Synthesis and crystal structure of new N,N′-Bis[1-(4-methoxyphenyl)- 5-methyl-1H-1,2,3-triazole-4-carbonyl]hydrazide

Article abstract of DOI:10.1007/s10870-008-9421-z

The N,N′-bis[1-(4-methoxyphenyl)-5-methyl-1H-1,2,3-triazole-4- carbonyl]hydrazide 6 was synthesized from aryl triazole acids and its structure is established by MS, IR, and ¹H NMR spectral data. Compound 6, C₂₂H₂₂N₈O₄, Mr = 462.48, crystallizes in the monoclinic space group P2(1)/c with unit cell parameters a = 15.3451(8), b = 8.6486(4), c = 16.8502(9) A, α = 90.00, β = 95.731(2), γ = 90.00°, V = 2225.1(2) A³, Z = 4, and Dx = 1.381 mg m^-3. The final R was 0.0450. The four aromatic rings are close to linear because of N???H-N hydrogen bonds.

Full text of DOI:10.1007/s10870-008-9421-z

J Chem Crystallogr (2009) 39:91–94
DOI 10.1007/s10870-008-9421-z
ORIGINAL PAPER
Synthesis and Crystal Structure of New N,N0-Bis[1-(4-
methoxyphenyl)-5-methyl-1H-1,2,3-triazole-4-carbonyl]hydrazide
Heng-Shan Dong Æ Yan-Fei Wang Æ Hong-Ru Dong Æ
Bin Wang Æ Bin Quan
Received: 7 May 2007 / Accepted: 7 May 2008 / Published online: 25 June 2008
Ó Springer Science+Business Media, LLC 2008
Abstract The N,N0-bis[1-(4-methoxyphenyl)-5-methyl-
1H-1,2,3-triazole-4-carbonyl]hydrazide 6 was synthesized
from aryl triazole acids and its structure is established
by MS, IR, and 1H NMR spectral data. Compound 6,
C22H22N8O4, Mr = 462.48, crystallizes in the monoclinic
space group P2(1)/c with unit cell parameters a =
metastasis [5] and as anti-HIV agents [6, 7]. For this rea-
son, the heterocyclic derivatives containing two 1,2,3-
triazoles nuclei are very interesting. The route of syntheses
is in Scheme 1.
˚
15.3451(8), b = 8.6486(4), c = 16.8502(9) A, a = 90.00,
3
N2 Cl-
+
˚
N3
b = 95.731(2), c = 90.008, V = 2225.1(2) A , Z = 4, and
NH2
Dx = 1.381 mg m-3. The final R was 0.0450. The four
aromatic rings are close to linear because of NꢀꢀꢀH–N
hydrogen bonds.
NaN3
NaNO2,HCl
0-5 oC
OCH3
OCH3
OCH3
Keywords Crystal structure ꢀ 1,2,3-triazole ꢀ
N,N0-Bis(1-aryl-5-methyl-1H-1,2,3-triazole-4-
carbonyl)hydrazide ꢀ Hydrogen bond ꢀ Crystal data
1
2
3
COOH
N
CH COCH COOC H
2 5
N
3
2
SOCl
CH
3
2
N
Introduction
NaOEt, HOEt
In recent years, certain compounds having 1,2,3-triazole
nucleus have been reported as antibacterial [1], antifungal
[2], antiviral [3], anti-inflammatory, and analgesic [4].
Recently, some new 1,2,3-triazole derivatives have been
synthesized to inhibit tumor proliferation, invasion and
OCH
4
3
O
O
H
N
COCl
CH
N
N
H
N
N
N
3
N
CH
N
N
NH NH H O
3
H.-S. Dong (&) ꢀ Y.-F. Wang ꢀ B. Wang
State Key Laboratory of Applied Organic Chemistry, Institute of
Organic Chemistry, College of Chemistry and Chemical
Engineering, Lanzhou University, Lanzhou, Gansu 730000,
China
2
2. 2
H C
3
N
N
OCH
e-mail: donghengshan@lzu.edu.cn
3
OCH
3
OCH
3
5
H.-R. Dong ꢀ B. Wang ꢀ B. Quan
6
College of Science and Engineering, Gansu Association
University, Lanzhou, Gansu 730000, China
Scheme 1 The synthesis route of title compound
123

92
J Chem Crystallogr (2009) 39:91–94
Experimental
Table 1 Crystal data and summary of data collection and structure
refinement
All melting points were determined on a Sapphire DSC
(Differential Scanning Calorimeter) which is made by
Perkin Elmer (USA). IR spectra were obtained in KBr discs
on a Shimadzu IR-435 spectrometer. MS were performed
on a HP-5988A spectrometer (EI at 70 eV). 1H NMR
spectroscopy (CDCl3) was recorded on a Varian Mercury
plus-300 instrument with TMS as an internal standard.
