Microwave-assistant synthesis, crystal structure and fungicidal activity of 3-Chloro-2-hydrazinylpyridine

Article abstract of DOI:10.14233/ajchem.2013.15329

A pyridine derivative i.e., 3-chloro-2-hydrazinylpyridine (C ₅H₆N₃Cl) was synthesized under microwave irradiation and its structure was studied by X-ray diffraction and ¹H NMR. The crystals are monoclinic, space group p2₁/c with a = 11.6276 (14), b = 3.8924 (5), c = 13.9558 (17) ?, α= 90.00, β= 103.447 (6), γ= 90.00°, V = 614.31(13)?³, Z = 4, F ₍₀₀₀₎ = 296, D_c = 1.552g/cm³, μ= 0.52 cm^-1, the final R = 0.0623 and wR = 0.1897. A total of 7008 reflections were collected, of which 1406 were independent (R_int = 0.0544). The fungicidal activity of this compound was also studied.

Full text of DOI:10.14233/ajchem.2013.15329

Asian Journal of Chemistry; Vol. 25, No. 15 (2013), 8708-8710
http://dx.doi.org/10.14233/ajchem.2013.15329
Microwave-Assistant Synthesis, Crystal Structure and
Fungicidal Activity of 3-Chloro-2-hydrazinylpyridine
1
1
2,*
WEI KE , NA-BO SUN and HONG-KE WU
1College of Biology and Environmental Engineering, Zhejiang Shuren University, Hangzhou 310015, Zhejiang Pronvince, P.R. China
2College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310014, Zhejiang Province, P.R. China
*Corresponding author: E-mail: wuhk910@gmail.com
(Received: 13 February 2013;
Accepted: 26 August 2013)
AJC-14031
A pyridine derivative i.e., 3-chloro-2-hydrazinylpyridine (C5H6N3Cl) was synthesized under microwave irradiation and its structure was
1
studied by X-ray diffraction and H NMR. The crystals are monoclinic, space group p21/c with a = 11.6276 (14), b = 3.8924 (5), c =
13.9558 (17) Å, α = 90.00, β = 103.447 (6), γ = 90.00º, V = 614.31(13)Å3, Z = 4, F(000) = 296, Dc = 1.552g/cm3, µ = 0.52 cm-1, the final R
= 0.0623 and wR = 0.1897. A total of 7008 reflections were collected, of which 1406 were independent (Rint = 0.0544). The fungicidal
activity of this compound was also studied.
Key Words: Microwave assistant synthesis, Crystal structure, Biological activity.
Crystal structure determination:The crystal of 3-chloro-
2-hydrazinylpyridine with dimensions of 0.12 mm × 0.08
mm × 0.06 mm was mounted on a Rigaku Saturn CCD area-
detector diffractometer with a graphite-monochromated MoKα
radiation (λ = 0.71073 Å) by using a phi and scan modes at
294(2) K in the range of 3.1º ≤ θ ≤ 27.7º. The crystal belongs
to monoclinic system with space group P21/C and crystal
parameters of a = 11.6276(14) Å, b = 3.8924(5) Å, c =
13.9558(17) Å, α = 90º β = 103.447(6)º, γ = 90º, V =
614.31(13) A3 Dc = 1.552 g/cm3. The absorption coefficient µ
= 0.520 mm-1 and Z = 4. The structure was solved by direct
methods with SHELXS-97 and refined by the full-matrix least
squares method on F2 data using SHELXL-97. The empirical
absorption corrections were applied to all intensity data. H
atom of N-H was initially located in a difference Fourier map
and were refined with the restraint Uiso(H) = 1.2Ueq(N). Other
H atoms were positioned geometrically and refined using a
riding model, with d(C-H) = 0.93-0.97 Å and Uiso(H) = 1.2
Ueq(C) or 1.5 Ueq(Cmethyl). The final full-matrix least
squares refinement gave R = 0.0623 and wR = 0.1897.
INTRODUCTION
In recent years, heterocyclic compounds had received
considerable attentions because of their important biological
activity1. So the synthesis of broader spectrum and highly
bioactive compounds becomes the mainstream in the medicinal
and agriculture chemistry field2. Pyridine derivatives also exhi-
bited excellent property, such as nicotinate mononucleotide
adenylyltransferase inhibitor3, antifungal activity4, antiinflam-
matory activity5, antimicrobial activities6, anticancer activity7,
antiviral activity8, cholesterol absorption inhibitors9. Micro-
wave technique has been widely used for a variety of organic
reactions, such as Claisen, heterocyclic synthesis, oxidation,
hydrolysis, esterification, etherification, etc.
In order to search for new compounds with good biological
activity, a pyridine compound was synthesized under micro-
wave irradiation. Their structures are confirmed by 1H NMR
and single crystal. The preliminary biological tests show that
these compounds had moderate fungicidal activity.
EXPERIMENTAL
Synthesis:A modified two-phase procedure was applied.
2,3-Dichloropyridine (0.2 mol), hydrazine hydrate (85 %, 1
mol) were put in a sealed vial, then refluxed at 100ºC for 0.5
h under microwave irradiation. The product was obtained after
filtrated. 1H NMR (CDCl3, 400 MHz): 3.97 (br. s, 2H, NH2),
6.21 (br. s, 1H, NH), 6.64 (m, 1H, pyridyl-H), 7.47 (d, 1H, J =
7.6 Hz, pyridyl-H), 8.09 (d, 1H, J = 4.9 Hz, pyridyl-H).
Melting points determined by aYanaco MP-241 apparatus
and uncorrected. Infrared spectra were recorded on a Bruker
Equinox55 spectrophotometer as KBr tablets. 1H NMR spectra
were measured on a Bruker AC-P500 instrument (300 MHz)
using TMS as internal standard and CDCl3 as solvent. Crysta-
llographic data of the compound collected on a BRUCKER
CCD SMART diffractometer.All chemicals were ofAR grade.

