Structure and synthesis of a new library of N,N-Bis-[1,2,4]triazol-1- ylmethyl-amino compounds

Article abstract of DOI:10.1080/00397910903318740

New N,N-bis(triazol-1-ylmethyl)amines have been prepared in one step by condensation of 1-(hydroxymethyl)triazole with a series of primary substituted aromatic amines. These reactions were carried out in refluxed CH₃CN for 4h. The products were recuperated with excellent and good yields (75-90.5%). The X-ray crystallography structure of one of them has been studied.

Full text of DOI:10.1080/00397910903318740

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Structure and Synthesis of a New Library
of N,N-Bis-[1,2,4]triazol-1-ylmethyl-
amino Compounds
Hanane Al Bay a , Rachid Touzani a b , Mustafa Taleb c , Nour-Eddine
Benchat a , Brahim El Bali d , Michal Dusek e , Karla Fejfarova e
Sghir El Kadiri a
&
a Laboratoire de Chimie Appliquée et Environnement, Département
de Chimie, Faculté des Sciences , Université Mohamed 1 er , Oujda,
Morocco
b Faculté Pluridisciplinaire de Nador , Université Mohamed 1 er ,
Nador, Morocco
c Département de Chimie , Faculté des Sciences, DEM, Fès , Morocco
d LCSMA, Département de Chimie, Faculté des Sciences , Université
Mohamed 1 er , Oujda, Morocco
e Institute of Physics , Prague, Czech Republic
Published online: 09 Aug 2010.
To cite this article: Hanane Al Bay , Rachid Touzani , Mustafa Taleb , Nour-Eddine Benchat , Brahim
El Bali , Michal Dusek , Karla Fejfarova & Sghir El Kadiri (2010) Structure and Synthesis of a New
Library of N,N-Bis-[1,2,4]triazol-1-ylmethyl-amino Compounds, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 40:18, 2767-2779,
DOI: 10.1080/00397910903318740
To link to this article: http://dx.doi.org/10.1080/00397910903318740
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Synthetic Communications1, 40: 2767–2779, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903318740
STRUCTURE AND SYNTHESIS OF A NEW LIBRARY OF
N,N-BIS-[1,2,4]TRIAZOL-1-YLMETHYL-AMINO
COMPOUNDS
Hanane Al Bay,1 Rachid Touzani,1,2 Mustafa Taleb,3
Nour-Eddine Benchat,1 Brahim El Bali,4 Michal Dusek,5
Karla Fejfarova,5 and Sghir El Kadiri1
1
´
Laboratoire de Chimie Appliquee et Environnement, Departement de
Chimie, Faculte des Sciences, Universite Mohamed 1 er, Oujda, Morocco
´
´
´
2
´
Faculte Pluridisciplinaire de Nador, Universite Mohamed 1 er, Nador,
Morocco
´
3
´
´
Departement de Chimie, Faculte des Sciences, DEM, Fes, Morocco
`
4
´
LCSMA, Departement de Chimie, Faculte des Sciences, Universite
Mohamed 1 er, Oujda, Morocco
´
´
5Institute of Physics, Prague, Czech Republic
New N,N-bis(triazol-1-ylmethyl)amines have been prepared in one step by condensation of
1-(hydroxymethyl)triazole with a series of primary substituted aromatic amines. These
reactions were carried out in refluxed CH3CN for 4 h. The products were recuperated with
excellent and good yields (75–90.5%). The x-ray crystallography structure of one of them
has been studied.
Keywords: Heterocyclic compounds; nitrogen-rich; synthesis and crystallography; triazole; tridentate
ligand
INTRODUCTION
Nitrogen-containing multipodal molecules are attracting current interest for
the building of polynuclear metal complexes, as models for bioinorganic chemistry,
for use in materials science and the transport and activation of small molecules, as
well as for the discovery of new catalyst precursors.[1–7] For example, polypyrazolyl
compounds have been used as mimics of active sites in copper oxidase.[8] The
triazolyl ring seems to play a key role in antifungal drugs; for example, fluconazole
is effective against oropharyngeal and esophageal candidiasis,[9,10] although fosfluco-
nazole is some less active than fluconazole in vitro but has similar efficacy in animal
models and patients[11,12] (Fig. 1).
Received August 8, 2009.
Address correspondence to Sghir El Kadiri or Rachid Touzani, Laboratoire de Chimie Appliquee
´
et Environnement, Departement de Chimie, Faculte des Sciences, Universite Mohamed 1er, BP 717, 60 000
´
Oujda, Morocco. E-mail: elkadiri_sghir@yahoo.fr; touzanir@yahoo.fr
´
´
2767