5-Methyl-1-(4-methoxyphenyl)-1,2,3-triazol-4-carboxylic
acid 4 was prepared by following methods in the literature
[8].
Compound no.
6
CCDC deposition number
Empirical formula
Color/shape
616414
C
22H22N8O4
Colorless/block
462.48
Formula weight
Temperature (K)
294(2)
˚
Wavelength (A)
0.71073
Crystal system
Space group
Monoclinic
P21/c
Cell dimensions
˚
a (A)
15.3451(8)
8.6486(4)
16.8502(9)
90
Preparation of 1-(4-Methoxyphenyl)-5-methyl-1,2,3-
˚
b (A)
triazol-4-carbonyl chloride 5
˚
c (A)
a (°)
b (°)
c (°)
In a 150 mL round bottomed flask was placed a mixture of 4
(20 mmol) and SOCl2 (20 mL) and the mixture was refluxed
gently for 5–8 h. After excessive SOCl2 was distilled from
the mixture, remaining SOCl2 was removed, which was
washed by absolute benzene (20 mL 9 2). The resulting
solid was purified by recrystallization from Et2O. The 1-(4-
methoxyphenyl)-5-methyl-1,2,3-triazol-4-carbonyl chloride
5 was obtained.
95.731(2)
90
3
˚
Volume (A )
2225.1(2)
4
Z
Dcalc (g cm-3
Absorption coefficient (mm-1
)
1.381
)
0.100
Diffractometer/scan
Smart apex II
CCD area detector x/2h
968
F(000)
N,N0-Bis(1-(4-methoxyphenyl)-5-methyl-1H-1,2,3-
triazole-4-carbonyl)hydrazide 6 was Prepared From 5
as Follows
h range for data collection (°)
Index ranges
2.43*28.79
-19 B h B 19
-11 B k B 11
-22 B l B 15
5251
A solution of 10 mmol (85% hydrazine hydrate) in 10 mL
of 20% NaOH was added drip to 1-(4-methoxyphenyl)-5-
methyl-1,2,3-triazol-4-carbonyl chloride 5 and it was
cooled with ice-water. Then, the solution of 5 (about
0.02 mol) and hydrazine hydrate was refluxed for 5 h with
stirring. The reaction mixture was cooled and the resulting
solid was purified by recrystallization from DMF to give
white blocks of compound 6 yield 30.5%, m.p. 282.6 °C.
1HNMR: 10.459 (s, 2H, –NHNH–), 7.526-7.556 (d, 4H,
J = 8.7 Hz, Ar-2,6), 7.136–7.165 (d, 4H, J = 8.7 Hz, Ar-
3,5), 3.842 (s, 6Hþ, Ar–OCH3), 2.507 (s, 6H, TRZ–CH3).
MS m/z: 514 (M: , FAB). IR: 3343, 3074, 2935, 2836,
1705, 1679, 1639, 1579, 1552, 1516, 1461, 1372, 1350,
1302, 1254, 1174, 1148, 1125, 1034, 1018, 1001, 981, 828,
771, 699, 646, 611, 530, 433.
Reflections collected
Independent reflection
Data/restrains/parameters
Extinction coefficient
Goodness-of-fit on F2
Final R indices [I [ 2r(I)]
R indices
3784
3015/0/312
0.0030(12)
0.527
R1 = 0.0450, wR2 = 0.1304
R1 = 0.1000, wR2 = 0.1797
-3
˚
Largest different peak and hole
0.225 and -0.173 eA
The crystal data and the refinement details are given in
Table 1.
The structure of the compound 6 is shown in Fig. 1.
Selected bond lengths are given in Table 2, selected bond
angles are given in Table 3. The geometric calculations
were performed using the program SHELX-97.
The purified product was dissolved in DMSO. Crystals
were obtained after 60 days by evaporation of the solvent.
