Synthesis and crystal structure of 1-methyl-3-(4-nitrophenyl)-1,2,3 triazolium perchlorate

Article abstract of DOI:10.1080/744818946

The isolation of stable carbenes of the Arduengo (1a) and Wanzlick (2a) type has prompted us to look for stable nitrenium ions of the related structural type 1-melhyl-3-(4-nitrophenyl)-1,2,3 triazolium perchlorate (6). The title compound (C₉ H<

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SYNTHESIS AND CRYSTAL
STRUCTURE OF 1-METHYL-3-
(4-NITROPHENYL)-1,2,3
TRIAZOLIUM PERCHLORATE
a
a
B. H. Doreswamy , M. Mahendra , M. A. Sridhar
a
a
b
,
J. Shashidhara Prasad , K. Mantelingu , K.
b
b
Basappa & S. Rangappa
a
Department of Studies in Physics, University of
Mysore, Manasagangotri, Mysore 570 006, India
b
Department of Studies in Chemistry, University of
Mysore, Manasagangotri, Mysore 570 006, India
Published online: 02 Feb 2011.
To cite this article: B. H. Doreswamy , M. Mahendra , M. A. Sridhar , J. Shashidhara
Prasad , K. Mantelingu , K. Basappa & S. Rangappa (2003) SYNTHESIS AND CRYSTAL
STRUCTURE OF 1-METHYL-3-(4-NITROPHENYL)-1,2,3 TRIAZOLIUM PERCHLORATE,
Molecular Crystals and Liquid Crystals, 403:1, 67-75
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Mol. Cryst. Liq. Cryst., Vol. 403, pp. 67–75, 2003
Copyright # Taylor & Francis Inc.
ISSN: 1542-1406 print/1563-5287 online
DOI: 10.1080/15421400390233977
SYNTHESIS AND CRYSTAL STRUCTURE OF
-METHYL-3-(4-NITROPHENYL)-1,2,3 TRIAZOLIUM
PERCHLORATE
1
B. H. Doreswamy, M. Mahendra, M. A. Sridhar, and
J. Shashidhara Prasad
Department of Studies in Physics, University of Mysore,
Manasagangotri, Mysore 570 006, India
K. Mantelingu, K. Basappa, and S. Rangappa*
Department of Studies in Chemistry, University of Mysore,
Manasagangotri, Mysore 570 006, India
The isolation of stable carbenes of the Arduengo (1a) and Wanzlick (2a) type
has prompted us to look for stable nitrenium ions of the related structural type
1
-methyl-3-(4-nitrophenyl)-1,2,3 triazolium perchlorate (6). The title compound
11 Cl N ) was isolated and structure was investigated by X-ray crys-
tallography. It crystallizes in the monoclinic space group P2 /c with cell
(C
9
H
4 6
O
1
˚
˚
˚
parameters a ¼ 9.704(1) A, b ¼ 12.580(2) A, c ¼ 13.684(8) A, Z ¼ 4. The mole-
cules appear to be stacked.
Keywords: nitrenium ions; carbenes; triazolium perchlorates; crystal structure
INTRODUCTION
Nitrenium ions are involved as highly reactive intermediates in a wide
variety of organic reaction [1]. For example, aromatic nitrenium ion
(
Figure 1) with R ¼ aryl, R ¼ H or C(O), CH , or SO are considered as
1
2
3
3
ultimate carcinogens in carcenogenesis initiated by aromatic amines [2].
Nitrenium ions are isoelectronic with carbenes R C containing a cationic [3]
divalent nitrogen atom R N . Recent time-resolved studies allowed the UV
2
2
þ
and IR spectra of some short-lived aryl nitrenium ions to be measured and
Received 10 February 2003; accepted 26 May 2003.
The authors would like to express their thanks to DST and AICTE, Government of India for
financial assistance under the projects SP/I2/FOO/93 and 8017/RD/MON-Sw/653/R&D/98-99/
2
000.
Corresponding author. E-mail: rangappaks@yahoo.com
*
67

