Syntheses, crystal structures, and spectral characterization of three new asymmetrical substituted triaryltriazoles

Article abstract of DOI:10.1002/jhet.949

Triaryltriazoles are of interest in iron(II) complexes designed to study spin-crossover properties. In this study, three new asymmetrical substituted triaryltriazoles, 3-(p-R-phenyl)-4-(p-chlorophenyl)-5-(2-pyridyl)-1,2,4- triazoles (R = OCH₃, 5a; Cl, 5b; Br, 5c), were successfully synthesized from 2-picolinic acid by a three-step reaction through an intermediate N-(p-R-phenylcarbonyl)-N'-(2-pyridylcarbonyl)hydrazine (4a-4c). Yield of 5a-5c is in the range from 74 to 87%. The compounds 5a-5c were characterized by UV, FTIR, ¹H-NMR, electrospray ionization mass spectrum spectra, and elemental analysis. Additionally, the absolute configurations of 5a-5c were determined by single crystal X-ray crystallography.

Full text of DOI:10.1002/jhet.949

1114
Syntheses, Crystal Structures, and Spectral Characterization of
Three New Asymmetrical Substituted Triaryltriazoles
Vol 49
Jian Zhao,a Guo‐Ping Shen,a Yu Zhang,b Xuan Shen,a and Dun‐Ru Zhua,b
*
aState Key Laboratory of Materials‐oriented Chemical Engineering, College of Chemistry
and Chemical Engineering, Nanjing University of Technology, Nanjing 210009, China
bJiangsu Key Laboratory for Chemistry of Low‐Dimensional Materials, Huaiyin Normal
University, Huaian 223300, China
*
E-mail: zhudr@njut.edu.cn
Received February 11, 2011
DOI 10.1002/jhet.949
Published online 26 October 2012 in Wiley Online Library (wileyonlinelibrary.com).
Triaryltriazoles are of interest in iron(II) complexes designed to study spin‐crossover properties. In this
study, three new asymmetrical substituted triaryltriazoles, 3‐(p‐R‐phenyl)‐4‐(p‐chlorophenyl)‐5‐(2‐pyridyl)‐
1,2,4‐triazoles (R = OCH3, 5a; Cl, 5b; Br, 5c), were successfully synthesized from 2‐picolinic acid by a
three‐step reaction through an intermediate N‐(p‐R‐phenylcarbonyl)‐N′‐(2‐pyridylcarbonyl)hydrazine
(4a–4c). Yield of 5a–5c is in the range from 74 to 87%. The compounds 5a–5c were characterized by
UV, FTIR, 1H‐NMR, electrospray ionization mass spectrum spectra, and elemental analysis. Additionally,
the absolute configurations of 5a–5c were determined by single crystal X‐ray crystallography.
J. Heterocyclic Chem., 49, 1114 (2012).
INTRODUCTION
systematically been studied. Structural studies, together with
spin‐crossover properties on the iron(II) complexes of these
ligands, are currently under investigation.
Over the past few decades, 1,2,4‐triazoles and their
derivatives, a kind of interesting heterocyclic compounds,
were found to possess important pharmacological activities,
and have been widespread used as antifungus, antitumor,
fungicide, weedicide, and so on [1]. Moreover, substituted
1,2,4‐triazoles also have attracted considerable attention in
coordination chemistry due to their rich and versatile coordi-
nation modes [2–4]. Especially, some iron(II) complexes with
substituted 1,2,4‐triazoles show fascinating spin‐crossover
properties which can be used in molecular electronics, as
information storage and switching materials [5–10].
RESULTS AND DISCUSSION
In general, there are three kinds of methods reported
for the preparation of 3,4,5‐trisubstituted 1,2,4‐triazoles
(Scheme 2) [26–28]. However, there is a relatively com-
plicated route and the lower yield of the triazole in methods
(b) and (c) compared with method (a). Especially, method
(a) is considered to be more powerful and practical route
for syntheses of 3,4,5‐triaryltriazoles. Hence, we choose
method (a) for the synthesis of our target compounds—
asymmetrical substituted triaryltriazoles 5a–5c.
