Crystal structure of 3-chloromethyl-(3-phenyl-oxiranyl)phenyl methanone: New monoclinic polymorph

Article abstract of DOI:10.14233/ajchem.2014.16095

The compound, 3-chloromethyl-(3-phenyl-oxiranyl)phenyl methanone [m.f. C16H13O2Cl] was a self-condensation product of phenacyl chloride where the reaction carried out in ethanol medium using inorganic base. This was crystalized in monoclinic with space group P2₁/c (no. 14), a = 10.1312 (2) ?, b = 11.7728 ?, c = 11.8566 ?, V = 1344.07 ?3, Z = 4 and ρ_calc. = 1.348 mg/mm₃. The dihedral angle between two aromatic rings is 73.46 (5). The epoxide ring is oriented at dihedral angles of 62.12 (9°) and 60.87 (7°) with respect to the phenyl and benzoyl rings. The non-classical intermolecular hydrogen bonding of C-HO type has been observed in the crystal structure of molecule.

Full text of DOI:10.14233/ajchem.2014.16095

Asian Journal of Chemistry; Vol. 26, No. 9 (2014), 2715-2717
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.16095
Crystal Structure of 3-Chloromethyl-(3-phenyl-oxiranyl)phenyl
Methanone: New Monoclinic Polymorph
1,2
1
1
MUHAMMAD NADEEM ARSHAD1,2,*, ABDULLAH M. ASIRI , KHALID A. ALAMRY , SALIH S. AL-JUAID ,
1,2
3
3
SHER BAHADAR KHAN , TANVEER HUSSAIN BOKHARI and MUHAMMAD SHAFIQ
1Chemistry Department, King Abdulaziz University, Jeddah 21589, Saudi Arabia
2Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, Jeddah 21589 Saudi Arabia
3Department of Chemistry, Government College University Faisalabad, Faisalabad, Pakistan
*Corresponding author: Tel: +966 580330428, E-mail: mnachemist@hotmail.com
Received: 24 July 2013;
Accepted: 6 December 2013;
Published online: 28 April 2014;
AJC-15104
The compound, 3-chloromethyl-(3-phenyl-oxiranyl)phenyl methanone [m.f. C16H13O2Cl] was a self-condensation product of phenacyl
chloride where the reaction carried out in ethanol medium using inorganic base. This was crystalized in monoclinic with space group
P21/c (no. 14), a = 10.1312 (2) Å, b = 11.7728 Å, c = 11.8566 Å, V = 1344.07 Å3, Z = 4 and ρcalc. = 1.348 mg/mm3. The dihedral angle
between two aromatic rings is 73.46 (5). The epoxide ring is oriented at dihedral angles of 62.12 (9°) and 60.87 (7°) with respect to the
phenyl and benzoyl rings. The non-classical intermolecular hydrogen bonding of C-H···O type has been observed in the crystal structure
of molecule.
Keywords: 3-Chloromethyl-3-phenyl-oxiranyl)phenyl methanone, Crystal structure, New polymorph.
methanone is also epoxy ketone and synthesized via self-
condensation of phenacyl chloride in the presence of sodium
hydroxide as base and crystalized in ethanol under slow evapo-
ration, Scheme-I. The crystal structure is being reported here
as another monoclinic polymorph of 3-chloromethyl-(3-phen-
yloxiranyl)phenyl methanone.
INTRODUCTION
The C-C bond formation is always been well knownchemistry
for the preparation of new organic compounds with novel
various properties. Darzens' reaction is also one of them which
used for C-C bond formation in synthetic branch of organic
chemistry1,2. This reaction also allows to prepare α,β-epoxy
carbonyl derivatives with new stereocenters via diastereo-
control mechanism. These condensation reactions are carried
out in the presence of strong base while organic solvents usually
used as medium3. In order to meet the modern methodologies
for betterment of environment and more socio-economic benefits
phase transfer catalyst (PTC) have also been applied as catalyst4-6.
Wang et al.7 reported the Darzens condensation reaction of
ethyl acetate with different aldehydes using newly synthesized
polystyrene-based quaternary ammonium compounds as catalysts.
The pharmaceutical significance (synthesis of diltiazem; a blood
pressure lowering drug) of Darzens reactions vindicates the
special consideration of researchers8,9. The epoxy ketones, both
in their racemic as well as optically active forms are considered
as useful building blocks for the synthesis of various organic
compounds10. The two active functionalities (keto and epoxy)
can be further derivatized to yield potential intermediates of
natural, industrial and biologically active compounds11-13. The
title compound i.e., 3-chloromethyl-(3-phenyl-oxiranyl)phenyl
Cl
O
H
Cl
NaOH
O
Aq. ethanol
O
1
2
Scheme-I: Synthesis of 3-chloromethyl-(3-phenyl-oxiranyl)phenyl
methanone (2)
EXPERIMENTAL
The phenacyl chloride (1 g, 6.47 mmol) was added to
aqueous ethanolic solution (1 : 1) of sodium hydroxide (0.52 g,
12.93 mmol) and the mixture was allowed to stir at room tempe-
rature for 2 h. The precipitate obtained was filtered off, washed
with cold water and recrystallized in ethanol under slow
evaporation to obtain a suitable crystal for X-ray diffraction
studies. The 1H NMR was recordede on BrukerAvance 600 MHz
spectrometer (Bruker, Germany), in CDCl3 as solvent. The values

