Synthesis and crystal structure of 2-benzoyl-4-methyl phenyl benzoate

Article abstract of DOI:10.1007/s10870-005-2221-9

The crystal structure of the title compound, C₂₁H ₁₆O₃, has been determined. The compound crystallizes in triclinic space group PI with cell parameters a = 9.2240(9) A, b = 9.8050(8) A, c = 10.1610(11) A, α = 94.749(6)°, β = 112.544(4)°, γ = 102.145(6)° and Z = 2. The structure exhibits both intra and intermolecular interactions of the type C-H...O. The intermolecular interaction between the molecules form centrosymmetric dimers.

Full text of DOI:10.1007/s10870-005-2221-9

ꢀC
Journal of Chemical Crystallography, Vol. 35, No. 6, June 2005 ( 2005)
DOI: 10.1007/s10870-005-2221-9
Synthesis and crystal structure of 2-benzoyl-4-methyl
phenyl benzoate
M. Mahendra,(1) B. H. Doreswamy,(1) M. A. Sridhar,(1) J. Shashidhara Prasad,(1)∗
S. A. Khanum,(2) S. Shashikanth,(2) and T. D. Venu(2)
Received October 15, 2004; accepted December 21, 2004
The crystal structure of the title compound, C21H16O3, has been determined. The com-
¯
˚
pound crystallizes in triclinic space group P1 with cell parameters a = 9.2240(9) A,
◦
◦
◦
˚
˚
b = 9.8050(8) A, c = 10.1610(11) A, α = 94.749(6) , β = 112.544(4) , γ = 102.145(6)
and Z = 2. The structure exhibits both intra and intermolecular interactions of the type
---
C
H · · · O. The intermolecular interaction between the molecules form centrosymmetric
dimers.
---
KEY WORDS: Benzophenone analogues; synthesis; crystal structure; C H · · · O.
Introduction
Compounds containing the benzophenone
ing to structural activity relationships, the interac-
tions of these compounds with the RT enzyme are
through hydrogen bonding of the amide and ben-
zophenones carbonyls and pi-orbital interactions
with the benzophenones nucleus and an aromatic
function separated from the benzophenones by a
suitable spacer group.1 In addition, they find place
in industrial chemistry.18–21
Literature survey revealed that no efforts
were directed towards the study of the crys-
tal structure of (2-benzoyl-4-methyl phenyl ben-
zoate). Encouraged by the above information, it
was considered valuable to synthesize compound
3 as outlined in Scheme 1 and characterised by
X-ray studies.
moiety find a unique place in medicinal chem-
istry and play a significant role as they are as-
sociated with immense biological activities.1–4 In
recent years, it has been shown that benzophenone
analogues exhibit antiallergic,5,6 anticancer,2,7–9
antiinflammatory,10–12 antiasthmatic,5,6 antima-
larial,13,14 antimicrobial,15,16 antimitotic17 and
antianaphylactic activities.5,6 These compounds
inhibit the release of leukutrienes (LT) C4 &
D4 in vitro from sensitized guinea pig chopped
lung. Some of the compounds inhibited the release
of leukutrienes from passively sensitized human
chopped lungs. These compounds are evaluated
as inhibitors of HIV reverse transcriptase (RT)
and the growth of HIV in MT-4 cells. Accord-
Synthesis and characterisation
(2-Hydroxy-5-methyl phenyl)phenyl
methanone (2)
(1) Department of Studies in Physics, University of Mysore, Man-
asagangotri, Mysore 570006, India.
(2) Department of Studies in Chemistry, University of Mysore, Man-
asagangotri, Mysore 570006, India.
A solution of anhydrous aluminum chloride
(3.2 g, 0.02 mol) in dry nitrobenzene (25 ml)
was added to 4-methyl phenyl benzoate (1, 5 g,
∗ To whom correspondence should be addressed; e-mail:
jsp@uomphysics.net.
463
ꢀ
C
1074-1542/05/0600-0463/0 2005 Springer Science+Business Media, Inc.