The readily available 2‐picolinic acid reacting with
anhydrous ethanol under the existence of 98% concen-
trated sulfuric acid gave ethyl pyridine‐2‐carboxylate (2)
[29]. Brief treatment of 2 with 80% hydrazine hydrate
afforded pyridine‐2‐carbonylhydrazine (3) in 74.5% yield.
Then N‐(p‐R‐phenylcarbonyl)‐N′‐(2‐pyridylcarbonyl)hydrazine
(4a–4c) [30] was obtained in a yield of 78–82% by stirring 3
with the corresponding p‐R‐benzoyl chloride (R = OCH3, 4a;
Cl, 4b; Br, 4c) in anhydrous pyridine at ambient temperature.
Finally, under argon atmosphere, the cyclization reaction of
Recently, some 4‐substituted 3,5‐di(2‐pyridyl)‐1,2,
4‐triazoles and their metal complexes have been prepared
successfully by our group [11–19] and others [2, 3].
However, the asymmetrical 3,5‐disubstituted triaryltriazoles
have been little reported so far [20–23]. As a continuation
of our investigation on the asymmetrical 3,5‐disubstituted
1,2,4‐triazoles and their complexes [24, 25], in this article,
we present the syntheses of a series of new asymmetrical
substituted triaryltriazoles, 3‐(p‐R‐phenyl)‐4‐(p‐chlorophenyl)‐
5‐(2‐pyridyl)‐1,2,4‐triazoles (R = OCH3, 5a; Cl, 5b; Br, 5c)
from 2‐picolinic acid (Scheme 1). The products 5a–5c were
1
characterized by UV, FTIR, H‐NMR, ESI‐MS spectra, and
elemental analysis. Their single crystal structures have
© 2012 HeteroCorporation

September 2012
Syntheses, Crystal Structures, and Spectral Characterization of Three
New Asymmetrical Substituted Triaryltriazoles
1115
Scheme 1
4a–4c with 4,4′‐dichlorophenylphosphazoanilide (1) produced
the corresponding 1,2,4‐triazoles 5a–5c (yield: 5a, 86.8%; 5b,
78.3%; 5c, 73.8%) in o‐dichlorobenzene at 190°C. It
is worthwhile to note that more reactive phosphazo
compounds 1 can be obtained in a yield of 50% by reaction
of p‐chloroaniline with phosphorus trichloride in a dried
toluene solution at 125–130°C [31] and should be stored in
an inert atmosphere.
These rings do not share a common plane. The substituted
phenyl rings and pyridyl ring lie in a propeller arrange-
ment around the central 1,2,4‐triazole ring. Some relevant
dihedral angles among the substituted phenyl rings, pyri-
dyl ring, and the 1,2,4‐triazole ring are listed in Table 3.
In addition, the N atom of the pyridyl group is oriented
toward the Cl1‐phenyl ring.
Although the bond lengths and bond angles in the
structures of 5a–5c are similar and can be comparable
with the related compounds [11–13, 20], the stacking
modes of 5a–5c are quite different. There is only one
kind of π–π interaction between two parallel triazole
planes in the crystal of 5a, whereas there are two kinds of
π–π interactions between two pairs of parallel triazole rings
in the crystals of 5b and 5c. These π–π interactions are sum-
marized in Table 4. In addition, the molecule of 5b is
further stabilized by three kinds of weak C H···π interactions
involving (i) C9‐H9A and the p‐Cl1‐phenyl ring [C9···π =
3.663(4) Å and C9‐H9A···π = 139.6(3)°], (ii) C4‐H4A and
The asymmetrical 3,4,5‐triaryltriazoles 5a–5c were fully
1
characterized by UV, FTIR, H‐NMR, ESI‐MS spectra,
and elemental analysis. The molecular structures of 5a–5c
were also confirmed by X‐ray crystallography (Table 1).