2768
H. AL BAY ET AL.
Figure 1. Structure of fluconazole and fosfluconazole.
Figure 2. Diverse and library compounds.

TRIAZOLYL HETEROCYCLIC COMPOUNDS
2769
Meanwhile, these compound derivatives have been involved in several types of che-
lating ligands. In particular, the bridging coordination mode of N-chelating substituted
1,2,4-triazoles has been actively explored in recent years; this may be able to lead to mate-
rials with interesting magnetic properties.[13] For instance, tris-triazolyl borates were
studied as tripodal ligands in metal complexes and had been adapted for the discovery
of new activation process and new catalytic reactions.[14–16] The N,N-bis(triazolyl)amines
are classified as six- and eight–electron-donating tridentate ligands with a two N-donor
sites of triazolyl rings and one N-donor site of amine. The coordination behavior of the
N,N-bis(triazolyl)amines and the reactivity of the corresponding metal complexes are
strongly dependent on the electron richness of the nitrogen atoms and the steric hin-
drance of the substituants. Thus, it seems crucial to synthesize a diversity of this type
of tridentate ligands (Fig. 2). The synthesis of new tridentate nitrogen donor compounds
that have biological activities such as antifungal[17] and anticancer[18] activities is one of
our research interests. In addition, we are very interested in the study of their catalytic
activities such as isomerization[19,20] and oxidation reactions.[21–23] To our knowledge,
the 1,2,4-triazole unit has never been incorporated into a tridentate symmetrical structure
(-N-CH2-N- junction) or screened for biological activities. We report here an easy and
facile synthesis of seven new N,N-bis(1,2,4-triazolyl)amines containing new bulky
aromatic groups at the central nitrogen atom with diverse substituants.
EXPERIMENTAL
Melting points are uncorrected, and P NMR spectra are of the compounds
dissolved in CDCl3 and dimethylsulfoxide (DMSO), obtained with a Bruker 300
spectrometer. Infrared (IR) spectra were recorded on a Perkin-Elmer 1310 spectro-
photometer. Mass spectra (MS) were determined on a Micromass LCT; tz refers to
triazol and ar refers to aromatic compounds.
General Procedure
A mixture of N-hydroxymethyl-1,2,4-triazole (10 mmol) and arylamines
(5 mmol) in acetonitrile (25 mL) was stirred and refluxed in a closed vessel for 4 h.
The acetonitrile layer was dried from the water formed by treatment with anhydrous
MgSO4. After filtration, the solvent was removed under vacuum, and the crude
products were washed with water, ether, or dichloromethane (DCM) and then
dried. The products were analyzed as such. The compounds 2a and 2c are known
and have spectral data in accordance with the literature data.[24,25]
Spectral Data
N,N-Bis((1H-1,2,4-triazol-1-yl)methyl)benzylamine
2b. White
solid
1
(82.5%); mp 81–83 ꢀC. H NMR (300 MHz, CDCl3) d ppm: 8.14 (s, 2H, -CHtz);
7.99 (s, 2H, -CHtz); 7.40–7.28 (m, 5H, -CHar); 5.14 (s, 4H, -NCH2N-); 3.83 (s, 2H,
CH2). 13C NMR (75 MHz, CDCl3) d ppm: 152.35 (-CHtz); 143.93 (-CHtz); 135.99
(-CHar); 128.65 (-CHar); 64.86 (-NCH2N-); 54.18 (-CH2-Car). IR (KBr, n cmꢁ1):
=
=
3432; 3115 (-CHar); 1673 (-C C-); 1506 (-C N); 1272 (-C-N); 1136; 1017; 744;
678. MS (ES) (m=z) (%) ¼ 269.31 (10); 263.47 (24.5); 244.03 (83); 197.72 (100).