2716 Arshad et al.
Asian J. Chem.
TABLE-1
CRYSTAL DATA AND STRUCTURE REFINEMENT FOR 2
of proton are reported as chemical shifts (δ, ppm) along-with
their multiplicity (s, singlet; d, doublet; t, triplet; q quartet)
relative to the residual CDCl3 (7.26 ppm). The melting point
was recorded on Stuart scientific SMP3 (Bibby, UK) melting
point apparatus and is reported as uncorrected.
Empirical formula
C16H13O2Cl
272.71
296.15
Formula weight
Temperature (K)
Crystal System
monoclinic
1H NMR (600 MHz) (CDCl3)δ: 7.89 (2H, d, aromatic), 7.57
(1H, t, aromatic), 7.40 (2H, t, aromatic), 7.35 (2H, q, aromatic),
7.22 (2H, d, aromatic), 7.21 (1H, d, aromatic), 4.65 (1H, s, CH),
4.08 (2H, s, CH2). m.p. 152-153 °C.
Space group
P21/c
α (Å)
10.1312 (2)
11.7728 (2)
β (Å)
c (Å)
11.8566 (3)
108.116 (3)
1344.07 (5)
β (o)
Crystallization of compound 2 in ethanol under slow evapo-
ration gave colorless, block type crystals. A suitable crystal
was selected and mounted on an Agilent Super Nova Atlas
Dual Source, Agilent Technologies diffractometer using the
CrysAlis Pro software14. The crystal was kept at 296 K during
data collection. Using Xseed15, the structure was solved with
the ShelXS16 structure solution program using direct methods
and refined with the ShelXL16 refinement package using least
squares minimization.All the hydrogen atoms were positioned
geome-trically with dCaromatic-H = 0.93 Å, dCchiral-H = 0.97 Å
& dCmethylene-H = 0.98 Å and were refined using a riding model
with Uiso(H) = 1.2 Ueq(C). The figures were drawn with the help
of PLATON17 using WinGX18. The crystal data was deposited
at the Cambridge Crystallographic Data Centre and it has been
assigned the deposition number as CCDC 940725. This data can
be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/
cif.
Volume (Å3)
Z
4
ρcalcmg (mm3)
1.348
568.0
F(000)
Crystal size (mm3)
2θ range for data collection
Index ranges (h, k, l)
Reflectioned collected
Independent reflections
Data/restraints/parameters
Goodness-of-fit on F2
Final R indexes [I > = 2σ (I)]
Final R indexes [I > = 2σ (I)]
Largest diff. peak/hole / e Å-3
0.48 × 0.17 × 0.08
9.18 to 152.72o
-11≤ h≤12, -14≤k≤14,-14≤l≤12
12607
2789[R(int) = 0.0355]
2789/0/173
1.053
R1 = 0.0353, wR2 = 0.0967
R1 = 0.0392, wR2 = 0.1014
0.20/-0.26
TABLE-2
SELECTED BOND LENGTHS OF COMPOUND 2
Atom
Atom
Length (Å)
Cl1
O1
O1
O2
C1
C1
C1
C2
C3
C4
C4
C16
C1
C2
C3
C2
C10
C16
C3
C4
C5
1.7886(15)
1.4349(15)
1.4284(17)
1.2162(17)
1.4914(19)
1.4955(19)
1.504(2)
1.500(2)
1.4821(19)
1.390(2)
1.386(2)
RESULTS AND DISCUSSION
The title compound was synthesized through a simple self-
condensation using inorganic base and recrystallized in ethanol
as a new monoclinic polymorph. The cambridge structural
database (CSD)19 speaks about two other polymorphs20 with
codes QECFAF and QECFEJ. The spectroscopic and crystallo-
