Synthesis, characterization and crystal structure of 1-phenyl-3-methyl-4- (salicylidene hydrazide)-phenylethylene-pyrazolone-5

Article abstract of DOI:10.1007/s10870-007-9282-x

A new compound 1-phenyl-3-methyl-4-(salicylidene hydrazide)-phenylethylene- pyrazolone-5 (PMPeP-SHZ) has been synthesized and characterized by elemental analysis, IR spectrum, MS and single crystal X-ray diffraction. The compound crystallizes in a monoclinic, space group P2(1)/c with cell parameters: a = 10.8275(19) A, b = 24.689(4) A, c = 9.7167(16) A and β = 95.127(4)°, Z = 4, S = 1.097. In the crystal structure, the compound presents in the diketo form. The structure exhibits both intra- and intermolecular hydrogen bonding and the molecules are interlinked through hydrogen bonds forming an infinite 2D network. The fluorescent result shows blue emission at room temperature in solid state.

Full text of DOI:10.1007/s10870-007-9282-x

J Chem Crystallogr (2008) 38:151–155
DOI 10.1007/s10870-007-9282-x
ORIGINAL RESEARCH
Synthesis, Characterization and Crystal Structure of 1-Phenyl-3-
methyl-4-(salicylidene hydrazide)-phenylethylene-pyrazolone-5
Li Zhang Æ Guan-Cheng Xu Æ Lang Liu Æ
Guang-Fei Liu Æ Dian-Zeng Jia
Received: 13 August 2007 / Accepted: 12 October 2007 / Published online: 24 October 2007
ꢀ Springer Science+Business Media, LLC 2007
Abstract A new compound 1-phenyl-3-methyl-4-(sali-
cylidene hydrazide)-phenylethylene-pyrazolone-5 (PMPeP-
SHZ) has been synthesized and characterized by elemental
analysis, IR spectrum, MS and single crystal X-ray dif-
fraction. The compound crystallizes in a monoclinic, space
potential antitumourals [5, 6], but also are the focus of
research as potential antifungal agrochemicals and widely
used as antiviral, antipyretic analgesic, anti-inflammatory
in medicine. Furthermore, 4-acyl pyrazolone derivatives
have a potential to form different types of coordination
compounds due to the several electron-rich donor centers
[7, 8] and tautomeric effect of enol form and keto form [9,
10]. Meanwhile compounds containing acylhydrazine
make a critical factor in a more rational approach to pre-
˚
group P2(1)/c with cell parameters: a = 10.8275(19) A,
˚
˚
b = 24.689(4) A, c = 9.7167(16) A and b = 95.127(4)ꢁ,
Z = 4, S = 1.097. In the crystal structure, the compound
presents in the diketo form. The structure exhibits both
intra- and intermolecular hydrogen bonding and the mol-
ecules are interlinked through hydrogen bonds forming an
infinite 2D network. The fluorescent result shows blue
emission at room temperature in solid state.
determining
molecular
architectures
using
as
polyfunctional ligands. They also possess biological
activities, especially serving as potential inhibitors for
many enzymes [11].
In our previous work, series of 4-acyl pyrazolone
derivatives and some transition metal complexes have been
reported [12–15] and one of recently results show that
copper complex [CuL(EtOH)] (L = 1-phenyl-3-methyl-4-
(salicylidene hydrazide)-propylidene-pyrazolone-5 anion)
might be a promising compound benefiting cancer che-
motherapy [16] which encourage us to further investigate
the structure and properties of the similar pyrazolone
derivatives. Herein this paper presents the synthesis and
crystal structure of a novel functional compound 1-phenyl-
3-methyl-4-(salicylidene hydrazide)-phenylethylene-pyr-
azolone-5.
Keywords Crystal structure Á Pyrazolone derivative Á
Salicylidene hydrazide Á Fluorescence property
Introduction
4-Acyl pyrazolones and their derivatives, reported to
behave as effective chelating and extracting reagents for
many metal ions [1, 2], not only play a key role in coor-
dination compounds which have wide application in
several fields, from new materials to catalysts [3], as pre-
cursors for CVD in the microelectronic industry [4] and as
Experimental
Electronic supplementary material The online version of this
article (doi:10.1007/s10870-007-9282-x) contains supplementary
material, which is available to authorized users.
Materials and Measurements
1-Phenyl-3-methyl-4-phenylacetyl-pyrazolone-5 and sali-
cylic hydrazide were synthesized according to the
references [17, 18]. Other chemicals and solvents were
analytical grade and commercially available.
