Synthesis and crystal structure of 3-methyl-4-phenyl-5-(2-pyridyl)-1,2,4- triazole

Article abstract of DOI:10.1007/s10870-009-9583-3

The title compound, 3-methyl-4-phenyl-5-(2-pyridyl)-1,2,4-triazole was synthesized by reaction of diphenylphosphazoanilide with N-acetyl-N-(2- pyridoyl)hydrazine. Crystals suitable for X-ray analysis were obtained from a mixed solution of water and ethano

Full text of DOI:10.1007/s10870-009-9583-3

J Chem Crystallogr (2009) 39:881–884
DOI 10.1007/s10870-009-9583-3
ORIGINAL PAPER
Synthesis and Crystal Structure of 3-Methyl-4-phenyl-5-(2-
pyridyl)-1,2,4-triazole
Chunyi Liu Æ Zuoxiang Wang Æ Hailian Xiao Æ
Yan Lan Æ Xiaomin Li Æ Songpei Wang Æ
Jie Tang Æ Zhengping Chen
Received: 9 September 2008 / Accepted: 7 June 2009 / Published online: 18 June 2009
Ó Springer Science+Business Media, LLC 2009
Abstract The title compound, 3-methyl-4-phenyl-5-(2-
pyridyl)-1,2,4-triazole was synthesized by reaction of
diphenylphosphazoanilide with N-acetyl-N0-(2-pyridoyl)
hydrazine. Crystals suitable for X-ray analysis were
obtained from a mixed solution of water and ethanol in
a one-to-one volume ratio. The crystal is orthorhombic,
space group P212121 with crystallographic parameters:
This arises, in part, because they can form complexes with
transition-metal ions, and some of them exhibit spin
crossover behavior, which can be used potentially in
molecular-based memory devices, displays and optical
switches [7–11].
1,2,4-triazoles with pyridine substituents are compounds
that have been known for many years and are widely used
in coordination chemistry. The first synthesized represen-
tative of this group of compounds was 3,5-di(4-pyridyl)-
1,2,4-triazole, obtained by the deamination of 4-amino-3,5-
di(4-pyridyl)-1,2,4-triazole [12]. A series of complexes
have been synthesized by the use of pyridyl-1,2,4-triazoles.
For example, the complexes [NiI2I(NH2dpt)2Cl2(H2O)2]
Cl2ꢀ4H2O [13], [CuII(NH2dpt)2(H2O)](HSO4)2 [14], [AgI
(mpdpt) (pph3)2]ClO4 [15], and [CuII(emppt)2](ClO4)2 [16]
have been described in the literature. In order to synthesize
and examine the novel complexes of transition-metal ions
with pyridyl-1,2,4-triazoles, the title compound was syn-
thesized by reaction of diphenylphosphazoanilide with N-
acetyl-N0-(2-pyridoyl)hydrazine in N,N-dimethylaniline at
463–473 K as shown in Scheme 1. The objective product
˚
˚
˚
a = 19.414(4) A, b = 17.172(3) A, c = 7.4850(15) A,
b = 90.00°, l = 0.079 mm-1, V = 2495.3(8) A , Z = 8,
3
˚
Dc = 1.258 g/cm3, F(000) = 992, T = 295(2) K. The
X-ray results showed that in the crystal structure of the title
compound, the 1,2,4-triazole, pyridine and benzene rings
are not coplanar.
Keywords 1,2,4-Triazole ꢀ Pyridine ꢀ Benzene ring ꢀ
pꢀꢀꢀp Interaction
Introduction
The coordination chemistry of substituted 1,2,4-triazoles
has gained considerable attention in recent years [1–6].
1
was characterized by HNMR, IR and MS, and its crystal
structure was determined by X-ray analysis.