2770
H. AL BAY ET AL.
N,N-((1H-1,2,4-Triazol-1-yl)methyl)-4-methoxybenzenamine 2d. Brown
1
oil (90.5%). H NMR (300 MHz, CDCl3) d ppm: 8.08 (s, 2H, -CHtz); 7.97 (s, 2H,-
CHtz); 6.84 (d, 2H, -CHar, J ¼ 2.71 Hz); 6.82 (d, 2H, -CHar, J ¼ 2.1 Hz); 5.60 (s,
4H, -NCH2N-); 3.73 (s, 3H, -OCH3). 13C NMR (75 MHz, CDCl3) d ppm: 156.68
=
=
=
=
(-C Car); 152.34 (-C N-tz); 143.46 (-C N-tz); 137.7 (-C Car); 115.08 (-CHar);
=
65.83 (-NCH2N-); 55.48 (-OCH3). IR (KBr, n cmꢁ1): 3116 (C-Har); 1614 (C C);
=
1510 (C N); 1246 (C-N); 1189; 1136; 1030; 825; 678. MS (ES) (m=z) (%) ¼ 269.13
(100); 253.51 (72.5); 175.85 (40.3).
N,N-Bis((1H-1,2,4-triazol-1-yl)methyl)-4-nitrobenzenamine 2e. Yellow
solid (82%); mp 133–135 ꢀC. 1H NMR (300 MHz, DMSO) d ppm: 8.66 (s, 2H, -CHtz)
8.05 (s, 2H, -CHtz); 8.01 (d, 2H, -CHar, J ¼ 9.3 Hz); 6.96 (d, 2H, -CHar, J ¼ 9 Hz);
13
=
5.47 (s, 4H, -NCH2N-). C NMR (75 MHz, DMSO) d ppm: 152.81 (-C Car);
=
152.00 (-C Ntz); 151.88 (-C Ntz); 138.58 (-C Car); 125.7 (-CHar); 114.49 (-CHar);
=
=
63.45 (-NCH2N-). IR (KBr, n cmꢁ1): 3112 (-CHar); 1610 (-C C-); 1508 (-C N-);
=
=
=
1479; 1268 (-C N-) 1336; 1195; 1137; 1117; 1025; 834; 750; 675. MS (ES) (m=z)
(%) ¼ 253.51 (100); 172.63 (10.9).
N,N-Bis((1H-1,2,4-triazol-1-yl)methyl)-4-chlorobenzenamine 2f. White
solid (83%); mp 90–92 ꢀC. 1H NMR (300 MHz, CDCl3) d ppm: 8.22 (s, 2H,
-CHtr); 7.97 (s, 2H, -CHtz); 7.24 (d, 2H, -CHar, J ¼ 8.7 Hz); 6.99 (d, 2H, -CHar,
J ¼ 6.9 Hz); 5.73 (s, 4H, -NCH2N-). 13C NMR (75 MHz, CDCl3) d ppm: 152.39
=
=
=
=
(-C Ntz); 143.32 (-C Ntz); 143.21 (-C Car); 129.46 (-C C-ar); 128.32 (-CHar);
114.84 (-CHar); 65.00 (-NCH2N-). IR (KBr, n cmꢁ1): 3115 (C-Har); 1601
=
(-C C-); 1502 (-C N-); 1272 (-C-N-); 1192; 1136; 957; 819; 676. MS (ES) (m=
=
z) (%) ¼ 253.51 (100).
N,N-Bis((1H-1,2,4-triazol-1-yl)methyl)-4-methylbenzenamine 2g. White
1
solid (82%); mp 88–90 ꢀC. H NMR (300 MHz, CDCl3) d ppm: 8.15 (s, 2H, -CHtz);
7.98 (s, 2H, -CHtz); 7.10 (d, 2H, -CHar, J ¼ 8.4 Hz); 6.89 (d, 2H, -CHar, J ¼ 6.6 Hz);
5.72 (s, 4H, -NCH2N-); 2.28 (s, 3H, -CH3). 13C NMR (75 MHz, CDCl3) d ppm:
=
=
=
=
152.31 (-C Ntz); 143.27 (-C Ntz); 142.04 (-C C-ar); 133.24 (-C Car); 130.50 (-CH-
ar); 118.40 (-CHar); 65.05 (-NCH2N-); 20.53 (-CH3). IR (KBr, n cmꢁ1): 3114 (-CHar);
2922; 2864 (-CH3); 1617 (-C C-), 1578; 1519 (-C N-); 1271 (-C-N ¼); 1190; 1136;
1013; 958; 810; 753; 677; 642. MS (ES) (m=z) (%) ¼ 269.67 (25.7); 255.97 (70.6);
253.71 (100); 237.13 (70.6).
=
=
N,N-Bis((1H-1,2,4-triazol-1-yl)methyl)-2,6-dibromo-4-methylbenzena-
1
mine 2h. White solid (86.6%); mp 86–88 ꢀC. H NMR (300 MHz, CDCl3) d ppm:
8.13 (s, 2H, -CHtz); 8.00 (s, 2H, -CHtz); 7.40 (s, 2H, -CHar); 5.63 (s, 4H,
-NCH2N-); 2.31 (s, 3H, -CH3). 13C NMR (75 MHz, CDCl3) d ppm: 152.21
=
=
=
=
(-C Ntz); 143.27 (-C Ntz); 141.13 (-C Car); 133.86 (-C Car); 125.48 (-CHar);
108.70 (-CHar); 65.39 (-NCH2N-); 20.46 (-CH3). IR (KBr, n cmꢁ1): 3460; 3346;
3200; 3115 (-C-H); 2922; 1620 (-C C-); 1585; 1505 (-C N-); 1477; 1270 (-C-N-);
1135; 1012; 854; 740; 676 (C-Br). MS (ES) (m=z) (%) ¼ 427.42 (50); 358.84 (23);
269.11 (100).
=
=

