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

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 C—H...π interactions involving the piperidine C—H 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 π–π stacking interactions between the tetrazole rings of two adjacent mol­ecules.

S1. Comment

This work forms part of a systematic investigation of the molecular and crystal structure of 5-(α-aminoalkyl)tetrazoles, which are of great interest in the field of bioorganic and medicinal chemistry. We previously reported the structures of 5-(piperidiniomethyl)-1-H-tetrazolide (Lyakhov et al., 2002) 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-[(1-phenyl-1H-1,2,3,4-tetrazol-5-yl)methyl]piperidine, (I) (Fig. 1).

The tetrazole and benzene rings are planar to within 0.0012 (7) and 0.0051 (9) Å, respectively, but they are not coplanar, their mean planes being inclined at 42.96 (5)° to one another.

The formal N2=N3 [1.2928 (15) Å] and N4=C5 double bonds [1.3169 (14) Å] are the shortest in the tetrazole ring, while the three remaining ring bonds have legnths in the narrow range 1.3510 (15)–1.3553 (17) Å (Table 1). This geometry is typical of 1,5-disubstituted tetrazoles with alkyl or aryl substitutents. An analysis performed with the Cambridge Structural Database (Version 5.25 of November 2003; Allen, 2002) gave the following mean values of the tetrazole ring bond lengths for such compounds (14 hits): N1—N2 = 1.355 (2) Å, N2=N3 = 1.295 (1) Å, N3—N4 = 1.357 (2) Å, N4=C5 = 1.320 (2) Å and N1—C5 = 1.340 (2) Å. The tetrazole ring bond lengths of (I) fall in the above ranges.

The piperidine fragment has a chair conformation (bond lengths are listed in Table 1).

There is short intramolecular C11—H11···N13 contact, with an H11···N13 distance of 2.648 (13) Å, a C11···N13 distance of 3.4395 (15) Å, and a C11—H11···N13 angle of 138.3 (10)°. This interaction may be resposible for the conformation adopted by the molecule in the solid.

Because of the lack of classical hydrogen-bond donors in the structure of (I), the packing is determined by weaker interactions, namely the C—H···π and π–π contacts.

C—H···π interactions arise, firstly, between piperidine atom H17A of one molecule and the benzene ring of another molecule at (3/2 − x, 1/2 + y, 3/2 − z), and, secondly, between piperidine atom H18A and the benzene ring of the molecule at (1 + x, y, z) (Table 2). These interactions are characterized by C—H···CgBz angles of 139.2 (11) and 152.1 (11)°, and by H···CgBz distances of 3.246 (15) and 2.726 (15) Å, for the interactions involving atoms H17A and H18A, respectively (CgBz is the centroid of the benzene ring). These interactions form two-dimensional networks, extending parallel to the xy plane (Fig. 2).

π···π stacking interactions exist between the tetrazole π-rings of two molecules related by the symmetry transformation (j), (1 − x, −y, 1 − z), with an intercentroid distance, CgTz···CgTz^j, of 3.7015 (13) Å (CgTz denotes the centroid of the tetrazole ring). These interactions connect the two-dimensional networks into a three-dimensional polymeric structure.

S2. Experimental

The title compound was prepared by aminomethylation of 1-phenyltetrazole with piperidine and formaldehide 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 trifluoroacetic acid (50 ml) was heated under reflux 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 solution with diethyl ether (3 × 30 ml), evaporation of diethyl ether and recrystallization of the residue from ethanol (yield 64%, 6.2 g; m.p. 361 K). ¹H NMR (100 MHz, DMSO-d₆, p.p.m.): 1.43–1.64 (m, 6H, 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.

S3. Refinement

H-atom positions were found from a difference Fourier map and all associated parameters were refined freely [C—H = 0.96 (1)–1.05 (2) Å].

Computing details

Data collection: R3m software (Nicolet, 1980); cell refinement: R3m software; data reduction: R3m software; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures

	Fig. 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.
	Fig. 2. A fragment of the crystal structure of (I), showing the two-dimensional network parallel to the xy plane. Dashed lines indicate C—H···π interactions (Table 2). H atoms, with the exception of atoms H17A and H18A, have been omitted.

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

Crystal data

C13H17N5	F(000) = 520
Mr = 243.32	Dx = 1.260 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 7.7537 (13) Å	θ = 12.4–20.3°
b = 10.436 (3) Å	µ = 0.08 mm^−1
c = 15.937 (3) Å	T = 293 K
β = 96.142 (13)°	Prism, colourless
V = 1282.2 (5) Å^3	0.54 × 0.50 × 0.46 mm
Z = 4