Single crystals of 5a–5c suitable for X‐ray diffraction study
were obtained upon slow evaporation from respective ethanol
solution at room temperature. The structural features of 5a–5c
with atom‐labeling scheme are shown in Figure 1 and se-
lected bond lengths and bond angles are listed in Table
2. The X‐ray structure analysis indicate that 5a–5c consist
of three aryl rings and one central 1,2,4‐triazole ring.
Scheme 2
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1116
J. Zhao, G.-P. Shen, Y. Zhang, X. Shen, and D.-R. Zhu
Vol 49
Figure 1. Views of 5a–5c showing the atom‐numbering scheme. Thermal ellipsoids are shown at the 50% probability level. Hydrogen atoms for 5a–5c
are omitted for clarity.
EXPERIMENTAL
the p‐Cl2‐phenyl ring at (1 − x, 1 − y, −z) [C4···π = 3.366
(4) Å and C4‐H4A···π = 116.6(3)°], and (iii) C12‐H12A and
Melting points were determined with an X‐4 digital micro-
the pyridyl ring at (1 − x, −y, −z) [C12···π = 3.427(4) Å and
scope melting‐point apparatus (Beijing) and are uncorrected.
C12‐H12A···π = 113.8(3)°], however, in the crystals of 5a
UV–vis spectra were recorded on a PerkinElmer Lambda 35 spec-
and 5c, there are only two kinds of weak C‐H···π interac-
tions involving (i) C4‐H4A and the p‐methoxyphenyl ring
trophotometer at room temperature in methanol solution. FTIR
spectra were recorded on a Nicolet 380 FTIR instrument using
1
KBr disks in the range 4000–400 cm−1. H‐NMR spectra were
measured on a Bruker AM 500 MHz spectrometer at ambient
temperature in CDCl3 or DMSO‐d6. Chemical shifts are reported
in parts per million (ppm) downfield from tetramethylsilane
(TMS). Electrospray ionization mass spectrum (ESI‐MS) was
recorded with an LCQ ADVANTAGE MAX mass spectrometer,
with MeOH on the mobile phase; the flow rate of the mobile
phase was 0.2 cm3·min−1. The spray voltage, the capillary volt-
age, and the capillary temperature were 4 kV, 40 V, and 260°C,
respectively. Elemental analyses (C, H, N) were carried out with
a Thermo Finnigan Flash 1112A elemental analyzer. All
at (2 − x, 1 − y, 1 − z) [C4···π = 3.474(3) Å and C4‐
H4A···π = 131.6(2)°] and (ii) C13‐H13A and the p‐chloro-
phenyl ring [C13···π = 3.583(3) Å and C13‐H13A···π =
133.3(2)°] in 5a, and (i) C10‐H10A and the pyridyl ring
at (1 − x, −y, 2 − z) [C10···π = 3.406(5) Å and C10‐
H10A···π = 111.9(3)°] and (ii) C13‐H13A and the p‐chloro-
phenyl ring [C13···π = 3.638(5) Å and C13‐H13A···π =
141.6(3)°] in 5c, respectively [25]. The crystal packing dia-
grams of 5a–5c showing π–π and C H···π stacking interac-
tions are presented in Figure 2.
Table 1
Crystallographic data for the compounds 5a–5c.
