Synthesis, structure and supramolecular properties of 1,7′-bis[4-(3-methyl-2,3-dihydro-pyrazol-1-yl)phenol]-1,4,7-trioxaheptane

Article abstract of DOI:10.14233/ajchem.2015.17871

A new pyrazole derivative, 1,7′-bis[4-(3-methyl-2,3-dihydro-pyrazol-1-yl)phenol]-1,4,7-trioxaheptane with m.f. C₂₄H₂₄N₄O₅ has been synthesized and the crystal structure was determined by single crystal X-ray diffraction. Interestingly, the title compound are linked by intermolecular O2-H22?N2 hydrogen bonds into a 36 atoms' macro-ring which is further held together into one dimensional beaded chain via C-H?O hydrogen bonding between another phenol oxygen atom and one methylene carbon atom.

Full text of DOI:10.14233/ajchem.2015.17871

Asian Journal of Chemistry; Vol. 27, No. 4 (2015), 1339-1341
A
SIAN
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OURNAL OF HEMISTRY
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http://dx.doi.org/10.14233/ajchem.2015.17871
Synthesis, Structure and Supramolecular Properties of
1,7'-bis[4-(3-Methyl-2,3-dihydro-pyrazol-1-yl)phenol]-1,4,7-trioxaheptane
*
BAO-YONG LIU , BIN ZHANG and XI YANG
School of Chemical and Biological Engineering, Lanzhou Jiaotong University, Lanzhou 730070, P.R. China
*Corresponding author: Fax: +86 931 4938755; Tel: +86 931 4938795; E-mail: liuby@mail.lzjtu.cn
Received: 22 April 2014;
Accepted: 11 June 2014;
Published online: 4 February 2015;
AJC-16787
A new pyrazole derivative, 1,7'-bis[4-(3-methyl-2,3-dihydro-pyrazol-1-yl)phenol]-1,4,7-trioxaheptane with m.f. C24H24N4O5 has been
synthesized and the crystal structure was determined by single crystal X-ray diffraction. Interestingly, the title compound are linked by
intermolecular O2–H22···N2 hydrogen bonds into a 36 atoms' macro-ring which is further held together into one dimensional beaded
chain via C–H···O hydrogen bonding between another phenol oxygen atom and one methylene carbon atom.
Keywords: Synthesis, Crystal structure, Supramolecular properties, Pyrazole.
carboxamide derivatives that exhibited potent antiproliferative
activities against HTC116, MCF-7 cells and Aurora-A kinase
inhibitory activities.
In view of the above-mentioned facts, we report herein
the syntheses and crystal structure of a new pyrazole derivative.
INTRODUCTION
The pyrazole ring is an important heterocyclic core
structure in a large number of biologically active compounds.
The spectrum of pharmaceutical action of pyrazole derivatives
encompasses, for example, substances acting on the central
nervous system, pharmacodynamic agents, drugs aimed at
metabolic diseases and chemotherapeutics1. Its derivatives are
also reported to have a broad spectrum of biological activities,
such as antitumour2, anticoagulant3, antihyperglycemic,
analgesic, antipyretic, antimicrobial and hypoglycaemic
activity4-8.Arylpyrazoles are important in medicinal and pesti-
cidal chemistry9,10. Some arylpyrazoles have non-nucleoside
HIV-1 reverse transcriptase inhibitory activity11. Li et al.12
have reported a series of N,1,3-triphenyl-1H-pyrazole-4-
EXPERIMENTAL
Commercially available chemicals were of analytical
grade and were used without further purification. X-ray single
crystal structure was determined on a Bruker Smart 1000 CCD
area detector. Melting points were determined on a Kofler
apparatus and the thermometer was uncorrected.
Synthesis of 1,7'-bis[4-(3-methyl-2,3-dihydro-pyrazol-
1-yl)phenol]-1,4,7-trioxaheptane: The synthetic route for the
compound is shown in Scheme-I. 2N NaOH was added to
2N NaOH
.
O
NHNH
O
NHNH
2
HCl
2
N
O
N
AcOH
Reflux
+
O
O
O
O
HO
OH
N
K CO
2
3
O
O
N
N
HO
N
TsO
OTs
+
O
DMF
N
N
O
O
Scheme-I: Synthetic route of the title compound

1340 Liu et al.
Asian J. Chem.
TABLE-1
CRYSTAL DATA AND STRUCTURE
REFINEMENT FOR THE TITLE COMPOUND
a clear aqueous solution of 10 g 4-methoxy-phenylhydrazine
hydrochloride to give 4-methoxyphenylhydrazine as a pale
white solid. 2-(4-Methoxy-phenyl)-5-methyl-2,4-dihydro-
pyrazol-3-one, 2-(4-hydroxy-phenyl)-5-methyl-2,4-dihydro-
pyrazol-3-one and diethylene glycol di-p-tosylate was prepared
according to the literature methods13,14, respectively.
To a stirred solution of 2-(4-hydroxy-phenyl)-5-methyl-
2,4-dihydro-pyrazol-3-one ( 1.98 g, 10.5 mmol) in dry DMF
was added 1.52 g (11 mmol) dried K2CO3 and the mixture
was stirred for 0.5 h at room temperature, then 2.07 g (5 mmol)
diethylene glycol di-p-tosylate in 20 mL of dry DMF was added
dropwise in 0.5 h and the resulting solution stirred and heated
to reflux for 24 h. After cooling down, inorganic salts were
separated by filtration and the solvent removed from the filtrate
under reduced pressure. The crude product was recrystallized
with ethanol to give a white solid 1.03 g, Yield 46 %, m.p.
245-246 °C. The title compound (0.045 g, 0.1 mmol) was
dissolved in ethanol (10 mL) and sealed for crystallization at
room temperature.After about three weeks colourless crystals
suitable for analysis were obtained.
Empirical formula, formula weight C24 H26 N4 O5, 450.49
Temperature (K), wavelength (Å)
Crystal system, space group
Unit cell dimensions, (Å, deg)
293(2), 0.71073
Monoclinic, C2/c
20.720(10), 90.00
12.431(6), 112.89(3)
19.655(13), 90.00
Volume (Å3), Z, calculated density 4664(4), 8, 1.283kg/m3
Absorption coefficient (mm-1)
Index ranges, hkl
0.091
-26≤h≤16, -16≤k≤15,
-25≤k≤25
1.95–27.42
5263/2894
5263/6/320
θ range for data collection (°)
Reflections collected/unique
Data/restraints/parameters
Independent reflections (Rint)
Goodness-of-fit indicator on F2
0.0669
0.952
R1 = 0.0664, wR2 = 0.1701
R1 = 0.1642, wR2 = 0.2243
Final R indices [I > 2σ(I)]
R indices (all data)
RESULTS AND DISCUSSION
X-ray structure determination: The single crystal of the
title compound with the approximate dimensions of 0.34 mm
× 0.28 mm × 0.21 mm was placed on a Bruker Smart 1 000 CCD
area detector. The reflections were collected using a graphite
monochromated MoKα radition (λ = 0.71073 Å) at 293 K. The
structure was solved by using the program SHELXL-97 and
Fourier difference techniques and refined by the full-matrix
least-squares method on F2. All non-hydrogen atoms were
subjected to anisotropic refinement and all hydrogen atoms
were added in idealized positions and refined isotropically.
Crystal data and details of the refinement are summarized in
Table-1, representative bond lengths (Å) and angles (°) are
presented in Table-2. CCDC reference numbers 980108.
X-ray crystal structure analyses reveal that the title
compound crystallized in the monoclinic space group C2/c.
As depicted in Fig. 1, the asymmetric unit consists of one title
compound. Upon careful investigation of the structure, it can
be seen that two title compound molecules are held together
to a 36 atom macro-ring via strong O-H···N hydrogen bonding
between one of the pyrazole N atoms (N2) and one of the
phenol oxygen atoms (O4) as shown in Fig. 2. The O4···N2
distance (2.737Å), O4-H22···N2 angle (169.38) are all within
the ranges of those reported O-H···N hydrogen bonds. In addi-
tion, the above mentioned macro-rings are further connected
into one dimensional beaded chain via C–H···O hydrogen
TABLE-2
SELECTED BOND LENGTHS (Å) AND ANGLES (°) FOR THE TITLE COMPOUND
C1-C6
C3-C4
C7-C8
C10-O2
C14-O3
C15-C16
C19-C24
C21-C22
1.384(4)
1.368(4)
1.506(5)
1.344(4)
1.434(4)
1.360(5)
1.381(4)
1.389(4)
1.506(11)
1.384(3)
C1-C2
C4-C5
C8-N2
C10-N1
C14-O3
C16-C17
C19-C20
C22-O4
C12A•O1
N3-N4
1.386(4)
1.377(4)
1.333(4)
1.353(4)
1.434(4)
1.376(5)
1.391(4)
1.371(4)
1.282(8)
1.383(3)
C2-C3
C5-C6
C8-C9
C13-O1
C15-N3
C17-N4
C19-N3
C22-C23
1.385(5)
1.386(4)
1.389(5)
1.420(5)
1.344(4)
1.324(4)
1.433(4)
1.376(4)
C3-O5
C6-N1
1.361(4)
1.431(4)
1.353(4)
1.464(5)
1.346(4)
1.512(5)
1.386(4)
1.384(4)
1.453(10)
C9-C10
C13-C14
C15-O3
C17-C18
C20-C21
C23-C24
C12B•O1
C11A-O2
N1-N2
C6–C1–C2
O5–C3–C2
C4–C5–C6
C5–C6–N1
C9–C8–C7
O2–C10–N1
O3–C14–C13
O3–C15–C16
N4–C17–C18
C24–C19–N3
C20–C21–C22
C23–C22–C21
C12A–C11A–O2
C10–N1–C6
C15–N3–N4
C17–N4–N3
C15–O3–C14
120.0(3)
C3–C2–C1
C4–C3–C2
C1–C6–C5
N2–C8–C9
C10–C9–C8
C9–C10–N1
N3–C15–O3
C15–C16–C17
C16–C17–C18
C20–C19–N3
O4–C22–C23
C22–C23–C24
O1–C12A–C11A
N2–N1–C6
120.4(3)
O5–C3–C4
118.0(3)
122.6(3)
120.5(3)
119.2(3)
129.5(3)
118.7(3)
108.6(3)
133.4(3)
119.6(3)
121.1(3)
120.5(3)
119.7(3)
108.0(8)
132.7(3)
109.7(3)
104.9(3)
116.1(3)
119.4(3)
119.0(3)
111.7(3)
105.1(3)
109.0(3)
118.3(3)
105.4(3)
128.6(4)
118.8(3)
122.8(3)
120.2(3)
110.8(12)
117.9(2)
130.6(3)
118.3(5)
C3–C4–C5
C1–C6–N1
N2–C8–C7
O2–C10–C9
O1–C13–C14
N3–C15–C16
N4–C17–C16
C24–C19–C20
C21–C20–C19
O4–C22–C21
C19–C24–C23
C10–N1–N2
C8–N2–N1
120.6(3)
121.8(3)
118.8(3)
132.3(3)
112.3(3)
108.2(3)
111.8(3)
120.1(3)
119.3(3)
117.5(3)
120.2(3)
109.4(2)
104.9(3)
119.7(2)
108.1(4)
C15–N3–C19
C12A–O1–C13
N4–N3–C19
C10–O2–C11A

Vol. 27, No. 4 (2015)
Synthesis of 1,7'-bis[4-(3-Methyl-2,3-dihydro-pyrazol-1-yl)phenol]-1,4,7-trioxaheptane 1341
Conclusion
In conclusion, we have presented herein the synthesis
and crystal structure of a new arylpyrazole derivative which
demonstrated interesting supramolecular properties.
ACKNOWLEDGEMENTS
This work was supported by the Young Scholars Science
Foundation of Lanzhou Jiaotong University (No. 2013011)
and the Natural Science Foundation of Gansu Province of
China (No. 1310RJZA066) .
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