A single crystal was selected and mounted on the tip of a
glass fiber. Preliminary examination and data collection
˚
were performed with MoKa radiation (k = 0.71073 A) on
a D8 Smart APEX II computer controlled APEX II detector
diffractometer 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).
Results and Discussion
The new N,N0-bis(1-(4-methoxyphenyl)-5-methyl-1H-1,2,
3-triazole-4-carbonyl)hydrazide 6 has been synthesized
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J Chem Crystallogr (2009) 39:91–94
93
Table 2 Selected bond
˚
lengths (A)
Atoms
Length
O1–C1
1.429(3)
1.354(2)
1.363(2)
1.433(2)
1.357(2)
1.359(2)
1.438(2)
1.302(2)
1.361(3)
1.217(2)
1.348(2)
1.381(2)
1.377(3)
1.391(3)
1.383(3)
1.387(3)
1.378(3)
1.364(2)
1.418(3)
1.215(2)
1.355(2)
1.479(2)
1.307(2)
1.476(2)
1.380(2)
1.483(3)
1.358(2)
1.389(3)
1.388(3)
1.381(3)
1.377(2)
1.485(3)
1.380(3)
1.385(3)
1.382(2)
1.385(3)
N8–C14
N8–N7
N8–C16
N1–C8
N1–N2
N1–C5
N6–N7
N6–C13
O3–C12
N5–C12
N5–N4
C21–C20
C21–C16
C2–C7
Fig. 1 ORTEP drawing of the compound 6 is showing the atom
numbering scheme
from 1-(4-methoxyphenyl)-5-methyl-1,2,3-triazol-4-carbox-
ylic acid 4. The structure of this compound was characterized
with 1HNMR, IR, and MS spectroscopy. IR absorption peaks
of 6 at 3373, 3074 cm-1 are assigned to its NH and 1679,
1705 cm-1 is assigned to its –CO– group. The chemical shift
of the triazole ring methyl group show in the range
d2.507 ppm in compound 6. The chemical shift of the triazole
ring Me-proton is in agreement with the values reported for
triazole (typical chemical shift of the triazole ring Me-proton
is at about d2.45 ppm in the NMR spectra) by Ykman [9] and
(typical chemical shift of the triazole ring Me-proton is at
about d2.26–2.62 ppm in the NMR spectra) (Dong [10]). The
crystal structure of 6 agrees with the structure (Fig. 1). The
1,2,3-triazole ring system is planar. The bond lengths N1–N2
C2–C3
C16–C17
O4–C19
O4–C22
C11–O22
C11–N4
C11–C9
N2–N3
C12–C13
C14–C13
C14–C15
N3–C9
C20–C19
C17–C18
C19–C18
C8–C9
˚
˚
˚
1.359(2) A, N2–N3 1.302(2) A, N7–N8 1.363(7) A, N6–N7
˚
1.307(2) A are in agreement with the values reported for tri-
˚
azole, N1–N2 1.361(5) A, N2–N3 1.295(5) A, but the bond
˚
C8–C10
C5–C4
˚
lengths of N4–N5 is 1.381(2) A.
The dihedral angles between 4-methoxyphenyl rings and
1,2,3-triazole rings are 50.1–56.1°[N2–N1–C5–C4—53.0(3),
C8–N1–C5–C4—125.0(2), C8–N1–C5–C6—56.1(3),
N2–N1–C5–C6—125.9(2)°, C14–N8–C16–C17—127.2(2),
N7–N8–C16–C17—50.1(3), C14–N8–C16–C21—55.4(3),
N7–N8–C16–C21—127.3(2), C15–N1–C17–C22—134.1(3)°],
the 4-methoxyphenyl ring and 1,2,3-triazole ring system is
not planar [also see Fig. 1b, c].
C5–C6
C6–C7
C3–C4
[N(5)–H(5)ꢀꢀꢀN(6)].The structure of the compound 6 is
shown in Scheme 2 and Fig. 1.
The dihedral angles between N4–C11–C9–N3 is
-13.0(3)°, bond angles N4–C11–C9 113.73(16); N5–N4–H4
120.3; N4–N5–H5 119.5; N5–N4–H4 120.3; N3–C9–C11
122.87(16); C11–N4–H4 120.3° in ring A, all atom are
close to a plane in the A ring system. And so is in ring B,
all atoms are close to a plane in the B ring system. The
intramolecular hydrogen bond is in the A and B ring sys-
The X-ray structure analysis indicated that the com-
pound 6 consisted of two phenyl rings and two triazole
ring. The four aromatic rings are approximately linear
because the intramolecular hydrogen bond is in the A and
B ring system. The most noticeable change is that the
signals of imino protons appeared in d10.459 ppm (1-(4-
ethoxyphenyl)-5-methyl-1,2,3-triazol-4-carbonylhydrazine
4.450–4.720 [broad peak, 3H, –NHNH2]) [8].
