Supramolecular structure of 1-phenyl-3-methyl-4-benzoylpyrazolon-5-one

Article abstract of DOI:10.14233/ajchem.2013.14437

The compound 1-phenyl-3-methyl-4-benzoylpyrazolon-5-one with the molecular formula C₁₇H14N₂O₂, exists in a keto-enamine tautomeric form. The pyrazolone ring makes dihedral angles of 28.36(3) and 59.31(5) with the two phenyl rings. The molecules are linked into twodimensional supramolecular structure by a combination of N-H···O and C-H···O hydrogen-bonding interactions.

Full text of DOI:10.14233/ajchem.2013.14437

Asian Journal of Chemistry; Vol. 25, No. 13 (2013), 7527-7528
http://dx.doi.org/10.14233/ajchem.2013.14437
NOTE
Supramolecular Structure of 1-Phenyl-3-methyl-4-benzoylpyrazolon-5-one
*
LI XU, ZHENG-KUN WANG, YIN-XIA SUN , YU-JIE ZHANG and XIU-YAN DONG
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R. China
Corresponding author: E-mail: sun_yinxia@163.com
Received: 16 August 2012;
*
(
Accepted: 5 July 2013)
AJC-13767
The compound 1-phenyl-3-methyl-4-benzoylpyrazolon-5-one with the molecular formula C17
H
14
N
2
2
O , exists in a keto-enamine tautomeric
form. The pyrazolone ring makes dihedral angles of 28.36(3) and 59.31(5)º with the two phenyl rings. The molecules are linked into two-
dimensional supramolecular structure by a combination of N-H···O and C-H···O hydrogen-bonding interactions.
Key Words: 1-Phenyl-3-methyl-4-benzoylpyrazolon-5-one, Supramolecular structure.
1-Phenyl-3-methyl-4-benzoylpyrazolon-5-one, an effec-
calcd. (%) for C17
H
14
N
2
O : C, 73.25; H, 5.04; N, 10.01. Found
2
tive β-diketonate, is widely used and well known for its
(%): C, 73.37; H, 5.07; N, 10.07.
1
-3
extractive ability . In recent years, its metal complexes have
also been found to have good antibacterial and biological prop-
Colourless needle-like single crystals suitable for X-ray
diffraction studies were obtained by slow evaporation from a
solution of dichloromethane at room temperature over a period
of approximately one month.
4
-6
erties. Its metal complexes have analgesic activity . For our
interest in super supramolecular chemistry, herein we've mainly
studied the supramolecular structure of the this compound.
TABLE-1
1
-Phenyl-3-methyl-5-pyrazolone was purchased from
CRYSTAL DATA AND REFINEMENT PARAMETERS
FOR THE TITLE COMPOUND
Alfa Aesar and used without any purification. The reagents
and solvents were analytical grade reagents from Tianjin
Chemical Reagent Factory. C, H and N analyses were carried
out with a GmbH VariuoEL V3.00 automatic elemental
analyzer. Melting points were measured by the use of a
microscopic melting point apparatus made in Beijing Taike
Instrument Limited Company and the thermometer was
uncorrected. X-Ray single crystal structure was determined
on a Bruker Smart APEX CCD area detector.
Empirical formula
Formula weight
Temperature
C H N O
17 14 2 2
278.30
298(2) K
Wavelength
0.71073 Å
Crystal system
Space group
Monoclinic
P2(1)/c
Cell dimensions
a = 13.4824(16) Å, b = 9.1016(11) Å,
c =11.4348(12) Å, β = 90.8170(10)
3
Volume
871.56(18) Å
General procedure: 1-Phenyl-3-methyl-5-pyrazolone
Z
4
3
(
3.75 g) was dissolved in 80 mL of 1,4-dioxane by heating.
Density (calculated)
Absorption coefficient
1.318 mg/m
0.088 mm
584
-1
Calcium hydroxide (6 g) was added followed by addition of
benzoyl chloride (3 mL) dropwise within 1 min. The tempe-
rature increased during the first few minutes and the reaction
mixture became a thick paste. The reaction mixture was
refluxed for 0.5 h. Calcium complex of the desired ligand
formed in the flask was decomposed by pouring the mixture
into dilute hydrochloric acid (50 mL). An orange precipitate
was formed slowly. It was filtered under suction, washed with
a little water and 1,4-dioxane and recrystallised from a slightly
acidified methanol-water mixture to destroy any undecom-
posed calcium complex. Yield 79.8 %. m.p. 89-91 ºC. Anal.
F(000)
Index ranges
-16 ≤ h ≤ 14, -10 ≤ k ≤ 9, -13 ≤ l ≤ 13
6863 / 2472 [Rint = 0.0548]
2472 / 0 / 192
Reflections collected/unique
Data/restraints/parameters
Goodness of fit indicator
Final R indices [I > 2σ(I)]
R indices (all data)
1.030
R =0.0468, wR
1
=0.1080
2
R =0.0858, wR =0.1371
1
2
-3
Largest diff. peak and hole
0.299 and -0.229 e Å
X-Ray structure determination: The single crystal of
the title compound with approximate dimensions of 0.45 mm

7
628 Xu et al.
Asian J. Chem.
TABLE-2
SELECTED BOND LENGTHS (Å) AND ANGLES (º) FOR THE TITLE COMPOUND
Bond
Lengths
Bond
Lengths
Bond
Lengths
N(1)-N(2)
N(1)-C(1)
N(1)-C(5)
N(2)-C(3)
C(6)-C(7)
C(7)-C(8)
C(8)-C(9)
C(9)-C(10)
1.377(3)
1.391(3)
1.418(3)
1.330(3)
1.375(4)
1.349(5)
1.370(5)
1.390(4)
O(1)-C(1)
O(2)-C(11)
C(1)-C(2)
1.247(3)
1.224(3)
1.433(3)
1.381(3)
1.490(3)
1.384(3)
1.385(3)
1.380(3)
C(2)-C(11)
C(3)-C(4)
C(5)-C(10)
C(5)-C(6)
C(14)-C(15)
C(15)-C(16)
C(16)-C(17)
–
1.466(3)
1.484(3)
1.371(4)
1.372(4)
1.372(4)
1.380(4)
1.382(4)
–
C(2)-C(3)
C(11)-C(12)
C(12)-C(17)
C(12)-C(13)
C(13)-C(14)
Bond
Angles
Bond
Angles
Bond
Angles
N(2)-N(1)-C(1)
C(3)-N(2)-N(1)
O(1)-C(1)-N(1)
C(3)-C(2)-C(1)
C(7)-C(8)-C(9)
C(8)-C(9)-C(10)
C(5)-C(10)-C(9)
O(2)-C(11)-C(2)
108.78(18)
109.26(19)
122.4(2)
107.3(2)
119.2(3)
120.6(3)
119.2(3)
120.5(2)
N(2)-N(1)-C(1)
C(3)-N(2)-N(1)
O(1)-C(1)-N(1)
108.78(18)
109.26(19)
122.4(2)
107.3(2)
119.9(2)
119.6(2)
118.6(2)
122.0(2)
C(2)-C(3)-C(4)
C(10)-C(5)-C(6)
C(5)-C(6)-C(7)
132.4(2)
120.1(2)
119.4(3)
121.6(3)
119.3(2)
119.9(3)
119.9(3)
120.7(2)
C(3)-C(2)-C(1)
C(8)-C(7)-C(6)
O(2)-C(11)-C(12)
C(2)-C(11)-C(12)
C(17)-C(12)-C(13)
C(17)-C(12)-C(11)
C(13)-C(12)-C(11)
C(14)-C(15)-C(16)
C(15)-C(16)-C(17)
C(16)-C(17)-C(12)
×
0.17 mm × 0.14 mm was placed on a Bruker Smart 1000
diffractmeter equipped withApex CCD area detector. The diff-
raction data were collected using a graphite monochromated
MoK radition (λ = 0.71073 Å) at 298(2) K. The structure
α
7
was solved by using the program SHELXS-97 and Fourier
difference techniques and refined by full-matrix least-squares
2
8
method on F using SHELXL-97 . Details of the data collection
and refinements of the title compound are given in Table-1.
The non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were added theoretically. CCDC: 894881.
The structure of the title compound is shown in Fig. 1. The
dihedral angles formed by the pyrazolone ring with the two
phenyl rings C5-C10 and C12-C17 are 28.36(3) and 59.31(5)º,
respectively. Two carbonyl oxygen atoms are available for coor-
dination with metals. The pyrazolone ring is planar and atoms
O1, N1, N2, C1, C2, C3, C4 and C11 are almost coplanar, the
largest deviation being 0.035 (3) Å for atom O1. But the O2
atom is not on the mean plane with a deviation of 0.652(2) Å.
The dihedral angle between this mean plane and the pyrazolone
ring of 1-phenyl-3-methyl-4-benzoylpyrazolon-5-one is 0.39(1)°.
A strong intermolecular N2-H2···O1 hydrogen bond (Table-2)
stabilized the molecules into a 1D infinite chain parallel to the c-
Fig. 2. View of the supramolecular structure within the title compound
hydrogen atoms, except those forming hydrogen bonds, are omitted
for clarity)
(
ACKNOWLEDGEMENTS
This work was supported by the Foundation of Preparative
Research of Jin-Chuan Corporation (No. 209125-1102, 1103).
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Fig. 1. Molecule structure of the title compound