Compounds
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
5a
5b
5c
C
20H15ClN4O
362.81
Monoclinic
P21/n
13.532 (6)
7.319 (3)
17.602 (8)
90.947 (7)
1743.0 (13)
4
C19H12Cl2N4
367.23
Monoclinic
P21/n
13.596 (3)
7.1736 (14)
17.390 (3)
93.274 (3)
1693.3 (6)
4
C19H12BrClN4
411.69
Monoclinic
P21/n
13.84 (3)
7.169 (14)
17.62 (3)
92.41 (3)
1747 (6)
b (Å)
c (Å)
β (°)
V (Å3)
Z
4
Dc (g cm−3
)
1.383
0.236
752
1.440
0.392
752
1.566
2.515
824
μ (mm−1
F (000)
)
Crystal size (mm)
θ Range
0.26 × 0.14 × 0.12
1.91–25.50
9202
3229 [Rint = 0.0598]
1770
0.24 × 0.12 × 0.10
1.96–25.50
11,768
3145 [Rint = 0.0539]
1614
0.24 × 0.16 × 0.10
1.83–25.50
9736
3219 [Rint = 0.0505]
1768
Reflections collected
Independent reflections
Reflections observed [I >2σ(I)]
Data/restraints/parameters
Goodness‐of‐fit on F2
R/wR [I >2σ(I)]
3229/0/235
0.911
0.0479/0.1083
0.1020/0.1285
0.214, −0.269
3145/0/226
0.967
0.0553/0.1329
0.1253/0.1546
0.358, −0.254
3219/0/226
0.926
0.0474/0.1188
0.1030/0.1369
0.559, −0.361
R/wR (all data)
Max., Min. Δρ (e·Å−3
)
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

September 2012
Syntheses, Crystal Structures, and Spectral Characterization of Three
New Asymmetrical Substituted Triaryltriazoles
1117
Table 2
Selected bond lengths (Å) and angles (°) for 5a–5c.
5a
5b
5c
N1‐C5
N2‐N3
N4‐C15
Cl1‐C18
1.331 (3)
1.390 (3)
1.436 (3)
1.732 (3)
1.369 (3)
107.7 (2)
117.6 (2)
105.0 (2)
124.6 (2)
119.4 (2)
N1‐C5
N2‐N3
N4‐C14
Cl1‐C17
Cl2‐C11
C6‐N2‐N3
C6‐C5‐N1
C7‐N4‐C6
C12‐C11‐Cl2
C16‐C17‐Cl1
1.337 (5)
1.390 (4)
1.450 (4)
1.735 (3)
1.746 (4)
107.8 (3)
117.4 (3)
105.9 (3)
119.9 (3)
118.7 (3)
N1‐C5
N2‐N3
N4‐C14
Cl1‐C17
Br1‐C11
C6‐N2‐N3
C6‐C5‐N1
C7‐N4‐C6
C12‐C11‐Br1
C16‐C17‐Cl1
1.347 (6)
1.390 (5)
1.450 (5)
1.736 (5)
1.902 (5)
107.5 (3)
117.5 (4)
105.7 (3)
118.6 (4)
118.7 (3)
O1‐C11
C6‐N2‐N3
C6‐C5‐N1
C7‐N4‐C6
C12‐C11‐O1
C19‐C18‐Cl1
chemicals used were of analytical grade and without further puri-
fication unless otherwise stated. Toluene was freshly distilled
from Na/benzophenone, while pyridine was distilled over NaOH.
4,4′‐Dichlorophenylphosphazoanilide (1). A solution of
phosphorus trichloride (1.5 mL, 0.017 mol) in dry toluene
(20 mL) was added dropwise to a stirring solution of
p‐chloroaniline (10.97 g, 0.086 mol) in 130 mL of
anhydrous toluene at room temperature. The suspension was
refluxed for 1 h at 125–130°C. Then the hot mixture was
immediately filtered and washed with hot toluene. Then
the filtrate was evaporated to dryness at reduced pressure
and washed thoroughly with petroleum ether and ethanol
to obtain 1 as a pure white solid (2.29 g, 50%). FTIR
(ν, cm−1): 3340, 3165, 3030, 2942, 1596, 1491, 1384,
1093, 972.