6
8
B. H. Doreswamy et al.
FIGURE 1 Stable carbene of the Arduengo (1a) and Wanzlick (2a) type.
provided important results on their structure and reactivity [4]. Although
electronically deficient molecules of the types mentioned above are
extremely short-lived, Arduengo [5(a)] and Wanzlick [5(b)] et al. recently
isolated and structurally characterized stable crystalline carbenes (Figure 1)
concomitantly. Stable crystals of nitrenium ions more precisely, ion pair of
nitrenium ions were synthesized and their crystal structures were deter-
mined [6]. From experimental data and theoretical calculations it emerged
that these molecules are stabilized by electronic delocalization [7]. Intra-
molecular rearrangement reaction of nitrenium ions have been reported
and established as useful intermediates in wide variety of biological
applications [8].
In our previous work, we described the synthesis of some stable nitre-
nium ions [6] and their comparison study with structurally related carbenes
and found that stable nitrenium ions (as their carbene analogues) are
electronically different from nonstable ones. To get further insight into
their exact nature and role of nitrenium ions, the title compound 6 was
synthesised as per Scheme 1 and characterized by X-ray diffraction
method.
EXPERIMENTAL
Synthesis and Characterization
3-(2-hydroxyethyl)-3-methyl-1-(4-nitrophenyl)triazene (5)
The preparation of 5 was by diazotization of 4-nitroaniline (10 gm,
.0724 mol). First, 4-nitroaniline was dissolved in 23 ml of concentrated
0

Synthesis and Structure of Triazolium Perchlorate
69
SCHEME 1
ꢀ
hydrochloric acid and 23 ml of water and cooled to 0–5 C in an ice bath.
Then we added sodium nitrite (7.4 gm, 0.0724 mol) in 16 ml of water to this
cold solution. The diazonium salt solution 4 was mixed with a cold solution
of 2-(methylamino)ethanol (5.42 gm, 0.0724 mol) in 25 ml of Na CO
2
3
ꢀ
solution (25%). The mixture was stirred for half an hour at 0–5 C, and
triazene 5 was extracted with ether and dried with anhydrous sodium
sulphate and evaporated the solvent. The product was obtained as red oil to
yield (54.4%).
1
H NMR (CDCl , 400 MHz); d(ppm): 3.38 (s, 4H, N–CH and OH), 3.86–
3
3
1
.93 (m, 4H, CH –CH ), 7.74 (d, 2H, Ar–H), 7.92 (d, 2H, Ar–H); C NMR
3
3
2 2
(
(
CDCl , 100 MHz); d(ppm): 49.9, 55.8, 62.8, 128.9, 130.8, 136.2, 145.8; IR
Nujol); nmax (cm ): 3429 (OH), 1548 (C–N). 1619 (C¼C), Ana. Calcd. for
3
ꢁ
1
C H N O : C, 48.21; H, 5.35; N, 25.01. Found: C, 48.32, H. 5.39, N, 25.22.
9 12 4 3
1
-methyl-3-(4-nitrophenyl)-1,2,3 triazolium perchlorate (6)
Triazene 5(1 gm, 4.46 mmol) was dissolved in dry dichloromethane and
ꢀ
cooled to ꢁ15 to ꢁ10 C. Triethylamine (0.450 gm, 4.46 mmol) was mixed
with triazene cold solution. Methyl-sulfonyl chloride (0.364 gm, 4.46 mmol)
in 0.9 ml of dry dichloromethane was added to a cold triazene solution
ꢀ
without raising the temperature above 5 C. The reaction mixture was
stirred for 40–50 min at the same temperature. We distilled out the solvent
under reduced pressure up to residueness. The residue was washed with
benzene and dissolved in ethanol. To the ethanolic solution aqueous solu-
tion of NaClO (2 gm of NaClO in 30 ml of water) was added. The product
4
4

