.org/10.1080/15421400902841551
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Mol. Cryst. Liq. Cryst., Vol. 503, 143–150, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 1542-1406 print=1563-5287 online
DOI: 10.1080/15421400902841551
Synthesis and Crystal Structure of [5-Chloro-2-(4-nitro-
benzyloxy)-phenyl]-(4-chloro-phenyl) Methanone
S. Neetha1, T. D. Venu2, M. A. Sridhar1,
J. Shashidhara Prasad1, and S. Shashikanth2
1Department of Studies in Physics, University of Mysore, Mysore, India
2Department of Studies in Chemistry, University of Mysore,
Mysore, India
The title compound, C20H13Cl2NO4, crystallizes in the monoclinic crystal system
˚
˚
and space group P21=n with cell parameters a ¼ 9.434(2) A, b ¼ 13.167(3) A, c ¼
3
ꢀ
˚
˚
15.087(4) A, b ¼ 105.289(8) , V ¼ 1807.7(7) A for Z ¼ 4. The structure exhibits
intermolecular hydrogen bonds of the type CꢁH . . . O.
Keywords: benzophenone; crystal structure; hydrogen bond
INTRODUCTION
Benzophenone is a prototypical aromatic carbonyl compound that has
been extensively studied [1] and are usually obtained from natural
products and by synthetic methods. The great importance of these sub-
stances is fundamentally due to the diverse biological and chemical
properties that they possess [2–11]. Subsequently, benzophenones
are frequently used in medicine and industry [12–17]. The proficiency
of benzophenone analogues as chemotherapeutic agent especially as
anti-inflammatory is well documented [18]. Several scientists have
reported benzophenon analogues as an effective anti-inflammatory
agents [19–22]. Recently, synthesis and structural activity relation-
ship of benzophenones as a novel class of p38 MAP kinase inhibitors
with high anti-inflammatory activity has been reported [23].
Functionalized phenols, such as 2-hydroxy benzophenones, repre-
sent important building blocks in organic and medicinal chemistry
Address correspondence to J. Shashidhara Prasad, Department of Studies in Physics,
Manasagangotri, University of Mysore, Mysore 570 006, India. E-mail: jsp@physics.
uni-mysore.ac.in
143

144
S. Neetha et al.
[24,25]. The in vitro and in vivo studies of novel nitro- and amino-
substituted benzophenones have been investigated as potential anti-
cancer agents with low cytotoxicity [26]. In continuation of the search
for new molecules with anti-inflammatory activity, encouraged us to
integrate p-nitro phenyl moiety in benzophenone framework, which
possess well-documented anti-inflammatory activity.
SYNTHESIS AND METHOD OF CRYSTALLIZATION
4-Chloro-benzoic acid 4-chloro-phenyl ester (3) was synthesized by
benzoylation of 4-chloro-phenol (1) with 4-chloro benzoyl chloride
(2) using 10% sodium hydroxide solution. (5-Chloro-2-hydroxy-
phenyl)-(4-chloro-phenyl)-methanone (4) was synthesized by Fries
rear-rangement of the above ester in presence of anhydrous
aluminium chloride. A mixture of 4 (1 g, 4.41 mmol) and 4-nitro ben-
zyl bromide (0.95 g, 4.41 mmol) was refluxed in dry acetone for 5 h, in
the presence of anhydrous potassium carbonate (1.83 g, 13.25 mmol).
The reaction mass was cooled, and the solvent was removed under
reduced pressure. The residual mass was triturated with ice-cold
water to remove potassium carbonate and then extracted with
dichloromethane (3 ꢂ 20 ml). The organic layer was washed with
10% sodium hydroxide solution (3 ꢂ 10 ml) followed with water
wash (3 ꢂ 15 ml) and then dried over anhydrous sodium sulfate and
evaporated to dryness under reduced pressure to obtain the crude
solid, which recrystallization with ethanol yielded [5-chloro-2-
(4-nitro-benzyloxy)-phenyl]-(4-chloro-phenyl) methanone (5) as pale
yellow crystals, the yield was good.
C,H,N analysis: Calculated %: C: (73.12), H: (5.30), N: (3.88). Found
%: C: (73.06), H: (5.28), N: (3.80). 1H NMR(CDCl3): d 2.31 (s, 3H, CH3),
2.41 (s, 3H, CH3), 4.9 (s, 2H, CH2), 7.17–7.36 ppm (m, 11H, Ar-H).
IR (Nujol): 1716 cmꢁ1 (C 0). M.P.: 167 C. Yield: 88% (1.40 g).
ꢀ
=
CRYSTAL STRUCTURE DETERMINATION
A
single crystal of the title compound with the dimensions
0.30 ꢂ 0.25 ꢂ 0.25 mm was chosen for the X-ray diffraction study.
The data were collected on a DIPLabo Image Plate system equipped
with a normal focus, 3 kW sealed X-ray source (graphite monochro-
mated MoKa). The crystal to detector distance was fixed at 120 mm
with the detector area of 441 ꢂ 240 mm2. Thirty-six frames of data
were collected at room temperature by the oscillation method. Each
exposure of the image plate was set to 400 s. Successive frames were

Crystal Structure of a Benzophenone
145
scanned in steps of 5ꢀ per minute with an oscillation range of 5ꢀ. Image
processing and data reduction were done using Denzo [27]. The reflec-
tions were merged with Scalepack [28]. All the frames could be
indexed using a primitive monoclinic lattice. Absorption correction
was not applied. The structure was solved by direct methods using
SHELXS-97 [29]. Least-squares refinement using SHELXL-97 [30]
with isotropic temperature factors for all the non-hydrogen atoms con-
verged the residual R1 to 0.1595. Subsequent refinements were
carried out with anisotropic thermal parameters for non-hydrogen
atoms and isotropic temperature factors for the hydrogen atoms which
were placed at chemically acceptable positions. The hydrogen atoms
were allowed to ride on their parent atoms. After eight cycles of refine-
ment, the residual converged to 0.0737. The details of crystal data and
TABLE 1 Crystal Data and Structure Refinement Table
CCDC
702891
C20H13 Cl2NO4
402.21
Empirical formula
Formula weight
Temperature
Wavelength
Crystal system
Space group
293(2) K
˚
0.71073 A
Monoclinic
P21=n
˚
Cell dimensions
a ¼ 9.434(2) A
˚
b ¼ 13.167(3) A
˚
c ¼ 15.087(4) A
b ¼ 105.289(8)ꢀ
3
˚
Volume
1807.7(7) A
Z
4
Density (calculated)
Absorption coefficient
F000
1.478 Mg=m3
0.386 mmꢁ1
824
Crystal size
Theta range for data collection
Index ranges
0.3 ꢂ 0.25 ꢂ 0.25 mm
2.09ꢀ to 25.00ꢀ
ꢁ11 ꢃ h ꢃ 11
ꢁ15 ꢃ k ꢃ 15
ꢁ17 ꢃ l ꢃ 17
Reflections collected
3918
Independent reflections
Absorption correction
Refinement method
Data=restraints=parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
2672 [R(int) ¼ 0.0450]
None
Full-matrix least-squares on F2
2672=0=245
1.063
R1 ¼ 0.0737, wR2 ¼ 0.1945
R1 ¼ 0.0900, wR2 ¼ 0.2206
0.001(9)
Extinction coefficient
Largest diff. peak and hole
ꢁ3
˚
0.255 and ꢁ0.257 e ꢄ A