Ethyl pyridine–2‐carboxylate (2). Ninety‐eight percent
concentrated sulfuric acid (25 mL) was added dropwise to a
solution of 2‐picolinic acid (24.6 g, 0.2 mol) in anhydrous
ethanol (120 mL) surrounded by a ice‐water bath. The mixture
was refluxed for 24 h. Upon cooling to ambient temperature, the
product was poured into 100 mL ice‐water. The resulting
solution was neutralized to pH = 7–8 with a solution of
potassium carbonate. The precipitate was filtered and the filtrate
was extracted with ether (4 × 100 mL). After drying over
magnesium sulfate, the organic phases were evaporated to
dryness under reduced pressure. The unpurified ester can be
used for next hydrazinolysis.
General procedure. Preparation of the N‐(p‐R‐phenylcarbonyl)‐
N′‐(2‐pyridylcarbonyl)hydrazine (4a–4c). A suspension of the
corresponding p‐substituted‐benzoyl chloride (0.012 mol) and dry
pyridine (10 mol) was added dropwise to a stirring solution of 3
(0.01 mol) in 30 mL of pyridine at 0°C. The mixture was stirred at
0°C for 1 h, then at room temperature for 8 h. Then the mixture was
poured into 50 mL ice‐water, the precipitate was filtered, dried in
vacuo, and recrystallized from anhydrous ethanol to give 4a–4c as
white solids.
N‐(p‐Methoxyphenylcarbonyl)‐N′‐(2‐pyridylcarbonyl)hydrazine
(4a). This compound was obtained as a white solid 2.13 g (78.5%),
mp 153–155°C; FTIR (ν, cm−1): 3285, 3021, 2964, 1703, 1642,
1610, 1566, 1507, 1488, 1302, 1259, 1026, 998.4. 1H‐NMR
(DMSO‐d6, ppm): δ 3.88 (s, 3H, CH3), 7.18–7.20 (d, 2H, ArH),
7.63–7.66 (t, 1H, PyH), 8.05–8.09 (m, 3H, PyH, ArH), 8.24–8.26
(d, 1H, PyH), 8.80–8.81 (d, 1H, PyH), 10.51–10.53 (d, 2H, NH).
N‐(p‐Chlorophenylcarbonyl)‐N′‐(2‐pyridylcarbonyl)hydrazine (4b).
This compound was obtained as a colorless needle crystal 2.26 g
(82.2%), mp 168–170°C; FTIR (ν, cm−1): 3179, 3010, 1685,
1
1641, 1597, 1570, 1513, 1488, 1334, 1095, 1015, 844. H‐NMR
(DMSO‐d6, ppm): δ 7.60–7.63 (d, 2H, ArH), 7.66–7.69 (t,
1H, PyH), 7.93–7.95 (d, 2H, ArH), 8.03–8.07 (m, 2H,
PyH), 8.71–8.72 (d, 1H, PyH), 10.63–10.67 (d, 2H, NH).
N‐(p‐Bromophenylcarbonyl)‐N′‐(2‐pyridylcarbonyl)hydrazine
(4c). This compound was obtained as a white solid 2.50 g (78.2%),
mp 167–168°C; FTIR (ν, cm−1): 3173, 3010, 1690, 1637, 1591,
1
1508, 1484, 1399, 1072, 1010, 840. H‐NMR (DMSO‐d6, ppm):
Pyridine–2‐carbonylhydrazine (3). A mixture of above ester 2,
80% hydrazine hydrate (19 mL, 0.4 mol) and ethanol (50 mL) was
refluxed for 8 h. Then the solution was evaporated to dryness, and
the resulting white solid was recrystallized from anhydrous ethanol
to give 3 as colorless needles (20.4 g, 74.5% for a two‐step reaction),
mp 97–98°C (lit. mp 100–101°C [29]); FTIR (ν, cm−1): 3310, 3213,
3051, 1676, 1652, 1594, 1570, 1521, 1473, 1070, 998.
δ 7.62–7.65 (t, 1H, PyH), 7.71–7.73 (d, 2H, ArH), 7.84–7.85 (d,
2H, ArH), 7.99–8.05 (m, 2H, PyH), 8.68–8.69 (d, 1H, PyH),
10.58–10.61 (d, 2H, NH).