C. Liu ꢀ X. Li ꢀ S. Wang ꢀ J. Tang ꢀ Z. Chen (&)
The Key Laboratory of Nuclear Medicine, Ministry of Health
P.R. China, Jiangsu Institute of Nuclear Medicine, 20 Qianrong
Road, 214063 Wuxi, People’s Republic of China
e-mail: lcy_seu@yahoo.com.cn
Experimental
Materials and Physical Measurements
Z. Wang ꢀ Y. Lan
Department of Chemistry & Chemical Engineering,
Southeast University, 210096 Nanjing,
People’s Republic of China
The N-acetyl-N0-(2-pyridoyl)hydrazine and diphenyl-
phosphazoanilide were synthesized according to literature
methods [17, 18]. All other solvents and reagents were of
analytical grade and were used without further purification.
IR spectra in the range 4,000–400 cm-1 were obtained
from samples in the form of KBr pellets using a Nicolet
H. Xiao
New Materials & Function Coordination Chemistry Laboratory,
Qingdao University of Science & Technology, 266042 Qingdao,
People’s Republic of China
123

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J Chem Crystallogr (2009) 39:881–884
Scheme 1 Synthesis of
compound 2
N
N
N
O
O
N
CH3
C6H5N P NHC6H5
N,N-dimethylaniline
N
CNHNHCCH3
1
2
550 infrared spectrometer. MS spectra were recorded with
a VG ZAB-HS mass spectrometer. Proton NMR spectra
were obtained at 500 MHz on Bruker spectrometer in
CDCl3. Melting points were determined by using a RY-1
melting point apparatus.
full-matrix least-squares techniques on F2 with anisotropic
thermal parameters, using SHELXL-97 [20]. All H atoms
were located in a difference Fourier map and allowed to
˚
ride on their parent atoms at distances of 0.93 A (C–H
˚
aromatic) and 0.96 A (C–H methyl), with Uiso(H) values of
1.2–1.5 times Ueq of the parent atoms. The final full-matrix
least-squares refinement gave R = 0.0699, wR = 0.1961
for 1,150 reflections with I [ 2r(I); the weighting scheme,
w = 1/[r2(FO2 ) ? (0.1480P)2], where P = (FO2 ? 2F2C)/3.
The maximum and minimum difference peaks and holes
Synthesis of 3-Methyl-4-phenyl-5-(2-pyridyl)-1,2,4-
triazole (2)
To
a
solution of diphenylphosphazoanilide (8.6 g,
40 mmol) in anhydrous N,N-dimethylaniline (40 mL) under
stirring was added N-acetyl-N0-(2-pyridoyl)hydrazine
(7.2 g, 40 mmol). The mixture was heated under reflux at
463–473 K for 3 h, and the solvent was removed under
reduced pressure. The residue was then added to a mixture
of water (20 mL) and concentrated hydrochloric acid
(10 mL) and was hydrolyzed under reflux for 1 h. The
mixture was filtered, and K2CO3 was added to the filtrate
until the pH reached 8–9. The solid substance separated out,
and the crude product was recrystallized from acetone.
White crystals (4.7 g, 20 mmol) were obtained. Yield: 50%.
M.pt: 104–106 °C. MS, m/z: 237.1 [M ? H]?; 236.1 [M]?;
235.1 [M-H]?. IR (KBr, cm-1): 3,048; 1,591; 1,498; 1,444;
1,380. 1H NMR (CDCl3, 500 MHz; d): 2.37 (s, 3H, –CH3);
7.18–7.49 (m, 5H, –C6H5); 7.50–8.30 (m, 4H, –C5H4N).
The colorless single crystal of compound 2 was grown
from a mixed solution of water and ethanol in a one-to-one
volume ratio by slow evaporation at room temperature.
are 0.256 and -0.268 e A-3, respectively. S = 0.986 and
˚
(D/r)max = 0.000. The crystal data and refinement details
are listed in Table 1. The selected bond lengths and bond
angles are listed in Table 2.