˚
tem. The bond length of Donor-HꢀꢀꢀAcceptor is 2.41 A, the
˚
bond angle is 106° [N(4)–H(4)ꢀꢀꢀN(3)], and 2.32 A, 108°
123

94
J Chem Crystallogr (2009) 39:91–94
Table 3 Selected bond
angles (°)
O
N
CH3
O
Atoms
Angle
H3C
N
H
N
N
N
H
C2–O1–C1
117.29(16)
111.15(14)
130.92(15)
117.89(14)
111.54(14)
129.84(15)
118.59(15)
108.91(15)
120.97(17)
119.48(18)
116.36(17)
123.75(18)
119.88(17)
120.61(16)
118.80(16)
120.53(16)
117.74(17)
123.20(17)
123.06(17)
113.73(16)
106.78(14)
124.31(17)
122.91(17)
112.78(17)
103.42(15)
124.17(15)
132.40(16)
108.96(15)
120.32(18)
119.52(18)
124.95(18)
115.24(17)
119.80(17)
109.33(15)
121.32(16)
129.29(17)
119.30(16)
103.09(15)
123.81(16)
132.94(17)
109.61(15)
122.87(16)
127.47(17)
120.75(16)
118.28(16)
120.96(17)
107.19(15)
120.24(18)
119.28(18)
120.42(17)
119.87(19)
119.67(18)
N
N
O
C14–N8–N7
C14–N8–C16
N7–N8–C16
C8–N1–N2
N
CH3
H3C
O
Scheme 2 The hydrogen bonds of title compound
C8–N1–C5
Acknowledgements The authors wish to acknowledge that this
project is supported by Lanzhou University SKLAOC.
N2–N1–C5
N7–N6–C13
C12–N5–N4
C20–C21–C16
O1–C2–C7
References
1. Zhang ZY, Liu Y, Yang SY (1991) Pharmaceuceutica Simica
26:809
2. Abdou NA, Soliman SN, Abou Sier AH (1990) Bull Fac Pharm
28:29 (Chem Abstr 1992, 117, 69793n)
3. Srivastava AJ, Swarup S, Saxena VK, Chowdhury BL (1991)
J Indian Chem Soc 68:103
4. Cooper K, Steele J, Richardson K EP 329357 (Chem Abstr 1990,
112, 76957u)
5. Kohn EC, Liotta LA U.S. 637145 (Chem Abstr 1991, 115,
248099w)
6. Alvarez R, Velazquez S, San-Felix A, Aquaro S, De Clercq E,
Perno CF, Karlsson A, Balzarini J, Camarasa MJ (1994) J Med
Chem 37:4185
7. De Clercq E (2002) Med Res Rev 22:531
8. Dong HS, Wang B (2005) J Chin Chem Soc (Taipei) 52:103–108
9. Ykman P, L’Abbe G, Smets G (1971) Tetrahedron 27:5623
O1–C2–C3
C7–C2–C3
C17–C16–C21
C17–C16–N8
C21–C16–N8
C19–O4–C22
O2–C11–N4
O2–C11–C9
N4–C11–C9
N3–N2–N1
O3–C12–N5
O3–C12–C13
N5–C12–C13
N8–C14–C13
N8–C14–C15
C13–C14–C15
N2–N3–C9
´
10. Dong HS, Liu SQ (2003) J Chin Chem Soc (Taipei) 50:1215–
1219
C21–C20–C19
C16–C17–C18
O4–C19–C18
O4–C19–C20
C18–C19–C20
N6–C13–C14
N6–C13–C12
C14–C13–C12
C11–N4–N5
N1–C8–C9
N1–C8–C10
C9–C8–C10
N3–C9–C8
N3–C9–C11
C8–C9–C11
C4–C5–C6
C4–C5–N1
C6–C5–N1
N6–N7–N8
C19–C18–C17
C7–C6–C5
C6–C7–C2
C4–C3–C2
C5–C4–C3
123