General procedure. Preparation of the 3‐(p‐R‐phenyl)‐4‐
(p‐chlorophenyl)‐5‐(2‐pyridyl)‐1,2,4‐triazole (5a–5c). To a
solution of the corresponding N‐(p‐R‐phenylcarbonyl)‐N′‐(2‐
pyridylcarbonyl)hydrazine (4a–4c) (4 mmol) in o‐dichlorobenzene
Table 3
The dihedral angles (°) for 5a–5c.
Compounds
Py/Trz
Cl1‐Ph/Trz
CH3O‐Ph/Trz
Cl2‐Ph/Trz
Br1‐Ph/Trz
5a
5b
5c
23.7 (2)
18.5 (3)
16.3 (3)
73.5 (2)
75.6 (3)
74.9 (3)
30.4 (2)
24.5 (3)
22.6 (3)
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

1118
J. Zhao, G.-P. Shen, Y. Zhang, X. Shen, and D.-R. Zhu
Vol 49
Table 4
(CDCl3, ppm): δ 3.80 (s, 3H, CH3), 6.82–6.84 (d, 2H, ArH),
7.16–7.17 (d, 2H, ArH), 7.20–7.23 (m, 1H, PyH), 7.34–7.38 (t,
4H, ArH), 7.74–7.78 (t, 1H, PyH), 8.16–8.17 (d, 1H, PyH),
8.31–8.32 (d, 1H, PyH). ESI‐MS: m/z 363 (M+). Anal. Calcd.
for C20H15ClN4O: C, 66.21; H, 4.17; N, 15.44. Found: C,
66.08; H, 4.12; N, 15.52.
The π–π stacking interactions for 5a–5c.
π···π
interaction
Dihedral
angle
Compounds
cent···cent
3.575
π···π
5a
5b
π (trz)···π
(trz)a
3.381
3.394
3.738
3.396
3.731
0.0
0.0
0.0
0.0
0.0
3,4‐Di(p‐chlorophenyl)‐5‐(2‐pyridyl)‐1,2,4‐triazole (5b). This
compound was obtained as colorless block crystals 1.15 g
(78.3%), mp 213–215°C; UV (MeOH, nm): 224 (2.48), 272
(2.28). FTIR (ν, cm−1): 3050, 2979, 1587, 1573, 1493, 1461,
π (trz)b···π
3.514
(trz)c
π (trz)···π
(trz)d
3.956
1
1086, 1015, 999, 843, 753. H‐NMR (CDCl3, ppm): δ 7.15–7.19
(d, 2H, ArH), 7.22–7.24 (t, 1H, PyH), 7.28–7.31 (d, 2H, ArH),
7.35–7.40 (m, 4H, ArH), 7.75–7.81 (t, 1H, PyH), 8.17–8.20 (d, 1H,
PyH), 8.32–8.33 (d, 1H, PyH). ESI‐MS: m/z 367 (M+). Anal. Calcd.
for C19H12Cl2N4: C, 62.14; H, 3.29; N, 15.26. Found: C, 61.79; H,
3.21; N, 15.38.
3‐(p‐Bromophenyl)‐4‐(p‐chlorophenyl)‐5‐(2‐pyridyl)‐1,2,4‐triazole
(5c). This compound was obtained as colorless block crystals 1.20 g
(73.8%), mp 221–223°C; UV (MeOH, nm): 225 (1.76), 275 (1.65).
FTIR (ν, cm−1): 3046, 2921, 1587, 1561, 1494, 1460, 1085, 1076,
1000, 843, 740. 1H‐NMR (CDCl3, ppm): δ 7.15–7.18 (d, 2H, ArH),
7.22–7.24 (t, 1H, PyH), 7.30–7.33 (d, 2H, ArH), 7.36–7.39 (d, 2H,
ArH), 7.45–7.47 (d, 2H, ArH), 7.75–7.81 (t, 1H, PyH), 8.19–8.20 (d,
1H, PyH), 8.32–8.33 (d, 1H, PyH). ESI‐MS: m/z 413 (M+H+). Anal.