TRIAZOLYL HETEROCYCLIC COMPOUNDS
2771
Crystal Synthesis
A mixture of N-hydroxymethyl-1,2,4-triazole (10 mmol) and aniline (5 mmol)
in acetonitrile (25 mL) was stirred and refluxed in a closed vessel for 4 h. The
acetonitrile layer was dried from the water formed by treatment with anhydrous
MgSO4. After filtration, the solvent was removed under vacuum, and the crude
product was solubilized in hot DCM. After solvent evaporation under ambient con-
ditions, colorless crystals were obtained.
Data collection and refinements. A colorless crystal of dimensions
0.3669 ꢂ 0.2087 ꢂ 0.1759 mm was selected for x-ray diffraction analysis. The data
were recorded at room temperature with an Oxford diffraction CCD diffractometer
Gemini equipped with an Atlas area detector using graphite monochromatized
˚
MoKa radiation (k ¼ 0.7173 A). Data were processed with the program Crysalis
RED.[26,27] The phase problem was solved by direct methods using the program
SIR2002,[28] and the structure was refined with Jana 2006.[29] Crystal structure fig-
ures were drawn using the Diamond program.[30] All hydrogen atoms were discern-
ible in difference Fourier maps and could be refined to reasonable geometry.
According to common practice, hydrogen atoms in organic molecules were kept in
ideal positions during the refinement. The O-H distances in water molecule were
˚
restrained to 0.82 A. The isotropic atomic displacement parameters of hydrogen
Table 1. Crystal and refinement data for 2c
Parameter
Value
Chemical name
N,N-Bis((1H-1,2,4-triazol-1-yl)methyl)
benzenamine monohydrate
C12H13N7, H2O
Chemical formula
M
F000
273.3 g=mol
288
Triclinic (P=–1)
Symmetry
Cell parameters
˚
a (A)
7.9361(6)
8.5605(6)
˚
b (A)
˚
c (A)
10.6075(8)
110.383(6)
a (ꢀ)
b (ꢀ)
c (ꢀ)
92.057(6)
99.486(6)
662.88(9)
3
˚
V (A )
Z
2
0.789
l
T min
0.680
0.870
T max
hmin
hmax
10.2
59.89
Reciprocal space
Number of parameters
Reflections number
R = Wr
ꢁ8 < h < 8, ꢁ9 < k < 9, ꢁ11 < l < 11
188
1665 [with I > 3 n r(I): 1412]
0.0447 =0.1379

