1-Phenyl-5-(piperidinomethyl)-1H-tetrazole

Article abstract of DOI:10.1107/S0108270104005554

The molecular and crystal structures of 1-Phenyl-5-(piperidinomethyl)-1H- terazole was investigated. It was observed that the tetrazole and benzene rings are planar to within 0.0012 (7) and 0.0051 (9) A respectively but are not coplanar. It was also observed that there is a short intramolecular C11-H11···N13 contact which may be responsible for the conformation adopted by the molecule in the solid state. π-π stacking interactions exist between the terazole rings of two molecules related by the symmetry transformation (1 - x, -y, 1 - z), the centroid-centroid distance being 3.7015 (13) A.

Full text of DOI:10.1107/S0108270104005554

organic compounds
Acta Crystallographica Section C
Crystal Structure
while the three remaining ring bonds have lengths in the
Ê
narrow range 1.3510 (15)±1.3553 (17) A (Table 1). This
Communications
geometry is typical of 1,5-disubstituted tetrazoles with alkyl or
aryl substitutents. An analysis performed using the Cambridge
Structural Database (Version 5.25 of November 2003; Allen,
2002) gave the following mean values of the tetrazole ring
ISSN 0108-2701
1-Phenyl-5-(piperidinomethyl)-1H-
tetrazole
Alexander S. Lyakhov, Sergei V. Voitekhovich, Pavel N.
Gaponik and Ludmila S. Ivashkevich*
Physico-Chemical Research Institute, Belarusian State University, Leningradskaya
Str. 14, Minsk 220050, Belarus
Correspondence e-mail: iva@bsu.by
Received 12 February 2004
Accepted 9 March 2004
Online 31 March 2004
In the molecule of the title 1,5-disubstituted tetrazole,
C13H17N5, the tetrazole and benzene rings are not coplanar,
having a dihedral angle of 42.96 (5)ꢀ between them. The
piperidine fragment adopts a chair conformation, and there is
a non-classical intramolecular contact between the benzene H
atom and the piperidine N atom. Intermolecular CÐHÁ Á Áꢀ
interactions involving the piperidine CÐH groups and the
benzene rings are responsible for the formation of two-
dimensional networks, extending parallel to the ab plane.
These networks are linked together into a three-dimensional
polymeric structure via ꢀ±ꢀ stacking interactions between the
tetrazole rings of two adjacent molecules.
Figure 1
A view of (I), with the atom-numbering scheme and displacement
ellipsoids at the 30% probability level. H atoms are shown as spheres of
arbitrary radii.
Comment
This work forms part of a systematic investigation of the
molecular and crystal structures of 5-(ꢁ-aminoalkyl)tetrazoles,
which are of great interest in the ®eld of bioorganic and
medicinal chemistry. We previously reported the structures of
5-(piperidiniomethyl)-1H-tetrazolide (Lyakhov et al., 2003)
and the copper(II) chloride complex of N,N-dimethyl-1-
(1-methyl-1H-tetrazol-5-yl)methanamine (Ivashkevich et al.,
2002). We present here the crystal structure of 1-phenyl-5-
(piperidinomethyl)-1H-tetrazole, (I) (Fig. 1).
Figure 2
A fragment of the crystal structure of (I), showing the two-dimensional
network parallel to the ab plane. Dashed lines indicate CÐHÁ Á Áꢀ
interactions (Table 2). H atoms, with the exception of atoms H17A and
H18A, have been omitted.
bond lengths for such compounds (14 hits): N1ÐN2
Ê
Ê
1.355 (2) A, N2 N 1.295 (1) A, N3ÐN4 1.357 (2) A, N4 C5
Ê
Ê
Ê
1.320 (2) A and N1ÐC5 1.340 (2) A. The tetrazole ring bond
lengths of (I) are consistent with these values.
The tetrazole and benzene rings are planar to within
Ê
0.0012 (7) and 0.0051 (9) A, respectively, but they are not
coplanar, their mean planes being inclined at 42.96 (5)ꢀ to one
another.
The piperidine fragment has a chair conformation (bond
lengths are listed in Table 1).
There is a short intramolecular C11ÐH11Á Á ÁN13 contact
(Table 2), which may be responsible for the conformation
adopted by the molecule in the solid state.
Ê
The formal N2 N3 [1.2928 (15) A] and N4 C5 double
Ê
bonds [1.3169 (14) A] are the shortest in the tetrazole ring,
Acta Cryst. (2004). C60, o293±o294
DOI: 10.1107/S0108270104005554
# 2004 International Union of Crystallography o293