Calcd. for C19H12BrClN4: C, 55.43; H, 2.94; N, 13.61. Found: C,
55.29; H, 2.86; N, 13.85.
Single‐crystal X‐ray diffraction analysis of 5a–5c. The well‐
shaped single crystals of 5a–5c were selected for lattice parameter
determination and collection of intensity data at 296 K on a
Bruker SMART CCD diffractometer with a detector distance of
5 cm and frame exposure time of 10 s using a graphite‐
monochromated Mo Kα (λ = 0.71073 Å) radiation. The
structures were all solved by direct methods and refined on F2
by full‐matrix least squares procedures using SHELXTL
5c
π (trz)···π
3.521
(trz)e
π (trz)···π
(trz)f
3.979
Symmetry codes: (a) 1 − x, 2 − y, − z; (b) 1/2 + x, 1/2 − y, 1/2 + z; (c) 1/2 −
x, 1/2 + y, 3/2 – z; (d) − x, 1 − y, 1 – z; (e) 1 − x, 1 − y, − z; (f) −1/2 + x, 3/2
− y, 1/2 + z
(25 mL) was added 4,4′‐dichlorophenylphosphazoanilide (1) (4.8
mmol) with stirring. The mixture was heated to 190°C for 5 h.
After all starting material had been consumed, the solvent was
removed under reduced pressure, and the residue was treated with
dilute hydrochloric acid (20 mL). The yellow solid was filtered off,
and the filtrate was neutralized with a 20% potassium carbonate
solution to pH = 9–10. The precipitate was filtered off, washed with
ether, and recrystallized from anhydrous ethanol to give 5a–5c as
colorless block crystals.
3‐(p‐Methoxyphenyl)‐4‐(p‐chlorophenyl)‐5‐(2‐pyridyl)‐1,2,4‐
triazole (5a). This compound was obtained as colorless block
crystals 1.25 g (86.8%), mp 200–202°C; UV (MeOH, nm): 223
(2.23), 278 (1.97). FTIR (ν, cm−1): 3046, 2983, 2830, 1613,
1
1586, 1561, 1496, 1466, 1254, 1084, 1028, 845, 742. H‐NMR
Figure 2. Views of the crystal packing for 5a–5c showing π–π stacking interactions.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

September 2012
Syntheses, Crystal Structures, and Spectral Characterization of Three
New Asymmetrical Substituted Triaryltriazoles
1119
[13] Zhu, D. R.; Song, Y.; Xu, Y.; Zhang, Y.; Fun, H. K.; You, X.
Z. Polyhedron 2000, 19, 2019.
[14] Zhu, D. R.; Xu, Y.; Mei, Y. H.; Tu, C.; You, X. Z. J Mol Struct
2001, 559, 119.
[15] Zhu, D. R.; Wang, T. W.; Zhong, S. L.; Xu, Y.; You, X. Z.
Chin J Inorg Chem 2004, 20, 508.
[16] Zhu, D. R.; Wang, Z. X.; Song, J.; Li, Y. Z.; Lan, D. Y. Chin J
Inorg Chem 2005, 21, 128.
software [32]. All nonhydrogen atoms were anisotropically
refined. All H atoms were located from a difference map and
refined isotropically. Details on crystal data of 5a–5c are
summarized in Table 1.
CCDC 810287 (5a), 810288 (5b), and 810289 (5c) contain the
supplementary crystallographic data for this article. These data
can be obtained free of charge from the Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[17] Zhou, J.; Yang, J.; Qi, L.; Shen, X.; Zhu, D. R.; Xu, Y.; Song,
Y. Transition Met Chem 2007, 32, 711.
[18] Qi, L.; Zhu, D. R.; Xie, D. J.; Wu, Y. F.; Shen, X. Chin J Inorg
Chem 2008, 24, 868.