2772
H. AL BAY ET AL.
atoms were evaluated as 1.2 ꢃ Ueq of the parent atom. The structure was a twin with
twinning matrix applied to indices as column vectors:
ꢁ1
0
0
0
1
0 ꢁ1
0:259 0:9
This led to partial overlaps of diffraction spots. See also Table 1.
RESULTS AND DISCUSSION
Synthesis
The syntheses of N,N-bis(1,2,4-triazol-1-ylmethyl)amines 2a–h are based on
the condensation of 1 equivalent of an aromatic amine with 2 equivalents of
1-(hydroxymethyl)-1,2,4-triazole 1 (Fig. 2). The electronic effect of the substituents
R as an electron-donating or electron-accepting group represents only one way to
modify the coordination properties of donor sites from the triazolyl rings. The
nature of the substituents R, particularly the electronic effect of alkyl versus aryl
group R, and the steric hindrance of R are also important factors. Thus, eight bulky
amines, differently substituted in ortho, meta, and para positions, were condensed
with the precursors 1.[31] These nine reactions were performed in a refluxed CH3CN
solvent during 4 h. The electronic impact of the different groups’ R is visible on the
chemical shift in proton and carbon NMR of the methylene bridge between the
central nitrogen atom and the triazolyl rings as well as on the two –CH triazolic.
As expected, the hydrogen atoms of the triazolyl rings are more strongly influenced
by the nature of R according to the observed values for 2c [8.01, 8.21 ppm (phenyl)],
2e [8.05, 8.66 ppm (phenyl and attracting group on para) and 7.97, 8.22 ppm (phenyl
and donating group on para)] (Table 2).
The variation of the proton and carbon shifts of the methylene groups (5.14 to
5.73 and 63.45 to 71.94) could be correlated to the tuning of the electron richness of
these ligands. One can envisage that with the new electron-attracting and=or bulky
substituants, these nine ligands have more potential for different coordination
Table 2. Chemical shift in 1H NMR and 13C NMR of the methylene bridge between the central nitrogen
atom and the triazolyl rings and the -CH triazolic
Yield
(%)
1H NMRd
ppm (N-CH2-N)
13C NMRd
ppm (N-CH2-N)
1H NMRd
ppm (H triazol)
13C NMRd
ppm (C triazol)
Compounds
2a
75
5.38; 5.63
64.43; 71.94
7.93; 7.99;
8.21; 8.34
7.99; 8.14
8.01; 8.21
7.97; 8.08
8.05; 8.66
7.97; 8.22
7.98; 8.15
8.00; 8.13
143.25; 146.62;
151.78; 152.17
143.93; 152.35
143.23; 152.41
143.46; 152.34
151.88; 152.00
143.32; 152.39
143.27; 152.31
143.27; 152.21
2b
2c
2d
2e
2f
82.5
87.2
90.5
82
5.14
5.79
5.60
5.47
5.73
5.72
5.63
64.86
64.63
65.83
63.45
65.00
65.05
65.39
83
82
2g
2h
86.6

