The synthesis and crystal structure of new bis(3-chlorophenyl)-[5-methyl-1- (4-methylphenyl)-1,2,3-triazol-4-yl]-methanol

Article abstract of DOI:10.1007/s10870-008-9424-9

The title compound bis(3-chlorophenyl)-[5-methyl-1-(4-methylphenyl)-1,2,3- triazol-4-yl]-methanol 8 has been synthesized and established by H NMR, IR and MS spectra and X-ray diffraction crystallography. Compound 8, C ₂₃H₂₉Cl₂N₃O, Mr = 424.31, crystallizes in the monoclinic space group P2₁/c with unit cell parameters a = 14.5402(6) A, b = 12.5888(5) A, c = 11.6510(5) A, α = 90°, β = 100.183°(2), γ = 90°, V = 2099.05(15) A³, D_x = 1.343 mg m^-3 and Z = 4. The final R was 0.0514. The molecular conformation and packing is stabilized by interactions of intermolecular O1-H1...;N3′.

Full text of DOI:10.1007/s10870-008-9424-9

J Chem Crystallogr (2009) 39:28–31
DOI 10.1007/s10870-008-9424-9
ORIGINAL PAPER
The Synthesis and Crystal Structure of New Bis(3-chlorophenyl)-
[5-methyl-1-(4-methylphenyl)-1,2,3-triazol-4-yl]-methanol
Heng-Shan Dong Æ Guo-Yong Huo
Received: 4 September 2006 / Accepted: 4 June 2008 / Published online: 19 June 2008
Ó Springer Science+Business Media, LLC 2008
Abstract The title compound bis(3-chlorophenyl)-[5-
methyl-1-(4-methylphenyl)-1,2,3-triazol-4-yl]-methanol 8
has been synthesized and established by H NMR, IR and
MS spectra and X-ray diffraction crystallography. Com-
pound 8, C23H29Cl2N3O, Mr = 424.31, crystallizes in the
monoclinic space group P21/c with unit cell parameters
The route of syntheses of the title compound is in
Scheme 1.
Experimental Section
˚
˚
˚
a = 14.5402(6) A, b = 12.5888(5) A, c = 11.6510(5) A, a =
All melting points were uncorrected and determined on an
XT4-100x microscopic melting point apparatus. IR spectra
were obtained in KBr discs on a Nicolet NEXUS 670 FT-IR
spectrometer. MS were performed on a HP-5988A spec-
trometer (EI at 70 eV). 1H NMR spectroscopy (CDCl3) was
recorded on Varian Mercury plus-300 instrument with TMS
as an internal standard.
3
˚
908, b = 100.1838(2), c = 908, V = 2099.05(15) A , Dx =
1.343 mg m-3 and Z = 4. The final R was 0.0514. The
molecular conformation and packing is stabilized by
interactions of intermolecular O1–H1ꢀꢀꢀN30.
Keywords Crystal structure ꢀ Synthesis ꢀ
1H-1,2,3-triazole ꢀ H-bond ꢀ Methanol
Preparation of the Title Compound
Introduction
5-Methyl-1-(4-methylphenyl)-1,2,3-triazol-4-carboxylic
acid 3 was prepared following methods in the literature [8]
Mp182–183 °C(Lit. Mp182–183 °C).
5-Methyl-1-(4-methylphenyl)-1,2,3-triazol-4-carboxylic
acid ethyl ester 4 was prepared following methods in the
literature [8] Mp130–132 °C(Lit. Mp130–132 °C).
1-Bromo-3-chlorobenzene 6 was prepared following
methods in the literature [9].
In recent years in various publications, certain compounds
that 1-aryl-5-methyl-4-substituted-1,2,3-triazoles often
exhibit broad spectrum biological actions [1, 2], antibac-
terial [3], antifungal [4], antiviral [5], anti-inflammatory
and analgetic properties [6]. Some of 1,2,3-triazole deriv-
atives had been reported to inhibit tumor proliferation,
invasion and metastasis [7]. Therefore, it is worthwhile to
investigate these properties of 1,2,3-triazole. As a great
deal of interest has been focused on it, we synthesized a
new title compound.
3-Chlorophenylmagnesium bromide 7 was prepared
following methods in the literature [10].
Preparation of bis(3-chlorophenyl)-[5-methyl-1-(4-methyl-
phenyl)-1,2,3-triazol-4-yl]-methanol
method in the literature [10].
8
was following
A mixture of 3-chlorophenylmagnesium bromide 7
(4.31 g, 0.02 mol) and 35.0 mL ether was dripped to a
mixture of 5-methyl-1-(4-methylphenyl)-1,2,3-triazol-
4-carboxylic acid ethyl ester 4 (0.5 g, 0.002 mol) and
benzene 20.0 mL under stirring. After 3-chlorophenyl-
H.-S. Dong (&) ꢀ G.-Y. Huo
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
e-mail: donghengshan@lzu.edu.cn
123

J Chem Crystallogr (2009) 39:28–31
29
N3
N2+Cl-
Cl1
C4
NH2
CH3
HCl NaNO2
0-5°C
NaN3
0-5°C
C1
C6
C5
C18
C22
C2
O1
C14
C19
C16
CH3
CH3
2
C15
C23
C13
1
C3
C12
C20
C21
N1 C17
N3
C10
COOH
CH3
COOEt
CH3
N2
Cl2
C11
N
N
N
C7
C8
N
C9
N
N
CH3COCH2COOEt
EtOH
EtONa EtOH
H2SO4
Fig. 1 ORTEP diagram of the compound 8 showing 50% thermal
ellipsoids
CH3
3
CH3
4
Cl
Cl
Table 1 Crystal data and structure refinement details
Cl
HBr, NaNO2
0-5°C
CuBr
Empirical formula
Formula weight
Deposit no.
C23H29Cl2N3O
424.31
HBr
N2+Br-
Br
Cl
NH2
619676
294(2)
5
6
Temperature (K)
˚
Wavelength (A)
0.71073
25
Reflns. for cell determination
2h range for above
Crystal system
HO
N
C
10°-20°
Monoclinic
P21/c
Cl
N
N
CH3
Mg
4
Space group
Cl
˚
a = 14.5402(6) A
Et2O
Cell dimensions
MgBr
˚
b = 12.5888(5) A
8
˚
c = 11.6510(5) A
7
CH3
a = 90
b = 100.183(2)
Scheme 1 The synthesis route of compound 8
c = 90°
2099.05(2)
3
˚
Volume (A )
magnesium bromide was dripped, the mixture liquid was
stirred for 1 h. The 5 mL 6 N HCl was poured into the
reaction mixture and the thick and cloudy liquor was fil-
tered and then the resulting solution was evaporated. The
solid was purified by recrystallisated with EtOH to give
white blocks of compound 8, Yield 80% (0.85 g), Mp143–
Z
4
Density(calculated), mg/m3
Absorption coefficient (mm-1
Diffractometer/scan
1.343
)
0.328
Smart Apex II
CCD area detector x/2h
880
F(000)
1
144 °C. H NMR d(ppm): 4.437 (b, OH), 1.789 (s, 3H,
CH3), 2.428 (s, 3H, CH3), 7.186–7.401 (m, 12H, phenyl).
MS M/z (%): 423.8 (M+) 394 (7.2) 256 (6.7) 139 (45.5)
h range for data collection, deg
2.15–26
Index ranges
-17 B h B 15;
-15 B k B 14;
-9 B l B 14
4107
132 (44.2) 111 (31.7) 107 (84.2) 91 (100). IR(KBr) tmax
:
3376(w, OH), 2921(s), 1515(s), 1470(s), 1196(s), 1139(s),
1098(s), 1041(s), 876(s), 790(s), 751(s), 708(s).
Reflections collected
Independent reflection
Data/restrains/parameters
Extinction Coeff.
Goodness-of-fit on F2
Final R indices [I [ 2r(I)]
R indices
2348
The purified product was dissolved in ethyl acetate and
petroleum ether solvent. The crystal was obtained after 20d
by evaporation of the solvent.
4107/0/266
0.0030(12)
0.939
Single crystals were selected and mounted on the tip of a
glass fiber. Data were collected on a SMART APEX II
CCD using graphite monochromatized MoKa radiation
R1 = 0.0514, wR2 = 0.1420
R1 = 0.1000, wR2 = 0.1797
-3
˚
Largest diff. peak and hole
0.195 and -0.292 e A
˚
(k = 0.71073 A). The structure was determined by direct
123

30
J Chem Crystallogr (2009) 39:28–31
methods (SHELXS-97) and refined by full covariance
matrix methods (SHELXL-97). The structure of the title
compound is shown in Fig. 1. The crystal data and the
refinement details are given in Table 1. The selected bond
lengths are given in Table 2, selected bond angles are
given in Table 3. The geometric calculations were per-
formed using the program SHELX-97.
˚
Table 2 Selected bond lengths (A)
Results and Discussion
Atoms
Length
Atoms
Length
Title compound was obtained by the reaction of compound
4 and Grignard regent which was prepared with m-chlo-
robromobenzene from m-chloroaniline. The reaction of
compound 4 and Grignard regent excessively was an
addition reaction from ester function to hydroxyl group
through intermediate of carbonyl group function. The main
product of reaction was given by the addition reaction of
carbonyl group and Grignard regent.
C14ꢀꢀꢀN3
C14ꢀꢀꢀC15
C14ꢀꢀꢀC13
N3ꢀꢀꢀN2
N2ꢀꢀꢀN1
O1ꢀꢀꢀC13
C1ꢀꢀꢀC2
C1ꢀꢀꢀC6
C1ꢀꢀꢀCl-1
C2ꢀꢀꢀC3
C3ꢀꢀꢀC4
C4ꢀꢀꢀC5
C5ꢀꢀꢀC6
C5ꢀꢀꢀC13
C7ꢀꢀꢀC8
C7ꢀꢀꢀC12
1.358(3)
1.372(3)
1.512(3)
1.313(3)
1.353(3)
1.431(3)
1.378(4)
1.380(4)
1.737(3)
1.371(4)
1.387(4)
1.385(4)
1.382(4)
1.533(3)
1.372(4)
1.373(4)
C7ꢀꢀꢀCl-2
C8ꢀꢀꢀC9
1.744(3)
1.365(5)
1.381(4)
1.385(4)
1.386(4)
1.540(3)
1.355(3)
1.493(4)
1.440(3)
1.364(4)
1.370(4)
1.379(4)
1.373(4)
1.358(4)
1.502(4)
1.380(4)
C9ꢀꢀꢀC10
C10ꢀꢀꢀC11
C11ꢀꢀꢀC12
C11ꢀꢀꢀC13
C15ꢀꢀꢀN1
C15ꢀꢀꢀC16
N1ꢀꢀꢀC17
C17ꢀꢀꢀC22
C17ꢀꢀꢀC18
C18ꢀꢀꢀC19
C19ꢀꢀꢀC20
C20ꢀꢀꢀC21
C20ꢀꢀꢀC23
C21ꢀꢀꢀC22
An ORTEP diagram of the compound 8 showing 50%
thermal ellipsoids is show in Fig. 1. The X-ray structure
analysis indicated that the compound 8 consisted of three
phenyl rings and one triazole ring. The four aromatic rings
do not share a common plane. The two m-chlorophenyl
rings and a triazole ring are attached to the same carbon
atom (C13) which owe to the sp3 character. The force of
steric repulsion is obvious between two m-chlorophenyl
rings and a triazole ring. So the bond angles of O1–C13–
C14 [104.03(18)°], O1–C13–C5 [110.9(2)°], O1–C13–C11
[109.42(18)°], C11–C13–C14 [111.4(2)°], C11–C13–C5
[111.1(2)°] and C14–C13–C5 [109.75(19)°] have different
variety compared with the normal bond angles(109°280).
The dihedral angles between the phenyl rings and triazole
rings are 47.3–49.7° [N2–N1–C17–C22 47.3(3)°, C15–N1–
C17–C22 -134.1(3)°, N2–N1–C17–C18 -128.8(3)°, C15–
N1–C17–C18 49.7(4)°].
Table 3 Selected bond angles (°)
Atoms
Angle
Atoms
Angle
N3ꢀꢀꢀC14ꢀꢀꢀ C15
N3ꢀꢀꢀC14ꢀꢀꢀC13
C15ꢀꢀꢀC14ꢀꢀꢀC13
N2ꢀꢀꢀN3ꢀꢀꢀC14
N3ꢀꢀꢀN2ꢀꢀꢀN1
C2ꢀꢀꢀC1ꢀꢀꢀC6
108.7(2)
122.0(2)
129.3(2)
109.4(2)
106.52(18)
121.1(3)
119.7(2)
119.2(3)
118.7(3)
120.7(3)
120.5(3)
118.6(3)
119.6(2)
121.8(2)
120.4(3)
121.2(3)
119.2(3)
119.6(3)
118.6(3)
121.0(3)
120.7(3)
117.8(3)
123.3(2)
118.8(2)
C7ꢀꢀꢀC12ꢀꢀꢀC11
O1ꢀꢀꢀC13ꢀꢀꢀC14
O1ꢀꢀꢀC13ꢀꢀꢀC5
120.7(3)
104.03(18)
110.9(2)
109.75(19)
109.42(18)
111.4(2)
111.1(2)
104.1(2)
122.3(2)
133.5(2)
111.3(2)
118.08(19)
130.6(2)
119.7(3)
118.9(2)
121.3(2)
119.4(3)
122.1(3)
116.8(3)
121.6(3)
121.6(3)
122.6(3)
119.4(3)
C14ꢀꢀꢀC13ꢀꢀꢀC5
O1ꢀꢀꢀC13ꢀꢀꢀC11
C14ꢀꢀꢀC13ꢀꢀꢀC11
C5ꢀꢀꢀC13ꢀꢀꢀC11
N1ꢀꢀꢀC15ꢀꢀꢀC14
N1ꢀꢀꢀC15ꢀꢀꢀC16
C14ꢀꢀꢀC15ꢀꢀꢀC16
N2ꢀꢀꢀN1ꢀꢀꢀC15
In the crystal structure, there is an intermolecular O1–
H1ꢀꢀꢀN30 hydrogen bond involving the O–H atom and other
molecular triazole ring 3 positions N. The molecular
C2ꢀꢀꢀC1ꢀꢀꢀCl1
C6ꢀꢀꢀC1ꢀꢀꢀCl1
C3ꢀꢀꢀC2ꢀꢀꢀC1
C2ꢀꢀꢀC3ꢀꢀꢀC4
C5ꢀꢀꢀC4ꢀꢀꢀC3
C6ꢀꢀꢀC5ꢀꢀꢀC4
N2ꢀꢀꢀN1ꢀꢀꢀC17
C6ꢀꢀꢀC5ꢀꢀꢀC13
C4ꢀꢀꢀC5ꢀꢀꢀC13
C1ꢀꢀꢀC6ꢀꢀꢀC5
C15ꢀꢀꢀN1ꢀꢀꢀC17
C22ꢀꢀꢀC17ꢀꢀꢀC18
C22ꢀꢀꢀC17ꢀꢀꢀN1
C18ꢀꢀꢀC17ꢀꢀꢀN1
C17ꢀꢀꢀC18ꢀꢀꢀC19
C20ꢀꢀꢀC19ꢀꢀꢀC18
C21ꢀꢀꢀC20ꢀꢀꢀC19
C21ꢀꢀꢀC20ꢀꢀꢀC23
C19ꢀꢀꢀC20ꢀꢀꢀC23
C20ꢀꢀꢀC21ꢀꢀꢀC22
C17ꢀꢀꢀC22ꢀꢀꢀC21
C8ꢀꢀꢀC7ꢀꢀꢀC12
C8ꢀꢀꢀC7ꢀꢀꢀCl2
C12ꢀꢀꢀC7ꢀꢀꢀCl2
C9ꢀꢀꢀC8ꢀꢀꢀC7
C8ꢀꢀꢀC9ꢀꢀꢀC10
C9ꢀꢀꢀC10ꢀꢀꢀC11
C10ꢀꢀꢀC11ꢀꢀꢀC12
C10ꢀꢀꢀC11ꢀꢀꢀC13
C12ꢀꢀꢀC11ꢀꢀꢀC13
Fig. 2 The H-bond structure of the compound 8 (PWT drawing for
the Platon)
123

J Chem Crystallogr (2009) 39:28–31
31
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conformation and packing is stabilized by interactions of
intermolecular O1–H1ꢀꢀꢀN30. The bond length of Donor-
˚
˚
HꢀꢀꢀAcceptor is 2.93A (O–H 0.82; HꢀꢀꢀN3 2.20A), the bond
angle is 149°. The H-bond structure of the compound 8 is
shown in Fig. 2.
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Acknowledgements The authors wish to acknowledge that this
project is supported by Lanzhou University SKLAOC.
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123