L. Zhang Á G.-C. Xu Á L. Liu Á G.-F. Liu Á D.-Z. Jia (&)
Institute of Applied Chemistry, Xinjiang University,
Urumqi 830046, P.R. China
e-mail: jdz@xju.edu.cn
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J Chem Crystallogr (2008) 38:151–155
Elemental analyses of C, H and N were performed using a
Anal. Calcd. for C28H30N4O5 (%): C, 66.92; H, 6.02; N,
11.15. Found: C, 67.03; H, 6.10; N, 11.11. MS: m/z 425
(M–100.00), (PMPeP-SHZ formula weight: 426.47).
PE-240C analyzer. Melting point was measured with a
model Tech X-6 melting point apparatus. IR spectra were
recorded on a BRUKER EQUINOX-55 spectrophotometer
within 400–4,000 cm–1 with the samples prepared as pellets
with KBr. Mass spectra were obtained on an HP-5988 GC/
MS at an ionizing voltage of 110 eV by electron impact. The
crystal structure was determined by a Rigaku Mercury CCD
X-ray diffractometer. The emission and excitation spectra
were taken with a Hitachi F-4500 fluorescence spectropho-
tometer with a xenon arc lamp as the excitation light source.
Excitation and emission bandwidths of 2.5 nm were
employed and the fluorescence spectra were corrected for
nonlinear instrumental response and blank solvents.
Crystal Structure Determination
A crystal of PMPeP-SHZÁ(C3H6O)(H2O) having approxi-
mate dimension of 0.55 · 0.40 · 0.20 mm was placed on a
glass fiber and mounted on a Rigaku Mercury CCD X-ray
diffractometer. Diffraction data were collected at
193 1 K using graphite monochromated MoKa radiation
˚
(k = 0.71070 A). A multi-scan absorption correction was
performed. The structure was solved by direct methods and
all non-hydrogen atoms were refined anisotropically on F2
by the full-matrix least-squares technique using the
SHELXL-97 crystallographic software package [19]. The
crystallographic data and structure refinement parameters
of the titled compounds are summarized in Table 1.
CCDC: 282472
Synthesis and Basic Analytical Data
Approximately 20 mmol of 1-phenyl-3-methyl-4-pheny-
lacetyl-pyrazolone-5 was dissolved in 40 mL of hot
anhydrous ethanol. To which the ethanol solution of
equimolar salicylic hydrazide was slowly added with
constant stirring, adding a few drops of glacial acetic acid
as a catalyst. The mixture was stirred and further refluxed
for about 3 h. The yellow transparent reaction solution was
then concentrated to one-third of the initial volume by
rotary evaporation under reduced pressure. Then the pale
yellow precipitate was filtered off, washed with ethanol and
dried. Reaction mechanism is shown in Scheme 1.
Results and Discussion
IR Spectrum
The IR spectrum of the title compound shows a medium
intensity band around 3,247 cm–1, assigned to the hydrogen
bond NH and OH stretching vibrations [20], this is also
approved by the crystal structure analysis. The strong
absorption band at 1,659 and 1,639 cm–1 in the spectrum
are respectively allocated as t (C=O) of the hydarzide and t
Light-yellow block single crystals suitable for X-ray
diffraction analysis were obtained by slow evaporation of
its acetone solutions at room temperature. MP: 95–97 ꢁC.
Scheme 1 The reaction
mechanism of the compound
HO
HO
H3C
H3C
NH
O
OH
N
C
O
NH
H2N
C
O
+
N
N
OH
N
N
(I) enol-form
HO
H3C
NH
N
H
C
O
N
O
N
(II) keto-form
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J Chem Crystallogr (2008) 38:151–155
153
Table 1 Crystal data and structure refinements for PMPeP-
SHZÁ(C3H6O)(H2O)
CCDC No.
282472
Empirical formula
Formula weight
Temperature
C28H30N4O5
502.56
193.2 K
˚
Wavelength
0.71070 A
Monoclinic
P2(1)/c
Crystal system
Space group
˚
Unit cell dimensions
a = 10.8275(19) A, a = 90.00ꢁ
˚
b = 24.689(4) A, b = 95.127(4)ꢁ
˚
c = 9.7167(16) A, c = 90.00ꢁ
3
2587.1(7) A , 4
˚
Volume, Z
Density (calculated)
Absorption coefficient
F(000)
1.290 g cm–3
0.090 mm–1
1,064
Fig. 1 Molecular structure of PMPeP-SHZÁ(C3H6O)(H2O) with
Reflections collected
Independent reflections (Rint
25,433
intramolecular hydrogen bonds(30% thermal ellipsoids)
)
5,076 (0.0447)
4,215
Observed reflections (I [ 2r(I))
Absorption correction
˚
Multi-scan
Full-matrix least-squares on F2
Table 2 Selected bond lengths (A) and angles (ꢁ) for PMPeP-
SHZÁ(C3H6O)(H2O)
O(1)–C(7)
Refinement method
Goodness-of-fit on F2
1.097
1.242(2)
1.353(2)
1.324(2)
1.432(3)
1.385(2)
O(2)–C(19)
N(2)–C(9)
C(7)–C(8)
C(8)–C(11)
N(4)–C(19)
1.229(2)
Final R indices [I [ 2r(I)]
Largest diff. peak and hole
R1 = 0.0526, xR2 = 0.1509
˚
0.313 and –0.281 e A
O(3)–C(25)
N(3)–C(11)
C(8)–C(9)
1.309(2)
–3
1.443(2)
1.396(2)
N(3)–N(4)
1.349(2)
(C=O) of pyrazolone-ring [21, 22]. The strong absorption
band at 1,495 cm–1 is assigned to the stretching vibration of
pyrazolone-ring [23]. Meanwhile, the vibration t (C=O) of
acetone in the spectrum shows a band around 1,704 cm–1.
From above data analysis, it is concluded that the ligand is
mainly present in diketone form (Scheme 1 form II) in the
solid state.
O(1)–C(7)–N(1)
O(2)–C(19)–N(4)
125.76(16) O(1)–C(7)–C(8)
120.65(16) O(2)–C(19)–C(20)
129.70(16)
121.85(15)
121.55(16)
111.56(14)
111.18(15)
122.43(15)
117.98(15)
117.50(14)
121.56(15)
130.88(16)
O(3)–C(25)–C(20) 118.92(15) O(3)–C(25)–C(24)
N(1)–N(2)–C(9)
N(1)–C(7)–C(8)
N(2)–C(9)–C(10)
N(3)–N(4)–C(19)
106.99(14) C(7)–N(1)–N(2)
104.54(14) N(2)–C(9)–C(8)
117.93(17) C(11)–N(3)–N(4)
118.59(14) N(3)–C(11)–C(8)
N(3)–C(11)–C(12) 117.68(16) N(4)–C(19)–C(20)
Crystal Structure Analysis
C(7)–C(8)–C(9)
C(11)–C(8)–C(9)
105.73(15) C(7)–C(8)–C(11)
132.70(16) C(8)–C(9)–C(10)
A perspective view of the title compound including the
atomic numbering scheme is shown in Fig. 1. The selected
bond distances and bond angles are summarized in Table 2.
X-ray diffraction analysis reveals that the structure consists
of the compound PMPeP-SHZ, one crystalline acetone and
one water molecule. It is obvious that the C19–O2 with a
C(8)–C(11)–C(12) 124.34(16) C(11)–C(12)–C(13) 112.52(14)
˚
character. While the C11–N3 bond distance is 1.324(2) A,
slightly shorter than the normal C–N bond distance. Thus,
elongation of the C–N (C11–N3) bond and shrinkage of the
C–C (C8–C11) bond are observed, which suggests a more
large conjugate system is formed between the pyrazolone-
ring and the side chain group. These are convincing evidence
that PMPeP-SHZ does not adopt Schiff base. However, we
consider that PMPeP and SHZ form firstly the Schiff base
and intramolecular hydrogen bond (O1–HÁÁÁN3) present in
the tautomer I in Scheme 1. The hydrogen atom of O1 can
then transfer to N3 atom under the proper condition.
Therefore the other intramolecular hydrogen bond (O1ÁÁÁH–
N3) formed, which shows proton transfer in the compound
˚
bond length of 1.229(2) A is in good agreement with the
C=O double bond and C7–O1 bond is close to double bond
˚
with bond distance of 1.242(2) A [24]. While the C25–O3
˚
bond distance in salicylidene is 1.353(2) A, slightly shorter
than the normal C–O single bond distance. The C9–N2 bond
˚
distance value of 1.309(2) A consists well with the C=N
double bond distance. All of these demonstrate that the keto
tautomer is favoured over the enol form for the title com-
˚
pound. Similarly, the bond length of C8–C11 is 1.396(2) A
which is indicative of significant conjugate double bond
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J Chem Crystallogr (2008) 38:151–155
C7–C12) is nearly planar with the mean derivation of
˚
0.0150 A. The dihedral angle between plane I and plane II
Table 3 Dihedral angles of PMPeP-SHZÁ(C3H6O)(H2O)
Plane
Dihedral angle (ꢁ)
(defined by C19–C25 and O3) is 52.30ꢁ. The dihedral angle
between plane I and III is 25.61ꢁ. Furthermore, the plane
IV is nearly vertical to plane I with the dihedral angle of
78.99ꢁ. These data reveal that the whole molecule is non-
planar.
I
II
III
I{N1, N2, C7, C8,
C9, C10, C11,
C12, N3, N4, O1}
II{C19–C25, O3}
III{C1–C6}
52.30 (0.04)
25.61 (0.08)
78.99 (0.05)
The geometrical parameters of the intra- and intermo-
lecular hydrogen bonds observed in the structure are listed
in Table 4. The crystal packing diagram is shown in Fig. 2.
There are both intra- and intermolecular hydrogen bonds in
the structure, which helps in stabilizing the structure.
Hydrogen bonding involving the O1 atom is trifurcated. O1
forms two intramolecular hydrogen bonds with the HN3 of
the a amino moiety and HC6 of the benzene ring (N3ÁÁÁO1,
37.29 (0.07)
52.54 (0.06)
IV{C13–C18}
77.45 (0.06)
Table 4 Hydrogen bonds of PMPeP-SHZÁ(C3H6O)(H2O)
D–HÁÁÁA
HÁÁÁA
DÁÁÁA
D–HÁÁÁA
N4–HÁÁÁO3
2.02(2)
1.92(2)
1.89(4)
2.5300
2.4100
2.00(3)
1.70(3)
2.09(2)
2.639(2)
2.676(2)
2.797(2)
3.209(3)
2.966(2)
2.860(2)
2.621(2)
2.795(2)
127.2(19)
140.0(17)
166(4)
˚
˚
2.676(2) A, 140.0(17)ꢁ and C6ÁÁÁO1, 2.966(2) A, 117.00ꢁ),
N3–HÁÁÁO1
and one intermolecular hydrogen bond with the C27 atom
˚
O5–HÁÁÁO4
of acetone molecule (C27ÁÁÁO1, 3.209(3) A, 126.00ꢁ).
C27–HÁÁÁO1
C6–H5ÁÁÁO1
O5–HÁÁÁN2#1
O3–H26ÁÁÁO5#2
N4–H27ÁÁÁO2#2
126.00
Furthermore, the hydrogen of amino atom N4 forms a
117.00
hydrogen bond with hydroxyl O3 atom (N4ÁÁÁO3,
177(3)
˚
2.639(2) A, 127.2(19)ꢁ). The intramolecular hydrogen
177.5(16)
136.9(19)
bond link N4H–C19–C20–C25–O3 to form pseudo-six
membered ring. The water molecule donates its protons to
oxygen atom O4 of acetone and N2B of the neighboring
PMPeP-SHZ forming two intermolecular hydrogen bonds
O5–HÁÁÁO4 and O5–HÁÁÁN2B of lengths (2.797(2) and
D—donor; A—acceptor; H—hydrogen
Symmetry code: #1: –1 + x, y, z; #2: x, 1/2 – y, –1/2 + z
˚
and the tautomer I change to the tautomer II. The IR spectrum
of the compound also confirmed the findings.
2.860(2) A) and angles (166(4)ꢁ and 177(3)ꢁ). Further-
more, the oxygen atom O3 is intermolecularly hydrogen-
bonded to the O5 atom, with an O3ÁÁÁO5 contact of
2.621(2). Through the intra- and intermolecular hydrogen
Dihedral angles of main planes in the structure are listed
in Table 3. The plane I (defined by N1–N4, O1 and
Fig. 2 Crystal packing diagram
of PMPeP-SHZÁ(C3H6O)(H2O).
Dashed lines represent the
hydrogen bonds
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J Chem Crystallogr (2008) 38:151–155
155
35
30
25
20
15
10
5
the Scientific Research Foundation in Xinjiang Educational Institu-
tions (XJEDU2005S01) and Young Scholar Science Foundation of
Xinjiang Educational Institutions (XJEDU2004E01).
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CCDC: 282472 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge at http://www.ccdc.cam.ac.uk/conts/retrieving.
html [or from the Cambridge Crystallographic Data Center
(CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax:
+44(0)1223-336033; e-mail: deposit@ccdc.cam.ac.uk].
Acknowledgements This work was supported by the National
Natural Science Foundation of China (No. 20366005 and 20462007),
123