[19] Yang, J.; Bao, W. W.; Ren, X. M.; Xu, Y.; Shen, X. Zhu, D. R.
J Coord Chem 2009, 62, 1809.
[20] Zhang, S. P.; Liu, Z. D.; Shao, S. C. Acta Cryst 2006, E62,
o1279.
[21] Zhang, S. P.; Liu, Z. D.; Chen, S. D.; Yang, S.; Shao, S. C.
Acta Cryst 2006, E62, o1516.
Acknowledgments. This work was funded by the National Natural
Science Foundation of China (No. 20771059), the Natural Science
Foundation of Jiangsu Province (BK2008371), and the Open
Foundation of Jiangsu Key Laboratory for Chemistry of Low‐
Dimensional Materials (JSKC09057).
[22] Liu, Z. D.; Zhang, S. P.; Wei, Y.; Shao, S. C. Acta Cryst 2007,
E63, o4634.
REFERENCES AND NOTES
[23] Gong, X. N.; Wang, Z. X.; Liu, Y. Acta Cryst 2009, E65,
o3214.
[24] Lu, W.; Zhu, D. R.; Xu, Y.; Cheng, H. M.; Zhao, J.; Shen, X.
Struct Chem 2010, 21, 237.
[25] Zhao, J.; Cheng, H. M.; Shen, G. P.; Xu, Y.; Zhu, D. R. J
Coord Chem 2011, 64, 942.
[26] Erwin, K. J Org Chem 1958, 23, 1086.
[27] Gautun, O. R.; Carisen, P. H. Acta Chem Scand 1991,
45, 609.
[1] Potts, K. T. Chem Rev 1961, 61, 87.
[2] Haasnoot, J. G. Coord Chem Rev 2000, 200–202, 131.
[3] Klingele, M. H.; Brooker, S. Coord Chem Rev 2003, 241, 119.
[4] Beckmann, U.; Brooker, S. Coord Chem Rev 2003, 245, 17.
[5] Kahn, O.; Martinez, C. J. Science 1998, 279, 44.
[6] Haasnoot, J. G. In Magnetism: A Supramolecular Function;
Kahn, O., Ed.; Kluwer: Dordrecht, 1996; p 299.
[7] van Koningsbruggen, P. J. Top Curr Chem 2004, 233, 123.
[8] Zhu, D. R.; Xu, Y.; Yu, Z.; Guo, Z. J.; Sang, H.; Liu, T.; You,
X. Z. Chem Mater 2002, 14, 838.
[28] Klingele, M. H.; Brooker, S. Eur J Org Chem 2004,
3422.
[9] Krober, J.; Codjovi, E.; Kahn, O.; Groliere, F.; Jay, C. J Am
Chem Soc 1993, 115, 9810.
[10] Kitchen, J. A.; Brooker, S. Coord Chem Rev 2008, 252, 2072.
[11] Fun, H. K.; Chinnakali, K.; Shao, S. C.; Zhu, D. R.; You, X. Z.
Acta Cryst 1999, C55, 770.
[29] Saikachi, H.; Aramaki, Z.; Aoki, T. Pharm Bull 1955, 3, 194.
[30] Hua, G. X.; Li, Y.; Fuller, A. L.; Slawin, A. M. Z.; Woollins, J.
D. Eur J Org Chem 2009, 1612.
[31] Grimmed, H. W.; Guenther, A.; Morgan, J. F. J Am Chem Soc
1946, 68, 539.
[12] Zhu, D. R.; Xu, Y.; Zhang, Y.; Wang, T. W.; You, X. Z. Acta
Cryst 2000, C56,895.
[32] Sheldrick, G. M. SHELXL v5.10; Bruker AXS, Inc.: Wiscon-
sin, 1997.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet