Synthesis and crystal structure of (5-methyl-3-phenyl-1h-pyrazol-1-yl)-[5- (p-tolylamino)-2h-1,2,3-triazol-4-yl]methanone

Article abstract of DOI:10.1007/s10870-010-9798-3

(5-Methyl-3-phenyl-1H-pyrazol-1-yl)-[5-(p-tolylamino)-2H-1,2, 3-triazol-4-yl]methanone was synthesized and characterized by ¹H NMR, MS and IR spectra data. The structure of title compound was identified by X-ray diffraction. Compound, C_20<

Full text of DOI:10.1007/s10870-010-9798-3

J Chem Crystallogr (2010) 40:1078–1081
DOI 10.1007/s10870-010-9798-3
ORIGINAL PAPER
Synthesis and Crystal Structure of (5-Methyl-3-phenyl-1H-
pyrazol-1-yl)-[5-(p-tolylamino)-2H-1,2,3-triazol-4-yl]methanone
•
•
•
Zi-Ping Cao Hong-Ru Dong Guo-Liang Shen
Heng-Shan Dong
Received: 27 March 2008 / Accepted: 20 May 2010 / Published online: 9 June 2010
Ó Springer Science+Business Media, LLC 2010
Abstract (5-Methyl-3-phenyl-1H-pyrazol-1-yl)-[5-(p-tol-
ylamino)-2H-1,2,3-triazol-4-yl]methanone was synthesized
and characterized by 1H NMR, MS and IR spectra data. The
structure of title compound was identified by X-ray diffrac-
tion. Compound, C20H18N6O, Mr = 358.40, crystallizes in
the triclinic space group P-1 with unit cell parameters
butane-1,3-dione. The route of synthesis is shown in
Scheme 1.
Experimental Section
˚
a = 10.303(6), b = 12.489(7), c = 15.305(9) A, a =
Melting points were determined on an XT4-100X micro-
scopic melting point apparatus (uncorrected). IR spectra
were obtained in KBr pellets on a Nicolet 170SX FT-IR
spectrometer. The mass spectrum was performed on a HP-
108.489(12), b = 101.920(11), c = 96.971(13)°, V =
3
3
1790.0(17) A , Z = 4, Dx = 1.330 mg/cm . The final R was
˚
0.0520.
1
5988A spectrometer (EI at 70 eV). H NMR spectroscopy
Keywords Pyrazole Á Crystal structure Á Synthesis Á
2H-1,2,3-Triazole Á 1H-1,2,3-Triazole
was recorded at Varian Mercury Plus-300NMR instrument
with TMS as an internal standard.
Preparation of Ethyl 5-Amino-1-p-tolyl-1H-1,2,3-
triazol-4-carboxylate 4
Introduction
In recent years, 1,2,3-triazole derivatives have been found
on a variety of biological activity and outstanding properties
in many fields such as pharmacy [1, 2], pesticide [3],
material [4], etc. The heterocyclic derivatives containing
1H-1,2,3-triazole and pyrazole nucleus had been develop-
ing, but they had been studied and reported a little in the
literature till now. For this reason, we obtained (5-methyl-
3-phenyl-1H-pyrazol-1-yl)-[5-(p-tolylamino)-2H-1,2,
3-triazol-4-yl]methanone in reaction of 5-amino-1-p-tolyl-
2H-1,2,3-triazole-4-carboxylic acid hydrazide and 1-phenyl-
Preparation of ethyl 5-amino-1-p-tolyl-1H-1,2,3-triazol-4-
carboxylate 4 was following method in the literature [5].
Synthesis of 5-(p-Tolylamino)-2H-1,2,3-triazol-4-
carbohydrazide 5
To add ethyl 5-amino-1-p-tolyl-1H-1,2,3-triazol-4-carbox-
ylate 4 (0.003 mol) and hydrazine hydrate (0.012 mol) in a
100 mL flask, the mixture was heated at 80 °C for 1 h and
refluxed in EtOH (25 mL) for 5 h. After it was cooled to
room temperature and the solid was filtered. The filtrate
was neutralized with diluted HCl, and the precipitated solid
was filtered and dried. Compound 5, 5-(p-tolylamino)-
2H-1,2,3-triazol-4-carbohydrazide was given. Yield 35%,
mp 199–200 °C, IR tmax: 3388, 3356, 3325, 3304, 3118
(b, NH or NH2), 3032, 2966(m, Ar-H), 2914(m, CH3),
1641(s, C=O), 1599(C=N), 1549, 1514(s, Ar), 981(m, tri-
Z.-P. Cao Á H.-R. Dong Á G.-L. Shen Á H.-S. Dong (&)
State Key Laboratory of Applied Organic Chemistry, Institute
of Organic Chemistry, College of Chemistry and Chemical
Engineering, Lanzhou University, Lanzhou, Gansu 730000,
People’s Republic of China
1
azole ring)cm-1; HNMR(DMSO) dH: 2.241(s, 3H, CH3),
e-mail: donghengshan@lzu.edu.cn
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J Chem Crystallogr (2010) 40:1078–1081
1079
1H
NH2
Ar), 1261(m, C=N–N), 945(w, N=N–N)cm-1
;
N2+Cl-
N3
NMR(CDCl3) dH: 2.341(s, 3H, CH3), 2.782(s, 3H, CH3);
6.616(s, 1H, CH), 7.173–7.200(d, 2H, J = 8.1 Hz,
p-MeC6H4-H), 7.636–7.663(d, 2H, J = 8.1 Hz, p-MeC6H4-
H), 7.495–7.519(m, 3H, Ph-H), 7.825–7.851(d, 2H, Ph-H),
NaNO2,HCl
0-5oC
NaN3
0-5oC
NCCH2COOC2H5
EtONa
CH3
CH3
CH3
1
2
3
8.382(b, 1H, NH)ppm; MSm/z: 358(
, 27%), 359(M ? 1,
O
6), 330(7), 301(7), 212(4), 196(6), 184(6), 172(4), 159(100),
144(12), 128(17), 117(63), 107(12), 91(78), 77(47), 65(38),
57(30), 51(25), 43(27), 39(16).
N H
2
3
OEt
N
N
O
O
O
N
N
NH
2
Ph
1.N H .H O
2
4
2
HN
(3-Methyl-5-phenyl-1H-pyrazol-1-yl)-[5-(p-tolylamino)-
2H-1,2,3-triazol-4-yl)methanone 7. Yield 34%, mp 179–
180 °C, IR tmax: 3359(b, triazole-NH), 3210, 3135 (b,
N–H_O=C), 2919(w, CH3), 1668(s, C=O), 1613(C=N),
1570, 1512, 1444, 1409(s, Ar), 1275(b, C=N–N), 973(m,
NH
N
EtOH
2.HCl
H C
3
CH
3
4
5
Table 1 Crystal data and summary of data collection and structure
refinement
N
N
N
N
N
O
O
Compound
C20H18N6O
635047
N
CCDC deposit no.
Color
+
HN
HN
NH
NH
Light yellow
358.40
N
N
Formula weight
Temperature, °C
Crystal system
Space group
21(294 K)
Triclinic
P-1
H3C
H3C
6
7
˚
a = 10.303(6) A; b = 12.489(7) A;
˚
Unit-cell dimensions
˚
c = 15.305(9) A;
Scheme 1 The synthesis route of title compound
a = 108.489(12)°;
b = 101.920(11)°;
c = 96.971(13)°
7.091–7.118(d, 2H, J = 8.1 Hz, p-MeC6H4-H), 7.386–
7.413(d, 2H, J = 8.1 Hz, p-MeC6H4-H)ppm; MS m/z:
3
˚
Volume (A )
1790.0(17)
232(
100%), 233(M ? 1,14), 217(1), 201(39), 188(1),
Z
4
calc, g cm-3
1.330
752
175(9), 173(16), 158(9), 146(28), 145(18), 133(9), 118(24),
106(11), 91(93), 77(26), 65(55), 51(19), 44(33), 39(24).
D
F(000)
Absorption coefficient,
mm-1
0.087
Synthesis of (5-Methyl-3-phenyl-1H-pyrazol-1-yl)-
[5-(p-tolylamino)-2H-1,2,3-triazol-4-yl]methanone 6
and (3-Methyl-5-phenyl-1H-pyrazol-1-yl)-[5-(p-
tolylamino)-2H-1,2,3-triazol-4-yl]methanone 7
Diffractometer/scan
Enraf-Nonius CAD4, x/2h
Radiation/k
ka (graphite monochromator)/
˚
0.71073 A
h
min, hmax (°)
1.84–25.75
3055
To add 5-p-tolylamino-2H-1,2,3-triazol-4-carboxylic acid
(0.003 mol), 1-phenyl-butane-1,3-dione
Reflections measured
hydrazide
5
Independent/observed
reflections
4648
(0.003 mol) and EtOH (25 mL) in a 100 mL flask. The
mixture was controlled at 80 °C till completely dissolved
and refluxed for 4 h. It was cooled to room temperature and
the solid was filtered, washed with a cool anhydrous ethanol
and dried. The solid was separated by chromatographic
column (silica gel, eluent for ethyl acetate:petroleum
ether = 1:6). Compounds 6 and 7 were given.
Data/restraints/
parameters
6529/0/492
Refinement method
Goodness-of-fit on F2
Shift/su_max
Full-matrix least-squares on F2
1.011
0.000
Final R indices
R1 = 0.0520, WR2 = 0.1489
R1 = 0.0760, WR2 = 0.1714
0.0067(13)
R indices[I [ 2r(I)]
Extinction coefficient
(5-Methyl-3-phenyl-1H-pyrazol-1-yl)-[5-(p-tolylamino)-
2H-1,2,3-triazol-4-yl]methanone 6. Yield 39%, mp 170–
171 °C, IR tmax: 3437, 3348(b, NH), 3106(Ar–H), 2922(w,
CH3), 1661(s, C=O), 1607(C=N), 1570, 1510, 1448, 1408(s,
-3
˚
0.512 and -0.413 e A
Largest diff. peak and
hole
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1080
J Chem Crystallogr (2010) 40:1078–1081
evaporation of the solvent from this solution. The yellow
needlelike crystals were produced in 2 weeks.
Crystal Structure Determinations and Refinement
Single crystals were selected and mounted on the tip of a
glass fiber. Preliminary examination and data collection
´
˚
were performed with Mo Ka radiation (k = 0.71073 A) on
a Bruker SMART CCD area detector operating in the x/2h
scanning mode. The structure was determined by direct
methods (SHELXS-97) and refined by full covariance
matrix methods (SHELXL-97). The crystal data, data col-
lection and the refinement parameter for the structure are
given in Table 1.
The structure of the title compound 6 is shown in Fig. 1.
The H-bond of the title compound 6 is shown in Fig. 2.
Selected bond lengths, angles and dihedral angles are given
in Tables 2, 3, and 4. The geometric calculations were
performed using the program SHELX-97.
Fig. 1 Mercury view (CCDC, 2005) of the molecular structure for
the title compound 6 showing the atom numbering scheme
N=N–N)cm-1 1HNMR(CDCl3) dH: 2.305(s, 3H, CH3),
;
2.444(s, 3H, CH3), 6.324(s, 1H, CH), 7.114–7.142(d, 2H,
J = 8.4 Hz, p-MeC6H4-H), 7.549–7.577(d, 2H, J = 8.4,
p-MeC6H4-H), 7.475(s, 5H, Ph-H), 8.161(b, 1H, NH)ppm;
´
˚
Table 2 Selected bond lengths (A) (of the molecule A)
Atoms
Length
Atoms
Length
MS m/z: 358( +, 7.5%), 359(M ? 1, 1), 330(1), 301(1),
M
246(2), 232(5), 219(3), 188(2), 158(52), 145(15), 117(26),
111(21), 97(31), 91(61), 77(43), 69(60), 65(32), 57(100),
51(25), 43(94), 39(22).
N1–C5
N1–C8
N4–C9
N4–N3
N2–N3
N2–C8
1.400(3)
1.371(3)
1.370(3)
1.319(3)
1.325(3)
1.354(3)
C9–C8
1.388(3)
1.221(2)
1.393(3)
1.380(2)
1.324(3)
1.391(3)
O1–C10
N5–C10
N5–N6
N6–C14
N5–C12
The purified product (5-methyl-3-phenyl-1H-pyrazol-
1-yl)-[5-(p-tolylamino)-2H-1,2,3-triazol-4-yl]methanone 6
was dissolved in a mixture solvent of ethyl acetate and
petroleum ether. Crystals were grown by especially slow
Fig. 2 The H-bond structure of
the compound 6 (PWT drawing
for the Platon)
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J Chem Crystallogr (2010) 40:1078–1081
1081
Identified as a pyrazole compound showing 1HNMR
Table 3 Selected bond angles (°) (of the molecule A)
d(comp.7,CH) = 6.324 ppm and d(comp.6,
= 6.616 ppm,
CH)
Atoms
Angle
Atoms
Angle
the chemical shift value is basic agreement with the
value(6.44 ppm) reported for pyrazole ring [12]. The bond
C4–C5–N1
C6–C5–N1
N1–C8–C9
N2–C8–C9
N2–C8–N1
N4–C9–C8
N4–C9–C10
N5–C10–C9
O1–C10–C9
O1–C10–N5
C13–C12–N5
124.4(2)
117.6(2)
N5–C12–C11
N6–C14–C15
N6–C14–C13
C8–N1–C5
124.6(2)
121.4(2)
´
˚
lengths is more agreement with [N1–N2 1.361(5) A; N2–
´
˚
N3 1.295(5) A] in 1,2,3-triazole ring [13]. The all plane of
124.9(2)
110.9(2)
109.64(19)
125.5(2)
129.95(19)
106.83(18)
109.87(18)
110.15(18)
127.73(18)
111.65(17)
120.60(17)
104.65(17)
ring system are basically on the plane in title comp. 6 (in
the molecule labeled with suffix A), because there is the
conjugate of the k–k. It is shown in Table 4 selected
dihedral angles.
N3–N2–C8
103.50(18)
130.51(19)
119.61(19)
119.9(2)
N4–N3–N2
N3–N4–C9
In the crystal structure, there is an intra-molecular N1A–
H_O1A (N1B–H_O1B) hydrogen bond involving the
N–H atom and itself of molecular C=O [N1A–H 0.86
C12–N5–C10
N6–N5–C12
N6–N5–C10
C14–N6–N5
120.51(19)
105.3(2)
´
˚
H_O1A 2.14 N1A–H_O1A 2.784(3) A, N1A–H_O1A
1318; N1B–H 0.86 H_O1B 2.16 N1B–H_O1B
´
˚
2.799(3) A, N1B–H_O1B 1318] [14]. There is two
intermolecular hydrogen bond (N3A–H_N4B; N3B–
H_N4A) involving the N–H atom and other molecular
triazole ring 4 positions N [N3A–H 0.86 H_N4B 2.54
Table 4 Selected dihedral angles (°) (of the molecule A)
Atoms
Angle
Atoms
Angle
´
˚
N3A–H_N4B 3.156(3) A, N3A–H_N4B 1298; N3B–H
C8–N1–C5–C6
C8–N1–C5–C4
C5–N1–C8–N2
C5–N1–C8–C9
N4–C9–C10–O1
C8–C9–C10–O1
N4–C9–C10–N5
C8–C9–C10–N5
-171.5(2)
8.7(4)
N6–N5–C10–O1
C12–N5–C10–O1
N6–N5–C10–C9
C12–N5–C10–C9
N6–C14–C15–C16
C13–C14–C15–C16
N6–C14–C15–C20
178.71(19)
0.2(3)
´
˚
0.86 H_N4A 2.30 N3B–H_N4A 3.046(3) A, N3B–
H_N4A 1468]. A view of H-bond structure for the title
compound 6 is show in Fig. 2.
-0.4(4)
178.2(2)
176.3(2)
-3.9(3)
-3.8(3)
-1.2(3)
-179.8(2)
-0.6(3)
179.8(2)
178.9(2)
-0.7(3)
Acknowledgment The authors with to acknowledge this project is
supported by Lanzhou University SKLAOC.
176.08(19) C13–C14–C15–C20
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Results and Discussion
The structure of the title compound 6 is shown in Fig. 1. In
recent years, the synthesis and characteristics of 5-amino-
1-(4-chlorophenyl)-1,2,3-triazol-4-yl and 5-methyl-1-(4-
methylphenyl)-1,2,3-triazol-4-yl derivatives have been
investigated [6–8]. These heterocyclic compounds contain
1,2,3-triazole ring, and they were a series stable com-
pounds. In order to continue our studies, we now report the
crystal structure of (5-methyl-3-phenyl-1H-pyrazol-1-yl)-
[5-(p-tolylamino)-2H-1,2,3-triazol-4-yl]-methanone. 5-p-
tolylamino-2H-1,2,3-triazol-4-carboxylic acid hydrazide 5
was one Dirmorth rearrangement [9–11] product by
ethyl 5-amino-1-p-tolyl-1H-1,2,3-triazole-4-carboxylate and
hydrazine hydrate.
14. Spek AL (2003) J Appl Cryst 36:7–13
123