TRIAZOLYL HETEROCYCLIC COMPOUNDS
2773
behavior than other reported similar ligands[32,33] and more potential for biological
activities.
X-Ray Diffraction Analysis
The R value, based on data of the first domain and taking twinning into the
account for fully overlapped reflections, was 6%, goodness of fit (g.o.f.) 3.73. In
another attempt, we used an hklf5 file generated by the Crysalis program.[26,27] It
should take into the account overlaps, but in fact it did not improve the results
and yielded an R value of about 10% regardless of various options (deconvolution
limits, merging or not merging reflections, using data from the first domain or both
domains). Finally, we used a classical approach implemented in the program
Table 3. Fractional atomic coordinates and isotropic or equivalent isotropic dis-
2
placement parameters (A ) for 2c
˚
x
Y
z
Uiꢃso=Ueq
O1
N1
0.2511 (3)
0.2158 (3)
0.1299 (3)
0.0607 (3)
0.2612 (3)
0.3203 (3)
0.3954 (3)
0.4873 (3)
0.0396 (4)
0.1733 (4)
0.3385 (3)
0.1930 (3)
0.4939 (3)
0.3766 (4)
0.2432 (3)
0.2679 (3)
0.2591 (3)
0.2240 (4)
0.1971 (4)
0.2060 (3)
ꢁ0.035858
0.217809
0.421741
0.404782
0.147114
0.096768
0.564988
0.341893
0.291169
0.277637
0.218522
0.171553
0.186741
0.161 (3)
0.329 (3)
0.2433 (3)
0.1485 (3)
0.0868 (3)
ꢁ0.0953 (3)
0.4573 (3)
0.6450 (3)
0.7973 (3)
0.7724 (3)
ꢁ0.0592 (4)
0.0398 (3)
0.3103 (3)
0.5215 (3)
0.8675 (4)
0.6331 (4)
0.5299 (3)
0.4434 (3)
0.5191 (4)
0.6811 (4)
0.7660 (4)
0.6935 (3)
ꢁ0.134588
0.056771
0.308479
0.320887
0.428487
0.572498
0.978148
0.536992
0.330456
0.458185
0.733305
0.877999
0.755244
0.215 (4)
0.230 (4)
ꢁ0.0016 (2)
0.3192 (2)
0.4060 (2)
0.1895 (2)
0.4232 (2)
0.2957 (2)
0.3909 (2)
0.1870 (2)
0.3224 (3)
0.1927 (3)
0.3688 (3)
0.3268 (3)
0.3198 (3)
0.1764 (3)
0.5622 (3)
0.6499 (3)
0.7873 (3)
0.8422 (3)
0.7550 (3)
0.6183 (3)
0.353729
0.114569
0.435917
0.297267
0.2449
0.0338 (9)
0.0219 (9)
0.0256 (9)
0.0283 (10)
0.0205 (8)
0.0220 (9)
0.0249 (9)
0.0280 (10)
0.0264 (11)
0.0252 (11)
0.0223 (11)
0.0243 (11)
0.0252 (11)
0.0262 (11)
0.0208 (10)
0.0214 (11)
0.0269 (11)
0.0284 (11)
0.0284 (12)
0.0237 (11)
0.0317ꢃ
N2
N3
N4
N5
N6
N7
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
H1
H2
0.0303ꢃ
H3a
H3b
H4a
H4b
H5
0.0267ꢃ
0.0267ꢃ
0.0291ꢃ
0.360503
0.359532
0.094166
0.614246
0.845681
0.937626
0.791278
0.560722
ꢁ0.052 (3)
ꢁ0.052 (3)
0.0291ꢃ
0.0302ꢃ
H6
H8
0.0315ꢃ
0.0257ꢃ
H9
0.0323ꢃ
H10
H11
H12
H1a
H1b
0.034ꢃ
0.0341ꢃ
0.0284ꢃ
0.0405ꢃ
0.0405ꢃ

2774
H. AL BAY ET AL.
Jana2006 whereby pairs of reflections from different twin domains are discarded or
used based in their difference in degrees of theta. Reflections falling into an interval
where partial overlaps are suspected are discarded. The carefully chosen interval
between 0.25 and 0.50 degrees theta led to discarding 210 reflections (i.e., 11% of
the data set), and the resulting R value was 4.47%, g.o.f. 2.62 (see Table 1).
Table 1 reports crystallographic data and experimental details for 2c. Atomic coor-
dinates and isotropic displacement parameters are reported in Table 3.
Interatomic distances are summarized in Table 4. Supplementary tables of
crystal structure and refinements, as well as the anisotropic thermal parameters, have
been deposited at the CCDC data base, code CCDC 734067 (www.ccdc.cam.ac.uk).
Crystal Structure Description of 2c
The framework of the compound 2c is built up from isolated N,N-bis((1H-
1,2,4-triazol-1-yl)methyl)benzenamine molecules and water molecules. The organic
molecules are associated only by dipole–dipole interactions and weak C—H . . . N
hydrogen bonds. In Fig. 3, we can distinguish slabs parallel with the ab plane.
Water molecules are located between them and bound via weak O-H . . . C hydrogen
ꢀ
˚
Table 4. Bonds and angles in the structure of 2c (A,
)
Bond
Value
Angle
Value
O1—H1a
N5—C4
O1—H1b
N5—C6
N1—N2
N6—C5
N1—C2
N7—C5
N1—C3
N7—C6
N2—C1
C7—C8
N3—C1
C7—C12
N3—C2
C8—C9
N4—C3
C9—C10
N4—C4
C10—C11
N4—C7
C11—C12
N5—N6
0.83 (2)
1.471 (4)
0.83 (3)
H1a—O1—H1b
N2—C1—N3
N2—N1—C2
N1—C2—N3
N2—N1—C3
N1—C3—N4
C2—N1—C3
N4—C4—N5
N1—N2—C1
N6—C5—N7
C1—N3—C2
N5—C6—N7
C3—N4—C4
N4—C7—C8
C3—N4—C7
N4—C7—C12
C4—N4—C7
C8—C7—C12
N6—N5—C4
C7—C8—C9
N6—N5—C6
C8—C9—C10
C4—N5—C6
C9—C10—C11
N5—N6—C5
C10—C11—C12
C5—N7—C6
C7—C12—C11
106 (3)
115.6 (3)
109.9 (2)
110.8 (3)
121.2 (2)
114.4 (2)
128.8 (3)
113.4 (2)
101.8 (2)
115.2 (2)
102.0 (2)
110.6 (2)
116.5 (2)
121.0 (3)
122.1 (3)
121.2 (3)
121.3 (2)
117.8 (2)
122.4 (2)
120.7 (3)
109.6 (2)
121.3 (3)
128.0 (2)
118.1 (3)
102.2 (2)
121.6 (3)
102.4 (2)
120.6 (3)
1.333 (4)
1.363 (4)
1.320 (4)
1.332 (3)
1.354 (3)
1.468 (3)
1.327 (4)
1.322 (3)
1.403 (5)
1.357 (4)
1.403 (4)
1.330 (4)
1.383 (4)
1.438 (4)
1.384 (4)
1.445 (4)
1.390 (5)
1.410 (3)
1.374 (4)
1.363 (3)

TRIAZOLYL HETEROCYCLIC COMPOUNDS
2775
Figure 3. Projection along [100] from the structure of 2c; the color is polyedra as atoms. Molecules of N,N-
bis((1H-1,2,4-triazol-1-yl)methyl)benzenamine stack in slabs interconnected by H bonds via water molecules.
bonds. The C—H . . . N hydrogen bonds exist between the slabs as well as inside
the slabs.
Inside the organic slabs, the title molecules form zigzag chains as shown in
Fig. 4. C—H . . . N interactions link the two triazol fragments of two neighboring
N,N-bis((1H-1,2,4-triazol-1-yl)methyl)benzenamine molecules, both inside the hypo-
thetical chain as between two neighboring chains.
We report in Table 5 the short pꢁp interactions between five-ring triazol and
six-ring groups inside and between the chains. Notice that the strongest such inter-
˚
actions are between two triazol groups at 3.5736 A.
Because of steric effects in N,N-bis((1H-1,2,4-triazol-1-yl)methyl)benzenamine,
the molecule is not planar. This is expressed in terms of torsion angles as depicted in
Table 6.
Globally, N,N-bis((1H-1,2,4-triazol-1-yl)methyl)benzenamine shows usual
bonds, angles, and torsion angle features. Figure 5 depicts a perspective view of
N,N-bis((1H-1,2,4-triazol-1-yl)methyl)benzenamine.