464
Mahendra et al.
C14H12O2: C, 79.22; H, 5.70. Found: C, 79.08; H,
5.64%.
2-Benzoyl-4-methyl phenyl benzoate (3)
To a well-stirred ice cold solution of 2 (3 g,
0.014 mol) in 10% sodium hydroxide (20 ml),
benzoyl chloride (1.96 g, 0.014 mol) was added
dropwise and stirring was continued for about
15 min. The mixture was made alkaline by adding
10% sodium hydroxide. A white solid separated,
which was filtered and washed with water. On
recrystallization with alcohol this gave 3 in 75%
(3.35 g) yield. M.P. 90◦C.
−1
---
IR (Nujol): 1670.2 (C O), 1760 cm
---
(COO); H NMR (CDCl3, 300 MHz): δ 2.2 (s,
1
---
3H, CH3), 7.0–7.8 (m, 13H, Ar H); MS: m/z
316 (M+, 80), 239 (55), 211 (100), 105 (30), 77
(50); Anal. Cal. for C21H16O3: C, 79.73; H, 5.10.
Found: C, 79.68; H, 5.07%.
Scheme 1.
Crystal structure determination of 3
0.02 mol) dissolved in nitrobenzene (10 ml), the
mixture being protected from moisture by a cal-
cium chloride guard tube and refluxed with stir-
ring for 30 min. At the end of this period the so-
lution was cooled and decomposed by acidulated
ice-cold water. The nitrobenzene was removed by
steam distillation. The residual solid was crushed
into powder, extracted with 10% sodium hydrox-
ide (3 × 50 ml) and the basic aqueous solution
was neutralized with 10% hydrochloric acid. The
product was extracted into ether and the ether
layer was washed well with saturated sodium
chloride solution. Evaporation of the ether af-
ter drying over anhydrous sodium sulphate fol-
lowed by recrystallization from alcohol giving
(2-hydroxy-5-methyl phenyl) phenyl methanone
(2)in 85% (4.2 g) yield. M.P. 82◦C.
A single crystal of 3 of dimensions 0.2 mm ×
0.3 mm × 0.25 mm was chosen for X-ray diffrac-
tion studies. The measurements were made on
a DIPLabo Image Plate system with graphite
monochromated radiation (MoKα). Thirty six
frames of data were collected by oscillation
method. Successive frames were scanned in steps
of 3◦ per min with an oscillation range of 5◦.
Image processing and data reduction were done
by using Denzo.22 All frames could be indexed
with a triclinic primitive lattice. The structure
was solved by direct methods using SHELXS-
97.23 All the non-hydrogen atoms were revealed
in the first map. Full-matrix least-squares refine-
ment (using SHELXL-9724) based on 3305 ob-
served reflections (I > 2σ(I)) with isotropic tem-
perature factors for all the atoms converged resid-
ual to R1 = 0.1421. Refinement of non-hydrogen
atoms with anisotropic thermal parameters was
started at this stage. After eight cycles of re-
finement the residuals saturated at R1 = 0.0543.
The hydrogen atoms were placed at chemically
---
IR (Nujol): 1670.2 (C O), 3545–3649.1
---
cm−1 (OH); 1H NMR (CDCl3, 300 MHz): δ 2.3(s,
---
3H, CH3), 7.1–7.7 (m, 8H, Ar H), 9.8 (bs, 1H,
OH); MS: m/z 212 (M+, 87), 211 (100), 135
(60), 105 (35), 77 (56), 51(15); Anal. Cal. for