Data collection

Nicolet R3m four-circle diffractometer	Rint = 0.019
Radiation source: fine-focus sealed tube	θmax = 30.1°, θmin = 2.3°
Graphite monochromator	h = 0→10
ω/2θ scans	k = 0→14
4125 measured reflections	l = −22→22
3746 independent reflections	3 standard reflections every 100 reflections
2759 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.042	All H-atom parameters refined
wR(F^2) = 0.120	w = 1/[σ^2(Fo^2) + (0.0582P)^2 + 0.0879P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
3746 reflections	Δρmax = 0.17 e Å^−3
232 parameters	Δρmin = −0.25 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.480 (16)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.33395 (12)	0.14877 (8)	0.53722 (5)	0.0455 (2)
N2	0.23195 (15)	0.13018 (10)	0.46377 (6)	0.0598 (3)
N3	0.33297 (18)	0.13906 (11)	0.40455 (6)	0.0697 (3)
N4	0.49897 (16)	0.16229 (10)	0.43672 (6)	0.0632 (3)
C5	0.49825 (15)	0.16835 (9)	0.51921 (7)	0.0482 (3)
C6	0.26254 (13)	0.13607 (9)	0.61587 (6)	0.0433 (2)
C7	0.14675 (15)	0.03748 (11)	0.62453 (8)	0.0513 (3)
H7	0.1197 (17)	−0.0218 (14)	0.5794 (8)	0.063 (4)*
C8	0.07734 (16)	0.02440 (12)	0.70039 (8)	0.0589 (3)
H8	−0.006 (2)	−0.0446 (16)	0.7068 (9)	0.077 (4)*
C9	0.12399 (16)	0.10749 (14)	0.76591 (8)	0.0610 (3)
H9	0.0770 (19)	0.0923 (15)	0.8186 (9)	0.078 (4)*
C10	0.23807 (16)	0.20551 (14)	0.75615 (7)	0.0588 (3)
H10	0.267 (2)	0.2671 (17)	0.8010 (10)	0.086 (5)*
C11	0.30840 (14)	0.22187 (11)	0.68054 (7)	0.0502 (3)
H11	0.3870 (18)	0.2920 (13)	0.6702 (8)	0.060 (3)*
C12	0.65236 (15)	0.19014 (11)	0.58159 (7)	0.0508 (3)
H12A	0.6346 (16)	0.1446 (12)	0.6349 (8)	0.053 (3)*
H12B	0.7549 (18)	0.1512 (13)	0.5579 (8)	0.063 (4)*
N13	0.68014 (11)	0.32565 (8)	0.60180 (5)	0.0441 (2)
C14	0.73631 (16)	0.39423 (11)	0.52936 (7)	0.0519 (3)
H14A	0.6458 (19)	0.3857 (13)	0.4823 (8)	0.064 (4)*
H14B	0.849 (2)	0.3515 (14)	0.5120 (9)	0.070 (4)*
C15	0.76814 (18)	0.53468 (12)	0.54975 (9)	0.0615 (3)
H15A	0.8020 (19)	0.5799 (15)	0.4980 (10)	0.076 (4)*
H15B	0.657 (2)	0.5723 (15)	0.5626 (9)	0.071 (4)*
C16	0.90389 (17)	0.55095 (14)	0.62460 (9)	0.0633 (3)
H16A	1.017 (2)	0.5169 (15)	0.6112 (9)	0.075 (4)*
H16B	0.916 (2)	0.6458 (16)	0.6392 (11)	0.087 (5)*
C17	0.85428 (18)	0.47332 (14)	0.69841 (8)	0.0622 (3)
H17A	0.952 (2)	0.4698 (15)	0.7459 (9)	0.076 (4)*
H17B	0.749 (2)	0.5138 (15)	0.7203 (9)	0.074 (4)*
C18	0.81532 (16)	0.33599 (13)	0.67374 (8)	0.0558 (3)
H18A	0.927 (2)	0.2922 (14)	0.6587 (9)	0.073 (4)*
H18B	0.7723 (17)	0.2852 (14)	0.7186 (9)	0.067 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0559 (5)	0.0387 (4)	0.0416 (4)	−0.0051 (4)	0.0036 (4)	−0.0012 (3)
N2	0.0790 (7)	0.0532 (5)	0.0451 (5)	−0.0160 (5)	−0.0034 (5)	−0.0049 (4)
N3	0.1051 (9)	0.0591 (6)	0.0450 (5)	−0.0183 (6)	0.0086 (5)	−0.0077 (4)
N4	0.0893 (8)	0.0526 (6)	0.0506 (5)	−0.0091 (5)	0.0208 (5)	−0.0066 (4)
C5	0.0622 (6)	0.0353 (5)	0.0492 (5)	−0.0007 (4)	0.0150 (5)	0.0003 (4)
C6	0.0446 (5)	0.0417 (5)	0.0434 (5)	0.0028 (4)	0.0036 (4)	0.0014 (4)
C7	0.0528 (6)	0.0427 (5)	0.0589 (6)	−0.0021 (4)	0.0085 (5)	−0.0009 (5)
C8	0.0524 (6)	0.0566 (7)	0.0698 (7)	0.0006 (5)	0.0163 (5)	0.0103 (6)
C9	0.0528 (6)	0.0796 (9)	0.0519 (6)	0.0087 (6)	0.0115 (5)	0.0098 (6)
C10	0.0528 (6)	0.0760 (8)	0.0468 (6)	0.0031 (6)	0.0019 (5)	−0.0080 (5)
C11	0.0477 (5)	0.0533 (6)	0.0491 (6)	−0.0027 (5)	0.0023 (4)	−0.0052 (4)
C12	0.0505 (6)	0.0444 (5)	0.0588 (6)	0.0049 (4)	0.0115 (5)	0.0085 (5)
N13	0.0395 (4)	0.0463 (5)	0.0469 (4)	0.0018 (3)	0.0073 (3)	0.0066 (3)
C14	0.0538 (6)	0.0542 (6)	0.0475 (6)	−0.0066 (5)	0.0043 (5)	0.0086 (4)
C15	0.0617 (7)	0.0532 (6)	0.0679 (7)	−0.0081 (5)	−0.0010 (6)	0.0115 (6)
C16	0.0524 (7)	0.0644 (8)	0.0723 (8)	−0.0101 (6)	0.0033 (6)	−0.0018 (6)
C17	0.0549 (7)	0.0765 (9)	0.0549 (7)	−0.0032 (6)	0.0045 (5)	−0.0068 (6)
C18	0.0522 (6)	0.0669 (7)	0.0477 (6)	0.0028 (5)	0.0023 (5)	0.0097 (5)