2776
H. AL BAY ET AL.
Figure 4. Morphology of the organic slab; p–p interactions between triazol groups lead in chains of the
molecules connected by H bonds.
˚
Table 5. Short ring interactions in the molecule of 2c (distances <6 A)
Cg(I)
Cg(J)
Cg-Cg
a
Cg(1)
Cg(1)
Cg(1)
Cg(1)
Cg(2)
Cg(2)
Cg(2)
Cg(2)
Cg(3)
Cg(3)
Cg(3)
Cg(3)
Cg(3)
Cg(2)
Cg(2)
Cg(2)
Cg(3)
Cg(1)
Cg(1)
Cg(1)
Cg(3)
Cg(1)
Cg(1)
Cg(2)
Cg(2)
Cg(3)
5.7229 (18)
3.5736 (18)
5.3907 (16)
4.5603 (18)
3.5736 (18)
5.7228 (18)
5.3907 (16)
4.4730 (18)
5.7041 (19)
5.5206 (18)
5.5620 (17)
5.7290 (19)
5.1607 (17)
6.36
6.36
6.36
1.1459
ꢁ4.2070
2.4946
ꢁ2.2219
ꢁ6.1768
ꢁ1.1662
ꢁ2.2219
1.5064
0.4454
1.1459
Notes. Cg(X) ¼ Plane #(X). Ring (1): five-membered N(1), N(2), C(1), N(3), C(2). Ring
(2): five-membered N(15), N(6), C(5), N(7), C(6)]. Six-membered C(7), C(8), C(9), C(10),
C(11), C(12).a ¼ dihedral angle between planes I and J (ꢀ).

TRIAZOLYL HETEROCYCLIC COMPOUNDS
2777
Table 6. H bond interactions in the crystal structure of 2c
D-H
H . . . A
D . . . A
D-H . . . A
O(1)–H(1A) . . . N(3)
O(1)–H(1B) . . . N(7)
C(1) –H(1) . . . N(2)
C(2)–H(2) . . . O(1)
C(6)–H(6) . . . O(1)
C(8)–H(8) . . . N(2)
C(12)–H(12) . . . N(6)
0.83 (3)
0.83 (3)
0.96
2.11 (3)
2.08 (3)
2.59
2.925 (3)
2.898 (3)
3.288 (4)
3.147 (4)
3.174 (4)
3.226 (4)
3.191 (4)
169 (3)
171 (3)
129
0.96
0.96
2.32
2.33
144
146
0.96
0.96
2.56
2.57
126
123
Figure 5. Spatial representation of 2c crystal. Displacement ellipsoids are drawn at the 50% probability level.
CONCLUSION
In conclusion, we have synthesized new tripodal triazolic compounds with the
opportunity to change the substituents easily and generate good to excellent yields.
The x-ray structure of one of these compounds has been investigated. Such structural
and electronic diversity may have potential applications in medicinal or coordination
chemistry. Further developments on this subject are currently in progress.
ACKNOWLEDGMENTS
We thank the Centre National de la Recherche Scientifique et Technique,
´
CNRST (Morocco), and the Commission Universitaire pour le Developpement,
CUD (Belgium), for financial support. We also acknowledge Institutional research

2778
H. AL BAY ET AL.
plan No. AVOZ10100521 of the Institute of Physics and the project Praemium
Academiae of the Academy of Sciences of the Czech Republic.
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