organic compounds
Data collection
Because of the lack of classical hydrogen-bond donors in
the structure of (I), the packing is determined by weaker
interactions, namely CÐHÁ Á Áꢀ and ꢀ±ꢀ contacts.
Nicolet R3m four-circle
diffractometer
!/2ꢄ scans
4125 measured re¯ections
3746 independent re¯ections
2759 re¯ections with I > 2ꢆ(I)
Rint = 0.019
ꢄmax = 30.1ꢀ
h = 0 ! 10
k = 0 ! 14
CÐHÁ Á Áꢀ interactions arise, ®rstly, between piperidine
l = 22 ! 22
atom H17A of one molecule and the benzene ring of another
3
3 standard re¯ections
every 100 re¯ections
intensity decay: none
molecule at (32 x, 21 + y,
z), and, secondly, between
2
piperidine atom H18A and the benzene ring of the molecule at
(1 + x, y, z) (Table 2). These interactions form two-dimen-
sional networks, extending parallel to the ab plane (Fig. 2).
ꢀ±ꢀ stacking interactions exist between the tetrazole rings
of two molecules related by the symmetry transformation
(1 x, y, 1 z), the centroid±centroid distance being
Re®nement
Re®nement on F2
R[F2 > 2ꢆ(F2)] = 0.042
wR(F2) = 0.120
S = 1.06
3746 re¯ections
w = 1/[ꢆ2(F2o) + (0.0582P)2
+ 0.0879P]
where P = (F2o + 2Fc2)/3
(Á/ꢆ)max < 0.001
3
Ê
Áꢇmax = 0.17 e A
3
Ê
0.25 e A
232 parameters
All H-atom parameters re®ned
Áꢇmin
Extinction correction: SHELXL97
=
Ê
3.7015 (13) A. These interactions connect the two-dimen-
sional networks into a three-dimensional polymeric struc-
ture.
Extinction coef®cient: 0.480 (16)
Table 2
ꢀ
Ê
Hydrogen-bonding and CÐHÁ Á Áꢀ interaction geometry (A, ).
CgBz is the centroid of the benzene ring.
Experimental
The title compound was prepared by aminomethylation of
1-phenyltetrazole with piperidine and formaldehyde according to the
method described by Karavai & Gaponik (1991). A solution of
1-phenyltetrazole (5.8 g, 40 mmol), piperidine (3.5 ml, 40 mmol) and
paraform (3 g) in tri¯uoroacetic acid (50 ml) was heated under re¯ux
for 5 h. The solvent was removed in vacuo and the residue was
treated with an aqueous solution of sodium hydroxide (30%, 20 ml).
The title compound was isolated by extraction of the resulting solu-
tion with diethyl ether (3 Â 30 ml), evaporation of the diethyl ether
and recrystallization of the residue from ethanol (yield 64%, 6.2 g;
DÐHÁ Á ÁA
DÐH
HÁ Á ÁA
DÁ Á ÁA
DÐHÁ Á ÁA
C11ÐH11Á Á ÁN13
0.978 (14)
1.012 (16)
1.028 (16)
2.648 (13)
3.246 (15)
2.726 (15)
3.4395 (15)
4.0673 (19)
3.6679 (17)
138.3 (10)
139.2 (11)
152.1 (11)
C17ÐH17AÁ Á ÁCgBzi
C18ÐH18AÁ Á ÁCgBzii
3
2
Symmetry codes: (i)
x, 12 + y, 32 z; (ii) 1 + x, y, z.
H-atom positions were found from a difference Fourier map and
all associated parameters were re®ned freely [CÐH = 0.96 (1)±
Ê
1.05 (2) A].
1
m.p. 361 K). H NMR (100 MHz, DMSO-d6): ꢂ 1.43±1.64 (m, 6H,
Data collection: R3m Software (Nicolet, 1980); cell re®nement:
R3m Software; data reduction: R3m Software; program(s) used to
solve structure: SIR97 (Altomare et al., 1999); program(s) used to
re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
ORTEP-3 for Windows (Farrugia, 1997); software used to prepare
material for publication: SHELXL97 and PLATON (Spek, 2003).
3CH2), 2.40 (t, 4H, 2CH2), 3.82 (s, 2H, CH2), 7.58±7.66 (m, 3H, Ph),
7.80±7.88 (m, 2H, Ph). Single crystals of (I) suitable for analysis were
grown by slow evaporation from a 2-propanol solution at room
temperature in air.
Crystal data
C13H17N5
Mr = 243.32
Monoclinic, P21=n
Mo Kꢁ radiation
Cell parameters from 25
re¯ections
Supplementary data for this paper are available from the IUCr electronic
archives (Reference: AV1171). Services for accessing these data are
described at the back of the journal.
ꢄ = 12.4±20.3ꢀ
Ê
a = 7.7537 (13) A
Ê
1
b = 10.436 (3) A
Ê
ꢅ = 0.08 mm
T = 293 (2) K
c = 15.937 (3) A
ꢃ = 96.142 (13)ꢀ
Prism, colourless
0.54 Â 0.50 Â 0.46 mm
References
3
Ê
V = 1282.2 (5) A
Allen, F. H. (2002). Acta Cryst. B58, 380±388.
Z = 4
Dx = 1.260 Mg m
3
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C.,
Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J.
Appl. Cryst. 32, 115±119.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Table 1
Selected intermolecular distances (A).
Ê
Ivashkevich, D. O., Lyakhov, A. S., Voitekhovich, S. V., Gaponik, P. N. &
Ivashkevich, L. S. (2002). Acta Cryst. C58, m563±m564.
Karavai, V. P. & Gaponik, P. N. (1991). Khim. Geterotsikl. Soedin. pp. 66±71.
(In Russian.)
Lyakhov, A. S., Voitekhovich, S. V., Gaponik, P. N. & Ivashkevich, L. S. (2003).
Acta Cryst. C59, o22±o23.
Nicolet (1980). R3m Software. Nicolet XRD Corporation, Cupertino, Cali-
fornia, USA.
È
Sheldrick, G. M. (1997). SHELXL97. University of Gottingen, Germany.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7±13.
N1ÐC5
N1ÐN2
N1ÐC6
N2ÐN3
N3ÐN4
N4ÐC5
C5ÐC12
1.3510 (15)
1.3546 (12)
1.4296 (13)
1.2928 (15)
1.3553 (17)
1.3169 (14)
1.4878 (16)
C12ÐN13
N13ÐC14
N13ÐC18
C14ÐC15
C15ÐC16
C16ÐC17
C17ÐC18
1.4613 (15)
1.4637 (13)
1.4724 (14)
1.5158 (18)
1.5136 (19)
1.5116 (19)
1.508 (2)
ꢁ
o294 Alexander S. Lyakhov et al.
C13H17N5
Acta Cryst. (2004). C60, o293±o294