The synthesis and crystal structure of 5-methyl-1-(1-naphthyl)-1,2,3- triazol-4-carboxyl acid

Article abstract of DOI:10.1007/s10870-008-9408-9

5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxyl acid 3 was synthesized from 1-aminonaphthalene. The yielded product 3 was investigated with X-ray crystallographic, NMR, MS and IR techniques. Compound 3, C₁₄H ₁₁N₃O₂, Mr = 253.26, crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 10.068(2), b = 12.353(2), c = 20.102(4) A, V = 2500.1(8) A³, Z = 8, Dx = 1.346 Mgm^-3. The final R was 0.0474. The molecular packing is stabilized by intermolecular O-H???N interactions.

Full text of DOI:10.1007/s10870-008-9408-9

J Chem Crystallogr (2009) 39:87–90
DOI 10.1007/s10870-008-9408-9
ORIGINAL PAPER
The Synthesis and Crystal Structure of
5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxyl
Acid
Shi-Qiang Liu Æ Bin Quan Æ Hong-Ru Dong Æ
Heng-Shan Dong
Received: 30 October 2006 / Accepted: 7 May 2008 / Published online: 26 June 2008
Ó Springer Science+Business Media, LLC 2008
Abstract 5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxyl
acid 3 was synthesized from 1-aminonaphthalene. The
yielded product 3 was investigated with X-ray crystallo-
graphic, NMR, MS and IR techniques. Compound 3,
C H N O , Mr = 253.26, crystallizes in the orthorhombic
In this paper, we report the crystal structure of 5-methyl-
1-(1-naphthyl)-1,2,3-triazol-4-carboxylic acid 3.
The route of synthesis is in Scheme 1.
1
4 11 3 2
space group Pbca with unit cell parameters a = 10.068(2),
3
b = 12.353(2), c = 20.102(4) A, V = 2500.1(8) A , Z = 8,
Experimental Section
˚
˚
-3
Dx = 1.346 Mgm . The final R was 0.0474. The molecu-
lar packing is stabilized by intermolecular O–HꢀꢀꢀN interac-
tions.
Melting points were uncorrected and determined on an
XT -1009 microscopic melting point apparatus. IR spectra
4
were obtained in KBr discs on a Nicolet 170SX FT-IR
spectrometer. MS were performed on an HP-5988A spec-
1
trometer (EI at 70 eV). H NMR spectra (CDCl ) were
Keywords Crystal structure ꢀ 1,2,3-Triazol-4-carboxyl
acid ꢀ 5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxyl
acid ꢀ H-bond ꢀ Synthesis
3
recorded on a Varian Mercury plus-200 MHz instrument
with TMS as an internal standard.
The Preparation of 5-Methyl-1-(1-naphthyl)-1,2,3-
triazol-4-carboxylic Acid 3
Introduction
Certain compounds having 1,2,3-triazole nucleus have
been reported as antibacterial [1], antifungal, antiviral,
anti-inflammatory, immunity [2], analgesic [3], inhibitors
to tumor proliferation, invasion, metastasis [4], anti-HIV
5-Methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxylic acid 3
waspreparedfollowingmethodsintheliterature[3]. The yield
of 3 is a yellow crystalline solid, m.p. 185–186 C, (25%).
IRtmax: 3,429(O–H); 3,060, 2,987(C–H); 1,725(C=O); 1,598,
1,558,1,511,1,452(Ar-ring);1,274(C–O);1,185(C–N);964.5
[
5, 6] and useful in treating CRF-related disorders. For this
-1 1
reason, 5-methyl-1-(1-naphthyl)-1,2,3-triazol-4-carboxylic
acid was synthesized.
(N=N–N) cm . H NMR(200 MHz, CDCl )d : 2.479(s, 3H,
3
H
CH –), 7.175–7.211(d, 1H, J = 8Hz, Ar–H),7.553–7.726(m,
3
4
H, Ar–H); 8.022–8.059(d, 1H, J = 8 Hz, Ar–H), 8.131–
.171(d, 1H, J = 8 Hz, Ar–H), 12.80–13.25(b, 1H, –COOH)
8
þ
ppm. MS M/z(%): 253 (M ; 9%), 236(1, M-17), 225(1, M-28
:
S.-Q. Liu ꢀ H.-S. Dong (&)
State Key Laboratory of Applied Organic Chemistry,
Institute of Organic Chemistry, College of Chemistry and
Chemical Engineering, Lanzhou University, Lanzhou, Gansu
or –N ), 224 (2, 225-1), 209(4, M-44 or –CO ), 196(1, M-44-
2
2
13), 181(45), 180(100, M-28-45), 178(20), 169(3, C H N ),
10 7 3
730000, People’s Republic of China
e-mail: donghengshan@lzu.edu.cn
153(18, C H –NC), 140(9, C H N), 127(80, C H ),
10 7 10 6 10 7
115(6), 101(16), 83(36), 77(38), 75(22), 63(17).
The purified product was dissolved in a mixture of water
B. Quan ꢀ H.-R. Dong
and ethanol. The crystals were obtained by slow evapora-
tion of this solvent mixture after 10 days.
College of Science and Engineering, Gansu Association
University, Lanzhou, Gansu 730000, China
123