Results and Discussion
The title compound crystallized in the orthorhombic sys-
tem, space group P212121 with unit cell parameters:
˚
˚
˚
a = 19.414(4) A, b = 17.172(3) A, c = 7.4850(15) A,
b = 90.00°, l = 0.079 mm-1, V = 2495.3(8) A , Z = 8,
3
˚
Dc = 1.258 g/cm3, F(000) = 992, T = 295(2) K. The
molecular structure of compound 2 is shown in Fig. 1 and a
perspective view of the crystal packing in the unit cell is
shown in Fig. 2.
There are three aromatic rings in the structure of com-
pound 2, namely 1,2,4-triazole, pyridine and benzene.
None are coplanar. The dihedral angle between the 1,2,4-
triazole and pyridine rings is 16.56°, and that between the
1,2,4-triazole and benzene rings is 80.05°.
In the five-membered triazole ring, the interatomic dis-
˚
tances of N(2)–C(6) (1.303(8) A) and N(3)–C(7)
˚
(1.316(9) A) are shorter than typical carbon–nitrogen sin-
˚
gle bonds (1.336–1.416 A) [21], suggesting that they have
X-Ray Crystallography
A single crystal of the title compound with dimensions
0.30 9 0.25 9 0.20 mm was chosen for X-ray diffraction
study. The data were collected on a Enraf-Nonius CAD-4
diffractometer equipped with graphite-monochromatic Mo-
˚
Ka radiation (k = 0.71073 A) by using an x scan mode at
substantial double bond character. There is a little differ-
ence between the bond lengths of N(2)–C(6) and N(3)–
C(7) due to the asymmetry of the 1,2,4-triazole ring, which
is in accordance with the fact that the three substituents of
triazole are different. The bond lengths of N(4)–C(6)
295(2) K. In the range of 1.58° \ h \ 26.54°, a total of
3,081 reflections were collected, of which 2,879 were
independent (Rint = 0.0251) and 1,150 were observed with
I [ 2r(I).
˚
(1.374(8) A), N(4)–C(7) (1.354(8) A) and N(2)–N(3)
˚
The structure was solved by direct methods with
˚
(1.399(9) A) correspond to the typical carbon–nitrogen
SHELXS-97 [19]. Non-hydrogen atoms were refined by
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J Chem Crystallogr (2009) 39:881–884
883
˚
Table 1 Crystallographic data and structure refinement details
Table 2 Selected bond lengths (A) and angles (°)
CCDC deposit number
Empirical formula
Formula weight
701445
14H12N4
Bond lengths
C
N(1)–C(1)
N(1)–C(5)
N(2)–C(6)
N(2)–N(3)
N(3)–C(7)
N(4)–C(7)
N(4)–C(6)
N(4)–C(9)
C(1)–C(2)
C(2)–C(3)
Bond angles
1.334(9) C(3)–C(4)
1.336(8) C(4)–C(5)
1.303(8) C(5)–C(6)
1.399(9) C(7)–C(8)
1.316(9) C(9)–C(14)
1.354(8) C(9)–C(10)
1.374(8) C(10)–C(11)
1.439(8) C(11)–C(12)
1.356(10) C(12)–C(13)
1.401(11) C(13)–C(14)
1.393(13)
1.367(10)
1.497(10)
1.485(10)
1.367(12)
1.433(12)
1.388(11)
1.390(16)
1.418(17)
1.370(12)
236.28
Temperature (K)
295 (2)
˚
Wavelength (A)
0.71073
0.30 9 0.25 9 0.20
Orthorhombic
P212121
19.414 (4)
17.172 (3)
7.4850 (15)
90.00
Crystal size (mm)
Crystal system
Space group
˚
a (A)
˚
b (A)
˚
c (A)
a (°)
b (°)
c (°)
90.00
C(1)–N(1)–C(5) 115.7(7)
C(6)–N(2)–N(3) 105.9(6)