146
S. Neetha et al.
TABLE 2 Atomic Coordinates and Equivalent Thermal Parameters of the
Non-Hydrogen Atoms
Atom
x
y
z
Ucq
O1
N2
O3
C4
C5
C6
C7
C8
0.6628(3)
0.5750(3)
0.5187(5)
0.5374(4)
0.4516(4)
0.4219(4)
0.4732(3)
0.5578(4)
0.5903(4)
0.4394(4)
0.3801(3)
0.3398(3)
0.2678(3)
0.2314(3)
0.2635(4)
0.3326(4)
0.3705(4)
0.21317(1)
0.2326(4)
0.2537(4)
0.1665(3)
0.0763(4)
0.0127(4)
0.0439(4)
0.1336(4)
0.1927(4)
ꢁ0.03151(1)
1.0642(2)
1.0337(3)
1.0898(3)
0.9251(3)
0.8897(3)
0.7872(3)
0.7207(3)
0.7601(3)
0.8623(3)
0.6094(3)
0.5828(2)
0.4841(3)
0.4634(3)
0.3636(3)
0.2864(3)
0.3061(3)
0.4048(3)
0.16180(8)
0.5449(3)
0.5290(3)
0.6427(3)
0.6476(3)
0.7385(3)
0.8249(3)
0.8232(3)
0.7313(3)
0.94037(8)
0.2896(2)
0.3287(2)
0.3732(4)
0.3247(2)
0.3795(3)
0.3770(3)
0.3218(2)
0.2677(2)
0.2684(3)
0.3173(2)
0.39123(2)
0.3983(2)
0.4668(2)
0.4818(2)
0.4285(2)
0.3607(3)
0.3463(3)
0.44568(8)
0.5271(3)
0.60891(2)
0.4868(2)
0.3970(3)
0.3611(2)
0.4145(3)
0.5039(3)
0.5391(3)
0.36776(8)
0.0989(8)
0.0903(9)
0.1572(2)
0.0783(9)
0.0883(1)
0.0863(1)
0.0742(8)
0.0820(9)
0.0815(9)
0.0769(8)
0.0847(7)
0.0739(8)
0.0754(8)
0.0784(9)
0.0789(9)
0.0812(9)
0.0810(9)
0.0959(4)
0.0799(9)
0.1060(9)
0.0743(8)
0.0799(9)
0.0827(9)
0.0798(9)
0.0842(9)
0.0841(1)
0.1009(5)
C9
C10
O11
C12
C13
C14
C15
C16
C17
Cl18
C19
O20
C21
C22
C23
C24
C25
C26
Cl27
P P
Ucq ¼ ð1=3Þ
Uijðaꢅi aꢅj Þðai ꢄ ajÞ:
i
j
refinement are given in Table 1.1 Table 2 gives the atomic coordinates
and equivalent thermal parameters of the non-hydrogen atoms.
Tables 3 and 4 give the list of bond lengths and bond angles, respec-
tively, which are in good agreement with the standard values.
The schematic diagram and ORTEP of the molecule with thermal
ellipsoids drawn at 50% probability is shown in Fig. 1 and Fig. 2.
The title compound has independently planar phenyl ring system.
The dihedral angle between the two, 4-chloro-phenyl rings, bridged
1‘‘CCDC 702891 contains the supplementary crystallographic data for this article.
These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html
(or from The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK. Fax: þ44(0)1223-336033. E-mail: deposit@ccdc.cam.ac.uk’’

Crystal Structure of a Benzophenone
147
˚
TABLE 3 Bond Lengths A
Atoms
Length
Atoms
Length
O1-N2
N2-O3
N2-C4
C4-C9
C4-C5
C5-C6
C6-C7
C7-C8
C7-C10
C8-C9
C10-O11
O11-C12
C12-C17
C12-C13
C13-C14
1.207(4)
1.211(5)
1.470(5)
1.371(5)
1.381(5)
1.376(6)
1.381(5)
1.383(5)
1.498(5)
1.380(5)
1.417(4)
1.366(4)
1.382(5)
1.405(4)
1.392(5)
C13-C19
C14-C15
C15-C16
C15-C118
C16-C17
C19-O20
C19-C21
C21-C26
C21-C22
C22-C23
C23-C24
C24-C25
C24-C127
C25-C26
1.500(5)
1.379(5)
1.375(5)
1.746(4)
1.381(5)
1.215(4)
1.488(5)
1.394(5)
1.399(5)
1.383(5)
1.381(6)
1.391(6)
1.747(4)
1.379(6)
˚
by carbonyl group is 64.51(17) A. The atom C23 deviate from the
˚
Cremer and Pople plane C21=C22=C24=C25=C26 by 0.0123(39) A.