8
8
J Chem Crystallogr (2009) 39:87–90
Scheme 1 The synthesis route
of title compound
+
-
N Cl
NH2
2
NaNO -HCl
NaN3
2
o
o
0
~5 C
0~5 C
1
COOH
N
N
N3
CH3
N
CH COCH CO Et
3
2
2
EtONa,EtOH
2
3
Crystal Structure Determinations and Refinement
Table 1 Crystal data and summary of data collection and structure
refinement
Suitable single crystals were selected and mounted on the tip
of a glass fiber. Preliminary examination and data collection
Compound
14 11 3 2
C H N O
˚
CCDC deposit No.
Color
288148
were performed with MoJa radiation (k = 0.71073 A) on
Yellow/block
253.26
an Enraf-Nonius CAD4 computer controlled kappa axis
diffractometer operating in the x/2h scanning mode. The
structure was determined by direct methods (SHELXS-97)
Formula weight
Temperature, °C
Crystal system
Space group
20 (293 K)
Orthorhombic
Pbca
[
7] and refined by full covariance matrix methods (SHEL-
XL-97) [8]. The crystal data, data collection and refinement
parameters for the structure are given in Table 1.
The structure of the title compound is shown in Fig. 1.
Figure 1 is the ORTEP drawing of the title compound 3
showing the atom numbering scheme (Ellipsoids: 50%
probability). Bond lengths and angles are given in Tables 2
and 3. The geometric calculations were performed using
the program SHELX-97.
˚
a = 10.068(2) A
Unit-cell dimensions
˚
b = 12.353(2) A
˚
c = 20.102(4) A
3
˚
Volume (A )
2500.1(8)
8
Z
-3
Dcalc, g cm
F(000)
1.346
1,056
Index ranges
0 B h B 11;
0
0
B k B 14;
B l B 23
Results and Discussion
-
1
Absorption coefficient, mm
0.093
In recent years, the synthesis and characteristics of 5-
amino-1-(4-chlorophenyl)-1,2,3-triazol-4-yl and 5-methyl-
Diffractometer/scan
Enraf-Nonius CAD4,
x/2h
1
-(4-methylphenyl)-1,2,3-triazol-4-yl related derivatives
˚
Radiation/k
Moka/0.71073 A
have been investigated [9–12]. These heterocyclic com-
pounds also contain the 1,2,3-triazole ring. IR peaks at
h
min, hmax (°)
Reflections measured
2.03–24.94
2,182
-
1
3
,429 and 1,724 cm for compound 3 are assigned to m
for COOH. The N–N=N vibration at 964.5 cm is in
C=O
Independent/observed reflections
Data/restraints/parameters
Refinement method
1,240
-
1
2,182/0/172
Full-matrix
agreement with values reported for 1H-1,2,3-triazole [12]
1
and differs from 2H-1,2,3-triazole [13]. In the H NMR
2
Least-squares on F
spectrum for compound 3, the chemical shift for the methyl
group in the triazole ring, (d2.711 ppm), is agreement with
values reported [14] (d2.61–2.74 ppm).
2
Goodness-of-fit on F
1.06
shift/su_max
0.0495
Final R indices
R
R
1
1
= 0.0474, wR
= 0.1120, wR
2
2
= 0.1197
= 0.1604
The 1,2,3-triazole ring system is nearly planar [15]. The
˚
R indices [I [ 2r(I)]
Largest diff. peak and hole
˚
bond lengths N1–N2 1.356(3) A, N2–N3 1.303(3) A are
agreement with the values reported for triazole, N–N
-
3
˚
0.244 and -0.215e A
1
23