Synthesis and crystal structure of 2-benzoyl-4-methyl phenyl benzoate
465
◦
Table 1. Crystal Data and Experimental Crystallographic Details
˚
Table 2. Bond Lengths (A) and Bond angles ( )
Empirical formula
Formula weight
Temperature (K)
C21H16O3
316.34
293(2)
0.71073
Triclinic
¯
P 1
Bond length
----
----
1.384(3) C12 C13
C1 C2
1.385(2)
1.379(2)
1.380(2)
1.401(2)
1.360(2)
1.200(2)
1.483(2)
1.385(2)
1.389(2)
1.386(2)
1.375(3)
1.372(3)
1.388(2)
----
----
C1 C6
1.390(2) C13 C14
˚
Wavelength (A)
----
C2 C3
----
1.369(3) C14 C15
Crystal system
Space group
Cell dimensions
----
----
C3 C4
----
1.373(3) C15 O16
----
1.381(2) O16 C18
C4 C5
----
----
C5 C6
----
1.386(2) O17 C18
˚
a (A)
9.2240(9)
9.8050(8)
10.1610(11)
94.749(6)
112.544(4)
----
1.486(2) C18 C19
C6 C8
˚
b (A)
----
----
O7 C8
1.218(2) C19 C24
˚
----
----
c (A)
C8 C9
1.497(2) C19 C20
α (◦)
β (◦)
γ (◦)
----
----
C9 C15
1.389(2) C20 C21
----
----
C9 C10
1.397(2) C21 C22
----
----
102.145(6)
816.05(14)
C10 C12
1.387(2) C22 C23
3
˚
----
----
Volume (A )
C11 C12
1.503(2) C23 C24
Z
2
Bond angle
Density(calculated) (Mg/m3)
Absorption coefficient (mm−1
F000
1.287
0.086
332
---- ----
----
----
C2 C1 C6
119.7(2)
120.5(2)
120.2(2)
119.9(2)
120.4(2)
119.2(1)
121.6(1)
119.1(1)
121.3(1)
120.4(1)
118.3(1)
117.7(1)
123.2(1)
118.1(1)
122.4(2)
C14 C13 C12 121.2(1)
)
---- ----
C3 C2 C1
----
----
C15 C14 C13 119.1(1)
---- ----
---- ----
C2 C3 C4
C14 C15 C9 120.9(1)
---- ----
Crystal size
0.2 mm × 0.3 mm
× 0.25 mm
2.55–32.50◦
−13 ≤ h ≤ 13
−14 ≤ k ≤ 14
−15 ≤ l ≤ 15
7723
4824 [Rint = 0.0310]
Full-matrix least-squares
on F2
4824/0/218
1.067
R1 = 0.0515, wR2 = 0.1487
R1 = 0.0823, wR2 = 0.1836
0.351 and −0.344
213702
---- ----
C3 C4 C5
C14 C15 O16 115.4(1)
---- ----
---- ----
C6 C5 C4
C9 C15 O16 123.6(1)
---- ----
θ range for data collection
Index ranges
---- ----
C5 C6 C1
C18 O16 C15 120.3(1)
---- ----
---- ----
C5 C6 C8
O17 C18 O16 123.3(1)
---- ----
---- ----
C1 C6 C8
O17 C18 C19 125.4(1)
---- ----
---- ----
O7 C8 C6
O16 C18 C19 111.3(1)
---- ----
Reflections collected
Independent reflections
Refinement method
---- ----
O7 C8 C9
C24 C19 C20 119.5(1)
---- ----
---- ----
C6 C8 C9
C24 C19 C18 121.9(1)
---- ----
---- ----
C15 C9 C10
C20 C19 C18 118.6(1)
---- ----
---- ----
C15 C9 C8
C21 C20 C19 120.0(2)
---- ----
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2σ(I)]
R indices (all data)
Largest diff. peak and hole (eA
CCDC deposit no.
---- ----
C10 C9 C8
C22 C21 C20 120.1(2)
---- ----
----
----
C12 C10 C9
---- ----
C23 C22 C21 120.5(2)
---- ----
C13 C12 C10 117.8(1)
---- ----
C22 C23 C24 119.9(2)
---- ----
C13 C12 C11 121.2(2)
---- ----
C19 C24 C23 120.0(2)
−3
˚
)
C10 C12 C11 121.0(2)
their coplanarity by 68.95(9)◦, 80.85(10)◦ and
54.98(9)◦, respectively. The maximum deviation
is 0.013(2) A for C14. The structure exhibits both
acceptable positions and were not refined. The
details of crystal data and refinement are given in
Table 1.
˚
intra and intermolecular interactions of the type
---
C H · · · O. The intermolecular interaction be-
---
tween atoms is as follows: C20 H20 · · · O7 has
Results and discussion
◦
˚
length 3.459(2) A and an angle of 172.14 , with
symmetry code 1 − x, 1 − y, −z, respectively.
The interaction with a neighbouring molecule is
related to the other by a centre of inversion and
form hydrogen bonded dimer units. Each unit is
independently stacked when viewed down a axis
(Fig. 2). The crystal structure shows intermolecu-
Table 2 gives the bond distances and angles
of non-hydrogen atoms respectively. The bond
distances and bond angles are in good agree-
ment with the standard values. Figure 1 repre-
sents the ORTEP25 diagram of the molecule 3
with thermal ellipsoids at 50% probability. The
title compound has independent planar phenyl
---
lar interactions (C H · · · O type) through hydro-
--- ---
ring systems, which are bridged via CO and
gen bonding of the carbonyl (benzophenone moi-
ety) and ester substituent. There appears to be an
--- ---
OCO groups, and inturn rotated away from

466
Mahendra et al.
Fig. 1. ORTEP of the molecule at 50% probability.
Fig. 2. Packing of the molecules down a axis. Dashed lines represent the hydrogen
bonds.

Synthesis and crystal structure of 2-benzoyl-4-methyl phenyl benzoate
467
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˚
---
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˚
---
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The authors would like to express their
thanks to DST, Government of India for finan-
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Also the author Mahendra, would like to thank
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Research Fellowship.
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