7
0
B. H. Doreswamy et al.
was filtered off and followed by recrystallization with aqueous ethanol(1:1)
to yield as yellow crystalline solid (72%). The melting point (mp) of 6 was
ꢀ
found to be 159 C.
1
H NMR (DMSO-d , 400 MHz); d(ppm): 3.88 (s, 3H, N–CH ), 4.61 (t, 2H,
6
3
CH –CH ), 4.83 (t, 2H, CH –CH ), 7.59 (d, 2H, Ar–H), 7.89 (d, 2H, Ar–H);
2
2
2
2
13
C NMR (DMSO-d , 100 MHz); d(ppm): 45.2, 51.5, 56.3, 119.7, 120.9,
132.9, 135.8; IR (KBr); nmax(cm ): 1489, 1506 (C–N), 1099 (N–N–N).
Ana. Calcd. for C H N O Cl: C, 35.24; H, 3.60; N, 18.27. Found: C, 35.62;
6
ꢁ
1
9
11 4 6
H, 3.79; N, 18.76.
CRYSTAL STRUCTURE DETERMINATION
Single crystal of dimensions 0.2560.260.25 mm was chosen for X-ray
diffraction studies. The measurements were made on a DIPLabo Imaging
TABLE 1 Crystal Data and Experimental Crystallographic Details of 6
Empirical formula
Formula weight
Temperature
C
9
H
11 Cl N
4 6
O
306.67
293(2) K
˚
0.71073 A
Monoclinc
Wavelength
Crystal system
Space group
Cell dimensions
1
P 2 /c
˚
a ¼ 9.704(1) A
˚
b ¼ 12.580(2) A
˚
c ¼ 13.684(8) A
ꢀ
ꢀ
¼ 129.393(8)
3
˚
1291.0(3) A
Volume
Z
4
1.578 Mg/m
3
Density (calculated)
Absorption coefficient
ꢁ1
0.329 mm
632
brown
F
000
Crystal color
Crystal size
0.2560.260.25 mm
2.52 to 24.40
ꢀ
ꢀ
Theta range for data collection
Index ranges
ꢁ11 ꢂ h ꢂ 11
ꢁ
14 ꢂ k ꢂ 14
ꢁ
15 ꢂ l ꢂ 15
Reflections collected
Independent reflections
Refinement method
Data/parameters
3676
2043 [R(int) ¼ 0.0251]
Full-matrix least-squares on F
2043/182
2
2
Goodness-of-fit on F
Final R indices [I > 2ꢁ(I)]
R indices (all data)
1.100
R1 ¼ 0.0854
R1 ¼ 0.0989
Extinction coefficient
Largest diff. peak and hole
0.003(4)
ꢁ3
0.968 and ꢁ0.924 e.A˚