Torsion angle values of ꢁ136.23(33)ꢀ and 41.16(51)ꢀ for C14-C13-
C19-C21 and C14-C13-C19-C20, respectively, gives ꢁanti-clinal and
TABLE 4 Bond Angles (ꢀ)
Atoms
Angle
Atoms
Angle
O1-N2-O3
O1-N2-C4
O3-N2-C4
C9-C4-C5
C9-C4-N2
C5-C4-N2
C6-C5-C4
C5-C6-C7
C6-C7-C8
121.7(4)
119.6(3)
118.7(4)
122.3(3)
119.3(3)
118.5(3)
117.5(3)
122.4(3)
117.8(3)
122.9(3)
119.3(3)
121.6(3)
118.4(3)
109.3(3)
118.2(3)
124.7(3)
116.1(3)
119.1(3)
119.4(3)
118.2(3)
C12-C13-C19
C15-C14-C13
C16-C15-C14
C16-C15-C118
C14-C15-C118
C15-C16-C17
C16-C17-C12
O20-C19-C21
O20-C19-C13
C21-C19-C13
C26-C21-C22
C26-C21-C19
C22-C21-C19
C23-C22-C21
C24-C23-C22
C23-C24-C25
C23-C24-C127
C25-C24-C127
C26-C25-C24
C25-C26-C21
122.4(3)
120.0(3)
121.0(3)
119.3(3)
119.7(3)
119.3(3)
121.3(3)
120.2(3)
119.3(4)
120.4(3)
118.8(3)
120.0(3)
121.3(3)
120.7(3)
118.7(3)
122.4(4)
118.7(3)
119.0(3)
117.9(4)
121.6(3)
C6-C7-C10
C8-C7-C10
C9-C8-C7
C4-C9-C8
O11-C10-C7
C12-O11-C10
O11-C12-C17
O11-C12-C13
C17-C12-C13
C14-C13-C12
C14-C13-C19

148
S. Neetha et al.
FIGURE 1 Schematic diagram.
þsyn-clinal conformation. The torsion angle about C12=C11=C10=C7
˚
being 179.01(27) A reflects þanti-periplanar conformation w.r.t chloro
phenyl and nitroxy phenyl ring, respectively. The keto group in the
structure plays a vital role in the determination of some potent biolo-
gical activities [20]. The structure exhibits intermolecular hydrogen
˚
bonds of the type C–H . . . O. C9–H9 . . . O20 has a length of 3.489(5) A
with an angle of 168ꢀ, and C10ꢁH10B . . . O20 which has a length of
ꢀ
˚
3.353(5) A and an angle of 158 with symmetry codes 1=2 þ x, 3=2ꢁy,
ꢁ1=2 þ z, and 1ꢁx, 1ꢁy, 1ꢁz, respectively. The stability of the crystal
FIGURE 2 ORTEP of the molecule at 50% probability.

Crystal Structure of a Benzophenone
149
FIGURE 3 Packing of the molecules down the b axis. The dashed lines
represent the hydrogen bonds.
structure can be accounted for by these hydrogen bonds. Packing of
the molecules down b axis is shown in Fig. 3.
ACKNOWLEDGMENTS
The authors would like to express their thanks to DST, Government of
India, for financial assistance under the project SP=I2=FOO=93.
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