C(7)–N(3)–N(2) 107.5(6)
C(7)–N(4)–C(6) 104.3(5)
C(7)–N(4)–C(9) 124.5(6)
C(6)–N(4)–C(9) 131.0(6)
N(1)–C(1)–C(2) 126.7(8)
C(1)–C(2)–C(3) 116.8(9)
C(4)–C(3)–C(2) 117.6(9)
C(5)–C(4)–C(3) 120.0(8)
N(1)–C(5)–C(4) 123.0(7)
N(1)–C(5)–C(6) 118.1(6)
C(4)–C(5)–C(6) 118.6(7)
N(2)–C(6)–N(4) 111.5(7)
N(2)–C(6)–C(5)
N(4)–C(6)–C(5)
N(3)–C(7)–N(4)
N(3)–C(7)–C(8)
N(4)–C(7)–C(8)
122.7(7)
90.00
125.8(6)
110.5(7)
125.2(7)
124.1(6)
3
˚
V (A )
2495.3 (8)
8
Z
Dca (g cm-3
)
1.258
F (000)
992
C(14)–C(9)–C(10) 122.9(7)
Absorption coeff. (mm-1
h range (°)
Index ranges
)
0.079
C(14)–C(9)–N(4)
C(10)–C(9)–N(4)
120.2(9)
116.9(8)
1.58–26.54
0 B h B 23; 0 B k B 20;
-8 B l B 0
C(11)–C(10)–C(9) 116.2(9)
C(10)–C(11)–C(12) 121.1(10)
C(11)–C(12)–C(13) 120.9(7)
C(14)–C(13)–C(12) 118.7(11)
C(9)–C(14)–C(13) 120.3(11)
Reflections collected
Independent reflections
Observed reflections
3,081
2,879 [Rint = 0.0251]
1,150
Data/restraints/parameters
Goodness-of-fit on F2
2,879/0/326
0.986
R, wR indices [I [ 2r(I)]
R, wR indices (all data)
0.0699, 0.1961
0.2161, 0.2730
0.256, -0.268
-3
)
˚
Largest diff. peak and hole (e A
˚
single bonds (1.336–1.416 A) and nitrogen–nitrogen single
˚
bonds (1.366–1.454 A) [21], respectively.
pꢀꢀꢀp Interactions are important noncovalent intermo-
lecular forces. There are two different patterns of the
stacked arrangements in general aromatic systems for pꢀꢀꢀp
interactions: offset face-to-face and edge-to-face packing.
The distance between aromatic ring centriods with the
˚
range of 3.2–3.8 A is the valid value of pꢀꢀꢀp interactions in
the offset face-to-face stacking. Likewise, that between
hydrogen atom and aromatic ring centriod with the range of
˚
2.0–3.5 A is the valid value of pꢀꢀꢀp interactions in the
Fig. 1 The two symmetry-independent molecular structures of 3-
methyl-4-phenyl-5-(2-pyridyl)-1,2,4-triazole; 50% probability ellip-
soids are shown
edge-to-face stacking [22]. In the crystal, molecules of
compound 2 are stabilized by weak offset face-to-face pꢀꢀꢀp
interactions and edge-to-face pꢀꢀꢀp interactions. The dis-
tance between ring centroids of Cg1 [Cg1 is the five-
membered triazole ring (N2, N3, C7, N4, C6) with sym-
metry code: x, y, z] and Cg2 [Cg2 is the five-membered
triazole ring (N6, N7, C21, N8, C20) with symmetry code:
˚
between Cg1 and Cg2 is 3.606 A, and the angle between
the ring-centroid vector and the perpendicular vector of
two-five-membered triazole planes is about 8.58. The bond
lengths of H18AꢀꢀꢀCg3 [Cg3 is the six-membered pyridine
ring (N1, C1, C2, C3, C4, C5) with symmetry code: x, y,
˚
x, y, -1 ? z] is 3.646 A. The perpendicular distance
123

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J Chem Crystallogr (2009) 39:881–884
Science Foundation of the Health Department of Jiangsu Province
(H200401) and the High Technology Research and Development
Program of Jiangsu Province (BG2007603).
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123