Synthesis and Structure of Triazolium Perchlorate
71
TABLE 2 Atomic Coordinates and Equivalent Thermal Parameters of the
Nonhydrogen Atoms
Atom
x
y
z
U
eq
Cl1
N14
C10
C11
N15
N7
0.176(2)
0.2183(1)
0.1273(3)
0.2692(4)
0.2189(4)
0.0723(3)
0.4786(4)
ꢁ0.0065(3)
0.3915(4)
0.3428(4)
0.3567(4)
0.0794(4)
0.5204(3)
0.2570(4)
ꢁ0.0784(5)
ꢁ0.0099(4)
0.5052(4)
0.2883(6)
0.185(16)
0.263(10)
0.139(10)
0.1880(2)
0.2184(3)
0.0904(5)
0.2066(4)
0.1190(4)
0.1727(5)
0.1515(4)
0.1853(5)
0.3021(5)
0.0800(5)
0.3372(5)
0.0690(4)
0.3122(5)
0.0583(5)
0.2879(5)
0.2663(4)
0.1052(5)
0.1251(11)
0.2873(8)
0.2327(12)
0.0565(6)
0.0402(10)
0.0498(13)
0.397(11)
0.0441(10)
0.557(12)
0.0482(11)
0.0448(12)
0.0494(13)
0.0513(13)
0.0481(12)
0.0743(13)
0.0500(13)
0.0703(18)
0.0525(13)
0.0745(13)
0.134(3)
0.8103(5)
0.6008(7)
0.7170(6)
0.7553(5)
0.4195(6)
0.8568(6)
0.5296(6)
0.6500(7)
0.5053(7)
0.9652(7)
0.3130(6)
0.7444(7)
0.8317(9)
1.0107(7)
0.4384(6)
0.1703(9)
0.015(13)
0.211(2)
N16
C8
C13
C9
C18
O6
C12
C19
C17
O5
O1
O3
0.364(13)
0.299(9)
0.244(7)
O4
O2
0.288(2)
TABLE 3 Anisotropic Thermal Parameters of the Nonhydrogen Atoms
Atom
U
11
U
22
U
33
U
12
U
13
U
23
Cl1
N14
C10
C11
N15
N7
0.060(9)
0.037(2)
0.049(3)
0.035(2)
0.045(2)
0.042(2)
0.054(2)
0.037(2)
0.049(3)
0.045(3)
0.044(3)
0.060(3)
0.053(3)
0.095(5)
0.049(3)
0.073(3)
0.108(5)
0.116(7)
0.51(2)
0.066(10)
0.045(2)
0.062(3)
0.041(3)
0.046(2)
0.054(3)
0.048(2)
0.042(3)
0.053(3)
0.057(3)
0.054(3)
0.070(3)
0.050(3)
0.056(3)
0.048(3)
0.079(3)
0.167(6)
0.63(3)
0.050(9)
0.038(2)
0.037(3)
0.044(3)
0.041(2)
0.059(3)
0.042(2)
0.050(3)
0.044(3)
0.039(3)
0.039(3)
0.062(3)
0.039(3)
0.054(4)
0.047(3)
0.069(3)
0.079(4)
0.195(10)
0.099(6)
0.266(12)
0.004(6)
0.0021(17)
0.010(2)
0.0382(8)
0.0237(18)
0.027(2)
0.026(2)
0.273(19)
0.026(2)
0.031(2)
0.025(2)
0.029(2)
0.020(2)
0.023(2)
0.025(2)
0.025(2)
0.044(3)
0.024(2)
0.044(2)
0.037(3)
0.026(6)
0.165(10)
0.249(13)
0.0037(6)
0.0014(17)
0.02(2)
ꢁ0.0025(19)
0.0020(18)
0.000(2)
ꢁ0.0025(19)
0.0018(17)
ꢁ0.009(2)
0.0040(18)
ꢁ0.005(2)
ꢁ0.008(2)
0.006(2)
N16
C8
0.008(2)
ꢁ0.002(2)
ꢁ0.002(2)
0.013(2)
C13
C9
C18
O6
0.005(2)
0.023(2)
0.005(2)
0.000(2)
C12
C19
C17
O5
0.004(2)
0.018(3)
0.002(2)
ꢁ0.001(3)
0.004(2)
0.005(2)
0.013(2)
ꢁ0.016(2)
0.0414(4)
0.211(14)
0.031(6)
O1
O3
ꢁ0.052(4)
ꢁ0.139(12)
0.204(13)
0.220(12)
O4
O2
0.237(12)
0.237(11)
0.346(16)
0.154(10)