J Chem Crystallogr (2009) 39:87–90
89
Table 3 All non-hydrogen
bond angles (8)
Atoms
Angle
C12–N1–N2
C12–N1–C10
N2–N1–C10
N3–N2–N1
N2–N3–C13
C2–C1–C6
111.8(2)
129.0(3)
119.2(2)
105.9(2)
110.1(2)
121.2(3)
120.8(3)
120.8(3)
119.6(3)
123.4(3)
117.3(3)
119.3(3)
122.6(3)
118.3(3)
119.1(3)
121.5(3)
119.8(3)
120.1(3)
122.4(3)
118.9(3)
118.7(3)
103.7(3)
122.6(3)
133.7(3)
108.6(3)
120.3(3)
131.2(3)
124.8(3)
123.0(3)
112.1(3)
C1–C2–C3
C4–C3–C2
C3–C4–C5
C10–C5–C4
C10–C5–C6
C4–C5–C6
C1–C6–C7
C1–C6–C5
Fig. 1 ORTEP drawing of the title compound 3 showing the atom
numbering scheme (Ellipsoids: 50% probability)
C7–C6–C5
C8–C7–C6
C7–C8–C9
˚
Table 2 Bond lengths (A)
Atoms length
Atoms length
C10–C9–C8
C9–C10–C5
C9–C10–N1
C5–C10–N1
N1–C12–C13
N1–C12–C11
C13–C12–C11
N3–C13–C12
N3–C13–C14
C12–C13–C14
O1–C14–O2
O1–C14–C13
O2–C14–C13
O1–C14
O2–C14
N1–C12
N1–N2
N1–C10
N2–N3
N3–C13
C1–C2
1.201(4)
1.311(4)
1.350(4)
1.356(3)
1.440(4)
1.303(3)
1.355(4)
1.343(5)
1.410(5)
1.392(5)
1.369(5)
1.416(4)
1.415(4)
1.419(4)
1.411(5)
1.359(5)
1.401(5)
1.351(4)
1.480(4)
1.372(4)
1.470(4)
C1–C6
C2–C3
C3–C4
C4–C5
C5–C10
C5–C6
C6–C7
C7–C8
C8–C9
C9–C10
C11–C12
C12–C13
C13–C14
˚
.351(11), 1.287(11) A [16]. The C12–N1 1.350(4) A and
˚
1
˚
C13–N3 1.355(4) A are between the bond lengths of C=N
and C–N.
In the crystal structure, there is an intermolecular
0
O2–H(2)ꢀꢀꢀN3 hydrogen bond involving the carboxylic
acid O–H atom and the triazole 3 position N atom. The
molecular packing is stabilized by intermolecular O2–
0
H(2)ꢀꢀꢀN3 interactions. It is differ from molecules of
Fig. 2 The H-bond structure of the compound 3 (PWT drawing for
the Platon)
general carboxylic acid for instance 2,4-dimethylbenzoic
123

9
0
J Chem Crystallogr (2009) 39:87–90
acid, form typical centrosymmetric hydrogen-bonded
5. 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
dimers [17]. The bond length of Donor-HꢀꢀꢀAcceptor is
˚
˚
2
.72 A(O–H 0.94; HꢀꢀꢀN3 1.82 A), the bond angle is 162.
6
. De Clercq E (2002) Med Res Rev 22:531
The H-bond structure of the compound 3 is shown in
Fig. 2.
7. Sheldrick GM (1990) Acta Crystallogr A 46:467
8. Sheldrick GM (1997) SHELXL-97, program for crystal structure
refinement. Universit a¨ t G o¨ ttingen
9
. Zhang Z-Y, Dong H-S, Zhu Y (1996) Acta Chim Sin 54:1054
Acknowledgments The authors would like to acknowledge Lanz-
hou University SKLAOC for their support.
1
1
0. Zhang Z-Y, Dong H-S, Guan Z-W, Yang S-Y (1997) Chem Res
Chin Univ 13:27
1. Zhang Z-Y, Dong H-S, Yang S-Y Org Chem (1996) 16:430;
(
1998) 18:253
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