Vol. 25, No. 15 (2013)
Synthesis, Crystal Structure and Fungicidal Activity of 3-Chloro-2-hydrazinylpyridine 8709
TABLE-2
Cl
Cl
NH2NH2, MW
SELECTED BOND LENGTHS [Å] FOR THE TITLE COMPOUND
NH2
Bond lengths
Cl(1)-C(2)
N(3)-C(1)
N(3)-C(5)
N(1)-N(2)
N(1)-H(1A)
N(1)-H(1B)
C(1)-N(2)
C(1)-C(2)
X-Ray crystal
1.740(3)
1.335(4)
1.348(5)
1.403(4)
0.86
0.86
1.365(4)
1.412(4)
Bond lengths
N(2)-H(2A)
C(2)-C(3)
C(4)-C(5)
C(4)-C(3)
C(4)-H(4A)
C(5)-H(5A)
C(3)-H(3A)
–
X-Ray crystal
N
N
H
N
Cl
0.86
1.357(5)
1.369(6)
1.389(6)
0.93
0.93
0.93
Scheme-I: Synthesis route of 3-chloro-2-hydrazinylpyridine
RESULTS AND DISCUSSION
Synthesis and spectroscopic properties: The title
compound was synthesized under conventional and microwave
irradiation condition. If the title compound was synthesized
under refluxing, it should react with ethanolic solution of
NH2NH2 for 72 h. Surprisingly, it was synthesized for 0.5 h
–
TABLE-3
SELECTED BOND ANGLES [º] FOR THE TITLE COMPOUND
1
under microwave irradiation. H NMR spectrum of the title
compound tested shows 3.97 and 6.21 is the peak of NH2 and
NH, respectively. The 6.647.478.09 can be assigned to the
three CH of pyridine. The melting point is according to the
reference.
Structure of the title compound: Crystallographic and
refinement parameters are given in Table-1. The selected bond
lengths and bond angles listed in Tables 2-4, respectively. The
structure was solved by direct methods. Anisotropic displace-
ment parameters were applied to all nonhydrogen atoms in
full-matrix least-square refinements based on F2. The hydrogen
atoms were set in calculated positions with a common fixed
isotropic thermal parameter.
Bond
angles
X-Ray
crystal
118.1(3)
120
120
120
118.4(3)
120.7(3)
121.0(3)
121.5(3)
119.3
Bond
angles
X-Ray
crystal
120.9(3)
118.6(2)
118.4(3)
120.8
120.8
123.8(3)
118.1
C(1)-N(3)-C(5)
N(2)-N(1)-H(1A)
N(2)-N(1)-H(1B)
H(1A)-N(1)-H(1B)
N(3)-C(1)-N(2)
N(3)-C(1)-C(2)
N(2)-C(1)-C(2)
C(1)-N(2)-N(1)
C(1)-N(2)-H(2A)
N(1)-N(2)-H(2A)
C(3)-C(2)-C(1)
C(3)-C(2)-Cl(1)
C(1)-C(2)-Cl(1)
C(5)-C(4)-C(3)
C(5)-C(4)-H(4A)
C(3)-C(4)-H(4A)
N(3)-C(5)-C(4)
N(3)-C(5)-H(5A)
C(4)-C(5)-H(5A)
C(2)-C(3)-C(4)
C(2)-C(3)-H(3A)
C(4)-C(3)-H(3A)
118.1
118.6(3)
120.7
119.3
120.5(3)
120.7
TABLE-1
TABLE-4
CRYSTAL DATA AND STRUCTURE
REFINEMENT FOR THE TITLE COMPOUND
SELECTED BOND ANGLES [º] TORSIONAL
ANGELS (º) FOR THE TITLE COMPOUND
Items
Empirical formula
Formula weight
Crystal system
Space group
Values
Bond angles
X-Ray crystal
-177.6(3)
0.4(5)
-9.2(5)
172.8(3)
-0.3(5)
177.7(3)
178.4(3)
-3.6(5)
-0.1(5)
-0.3(6)
C5H6N3Cl
143.58
monoclinic
p21/c
C(5)-N(3)-C(1)-N(2)
C(5)-N(3)-C(1)-C(2)
N(3)-C(1)-N(2)-N(1)
C(2)-C(1)-N(2)-N(1)
N(3)-C(1)-C(2)-C(3)
N(2)-C(1)-C(2)-C(3)
N(3)-C(1)-C(2)-Cl(1)
N(2)-C(1)-C(2)-Cl(1)
C(1)-N(3)-C(5)-C(4)
C(3)-C(4)-C(5)-N(3)
C(1)-C(2)-C(3)-C(4)
Cl(1)-C(2)-C(3)-C(4)
C(5)-C(4)-C(3)-C(2)
Unit cell dimensions
11.6276(14)
3.8924(5)
13.9558(17)
Unit cell angles (º)
90
a (Å)
b (Å)
c (Å)
α
-0.2(6)
-178.8(3)
0.5(6)
103.447(6)
90
614.31(13)
4
β
γ
Volume (Å3)
Z
Temperature (K)
Wavelength (Å)
296(2)
0.71073
1.552
0.520
296
Calculated density (g/cm3)
Absorption coefficient (mm-1)
F(000)
Theta range for data collection (º) 1.80-27.72
Reflections collected
7008
Independent reflections
1406 [R(int) = 0.0544]
R1 = 0.0623, wR2 = 0.1897
Final R indices [I > 2σ(I)]
The molecular structure and atom labels are shown in
Fig. 1. The one-dimensional linework of hydrogen bonds
(dashed lines) is illustrated in Fig. 2, respectively.
In Table-3, the results indicate that the lengths of three C-
N bond C5-N3, C1-N2 and N3-C1 are 1.348(5), 1.365(4) and
1.335(4) Å, respectively, which are all longer than those in
the single heterocycle ring. However, the C5-N3, C1-N2
Fig. 1. Molecular structure of 3-chloro-2-hydrazinylpyridine