7
2
B. H. Doreswamy et al.
˚
TABLE 4 Bond Lengths (A) and Bond Angles ( )
ꢀ
Atoms
Length
Atoms
Length
Cl1-O3
Cl1-O4
1.280(8)
1.300(7)
1.306(8)
1.370(5)
1.301(5)
1.410(6)
1.471(6)
1.387(7)
1.387(7)
1.379(7)
N15-N16
N7-O5
N7-O6
1.263(6)
1.220(6)
1.222(6)
1.462(7)
1.453(7)
1.475(7)
1.377(7)
1.387(7)
1.365(7)
1.513(7)
Cl1-O2
Cl1-O1
N7-C8
N14-N15
N14-C11
N14-C18
C10-C11
C10-C9
C11-C12
N16-C19
N16-C17
C8-C9
C8-C13
C13-C12
C18-C17
Atoms
Angle
Atoms
Angle
O3-Cl1-O4
O3-Cl1-O2
104.0(2)
111.4(2)
104.7(7)
104.0(5)
116.9(8)
115.4
O5-N7-O6
O5-N7-C8
O6-N7-C8
123.6(5)
118.0(5)
118.4(5)
121.3(4)
113.9(4)
124.3(4)
121.6(5)
119.2(4)
119.1(5)
119.2(5)
119.1(5)
101.2(4)
119.9(5)
101.2(4)
O4-Cl1-O2
O3-Cl1-O1
N15-N16-C19
N15-N16-C17
C19-N16-C17
C9-C8-C13
C9-C8-N7
O4-Cl1-O1
O2-Cl1-O1
N15-N14-C11
N15-N14-C18
Cl1-N14-C18
Cl1-C10-C9
C12-C11-C10
C12-C11-N14
C10-C11-N14
N16-N15-N14
120.5(4)
113.1(4)
126.3(4)
119.0(5)
121.2(5)
118.8(4)
120.0(4)
109.7(4)
C13-C8-N7
C12-C13-C8
C8-C9-C10
N14-C18-C17
C13-C12-C11
N16-C17-C18
FIGURE 2 ORTEP of the molecule at 50% probability.

Synthesis and Structure of Triazolium Perchlorate
73
Plate system with graphite monochromated MoK radiation. Thirty six
a
frames of data were collected using oscillation method. Image processing
and data reduction were done by using Denzo [12]. The structure was
solved and refined using maXus [10–14] program. All the nonhydrogen
atoms were revealed in the first map. Full-matrix least-squares refinement
using SHELXL-97 [14] with isotropic temperature factors for all the atoms
converged residual to R ¼ 0.1864. Refinement of nonhydrogen atoms with
anistropic thermal parameters was started at this stage. After eight cycles
of refinement the residuals saturated at R ¼ 0.0854. The hydrogen atoms
were placed at calculated positions and were not refined. Table 1 gives the
details of crystal data, data collection, and refinement.
RESULTS AND DISCUSSION
The final positional coordinates with equivalent isotropic temperature fac-
tors for all nonhydrogen atoms are given in Table 2. Anisotropic thermal
FIGURE 3 Packing of the molecules down a axis.

7
4
B. H. Doreswamy et al.
parameter (U ) for the nonhydrogen atoms are listed in Table 3. Table 4
ij
gives the bond distances and angles of nonhydrogen atoms. The bond
distances and bond angles are in good agreement with the standard values.
ORTEP [11] of the molecule at 50% probability is shown in Figure 2.
Figure 3 represents the packing of the molecules and dashed lines repre-
sent the hydrogen bonds. It shows stacking of molecules in pairs when
ꢁ
viewed down a axis. The crystal structure shows that the anion ClO4 is not
directly connected to the positively charged part of the respective nitre-
ꢁ
ꢁ
nium ion. ClO4 holds cation by means of C–H ꢃ ꢃ ꢃ ClO hydrogen bonds
4
[
15,16] and their intermolecular interactions appear to be responsible for
molecular cohesion in the unit cell. The cationic part of the niternium ion is
planar, and phenyl and five-membered rings are independently planar. The
˚
ꢀ
intermolecular hydrogen bonds are: C18-H12B . . . O1 (3.336 A, 127.65 )
˚
ꢀ
and C19-H15A . . . O4 (3.119 A, 131.20 ) with symmetry codes 1þx, 1/2ꢁy,
/2þz and 1ꢁx, ꢁ1/2þy, 1/2ꢁz, respectively.
1
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(
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[
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Synthesis and Structure of Triazolium Perchlorate
75
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