graphic studies were taken out for the characterization of
product. According to the 1H NMR spectra of molecule it is
clear that the hydrogen atoms of the benzoyl rings appear
in the downfield region [7.89 (2H, d, aromatic), 7.57 (1H, t,
aromatic), 7.40 (2H, t, aromatic)] due to the de-shielding effect
of carbonyl group. On the other hand, five hydrogen atoms of
phenyl ring are appeared at 7.35 (2H, dd, aromatic), 7.22 (2H,
d, aromatic) and 7.21 (1H, dd, aromatic). The singlet peak of
the hydrogen atom attached to chiral carbon C2 appeared at
4.65 while the two hydrogen atoms of methylene CH2 group
appeared at 4.08. The Table-1 contains the detail of the crystal
data, data collection and structure refinements. Selected
bond lengths and bond angles are provided in Tables 2 and 3,
respectively. The ORTEP diagram of molecule 2 is shown in
Fig. 2, it reveals that the molecule contain two aromatic rings
(C4---C9) & (C10---C15) with root mean square (r.m.s)
deviation of 0.0018 (1) Å & 0.0033 (1) Å of the planes produced
from their atoms respectively. The oxirane ring (C1/C2/O2) is
exactly planer with 0.000 Å r.m.s. deviation of its fitted. The
three bond angles produced from fitted atoms are 62.78 (8°),
58.39 (8°) and 58.82 (8°).
C9
TABLE-3
SELECTED BOND ANGLES OF COMPOUND 2
Atom
Atom
Atom
C1
C2
C10
C16
C10
C16
C16
C1
C3
C3
C2
C4
Angle (°)
62.78(8)
58.39(8)
C2
O1
O1
O1
C2
C2
C10
O1
O1
C1
O2
O2
C4
C5
C9
O1
C1
C1
C1
C1
C1
C1
C2
C2
C2
C3
C3
C3
C4
C4
115.42(11)
114.29(11)
120.77(11)
115.83(12)
117.96(11)
58.82(8)
117.50(12)
120.21(12)
120.60(13)
121.99(13)
117.42(12)
123.09(13)
118.23(13)
C2
C3
C3
60.87 (7°) with respect to the phenyl (C10---C15) and benzoyl
(C4---C9) rings. The non-classical C---H···O type inter-
molecular hydrogen bonding have also been observed in the
molecule which may help to stabilize the crystal structure of
molecule Fig. 3 and Table-4. This interaction connects the
molecules along c-axes to make an infinite chain.
The dihedral angle between the plane produce through
the bonded atoms of two aromatic rings is 73.46 (5°). The
eoxirane ring is oriented at dihedral angle of 62.12 (9°) and

Vol. 26, No. 9 (2014)
Crystal Structure of 3-Chloromethyl-(3-phenyl-oxiranyl)phenyl Methanone 2717
TABLE-4
HYDROGEN BOND GEOMETRY (Å, O)
D-H…A
D-H
0.97
H…A
2.44
D…A
3.3750(19)
D-H…A
160.6
Symmetry code / symmetry operation
4_565 / iX, 1/2-Y, Z-1/2
C16-H16A … O2i
ACKNOWLEDGEMENTS
This project was funded by the Deanship of Scientific
Research (DSR), King Abdulaziz University, Jeddah, under
grant no. (169/130/1433). The authors, therefore, acknowledged
with thanks DSR technical and financial support.
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Fig. 3. Unit cell packing of compound 2 showing the hydrogen bonding
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