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of 1.27 Å. The N1-N2 bond lengths is 1.403(4) Å. The bond
angles of pyridine ring vary from 118.4(3) to 121.5(3)º with
the average of 120º.
The title compound has an extensive network of hydrogen
bonding involving the two acceptor atoms N. In the ac plane,
they are linked together by N(1)-H(1C)···N(2)# 2, N(1)-
H(1B)···N(3)# 2 hydrogen bonds. This hydrogen-bonding
sequence is repeated to form a ring. The ring has two N atoms
at the vertices, leading to a hydrogen-bond network defining
cyclic motifs denoted R22(6). The vertices are shared with
neighbouring decagon to form an infinite two-dimensional
network of hydrogen bonds in the ac plane.
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arachidicola, Botryosphaeria berengeriana f.sp. piricola
(Nose) koganezawa et Sakuma, Fusarium oxysporum f.sp.
cucumerinum, were determined according the reference. At
the dose of 50 µg/mL, the title compounds display moderate
fungicidal activity against Gibberella zeae (Schwein.) Petch.
(32 %), Alternaria solani (Ellis et Martin) Jones et Grout.
(44 %), Cercospora arachidicola (18 %), Botryosphaeria
berengeriana f.sp. piricola (Nose) koganezawa et Sakuma
(51 %), Fusarium oxysporum f.sp. cucumerinum (21 %),
respectively.
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