Geometric parameters (Å, º)

N1—C5	1.3510 (15)	C12—H12A	0.996 (13)
N1—N2	1.3546 (12)	C12—H12B	1.002 (14)
N1—C6	1.4296 (13)	N13—C14	1.4637 (13)
N2—N3	1.2928 (15)	N13—C18	1.4724 (14)
N3—N4	1.3553 (17)	C14—C15	1.5158 (18)
N4—C5	1.3169 (14)	C14—H14A	0.975 (14)
C5—C12	1.4878 (16)	C14—H14B	1.045 (15)
C6—C7	1.3821 (15)	C15—C16	1.5136 (19)
C6—C11	1.3828 (15)	C15—H15A	1.010 (15)
C7—C8	1.3816 (17)	C15—H15B	0.987 (15)
C7—H7	0.955 (14)	C16—C17	1.5116 (19)
C8—C9	1.3757 (19)	C16—H16A	0.989 (16)
C8—H8	0.981 (16)	C16—H16B	1.019 (17)
C9—C10	1.372 (2)	C17—C18	1.508 (2)
C9—H9	0.963 (15)	C17—H17A	1.012 (16)
C10—C11	1.3853 (16)	C17—H17B	1.013 (15)
C10—H10	0.970 (17)	C18—H18A	1.028 (16)
C11—H11	0.978 (14)	C18—H18B	0.976 (14)
C12—N13	1.4613 (15)
C5—N1—N2	108.35 (9)	C12—N13—C14	110.40 (9)
C5—N1—C6	131.51 (9)	C12—N13—C18	108.57 (9)
N2—N1—C6	119.95 (9)	C14—N13—C18	109.35 (9)
N3—N2—N1	106.10 (10)	N13—C14—C15	111.04 (10)
N2—N3—N4	111.21 (9)	N13—C14—H14A	108.2 (8)
C5—N4—N3	106.32 (10)	C15—C14—H14A	109.9 (8)
N4—C5—N1	108.03 (11)	N13—C14—H14B	109.2 (8)
N4—C5—C12	125.84 (11)	C15—C14—H14B	110.3 (8)
N1—C5—C12	126.11 (10)	H14A—C14—H14B	108.1 (11)
C7—C6—C11	121.71 (11)	C16—C15—C14	111.17 (11)
C7—C6—N1	118.24 (10)	C16—C15—H15A	111.8 (9)
C11—C6—N1	120.05 (9)	C14—C15—H15A	109.1 (9)
C8—C7—C6	118.62 (11)	C16—C15—H15B	109.9 (9)
C8—C7—H7	121.4 (8)	C14—C15—H15B	107.6 (9)
C6—C7—H7	120.0 (8)	H15A—C15—H15B	107.0 (12)
C9—C8—C7	120.43 (12)	C17—C16—C15	109.86 (11)
C9—C8—H8	120.4 (9)	C17—C16—H16A	106.3 (9)
C7—C8—H8	119.1 (9)	C15—C16—H16A	110.3 (9)
C10—C9—C8	120.28 (11)	C17—C16—H16B	111.6 (9)
C10—C9—H9	122.0 (9)	C15—C16—H16B	109.3 (10)
C8—C9—H9	117.6 (10)	H16A—C16—H16B	109.4 (13)
C9—C10—C11	120.60 (12)	C18—C17—C16	111.53 (11)
C9—C10—H10	120.9 (10)	C18—C17—H17A	105.9 (9)
C11—C10—H10	118.5 (10)	C16—C17—H17A	111.7 (8)
C6—C11—C10	118.35 (11)	C18—C17—H17B	109.9 (9)
C6—C11—H11	118.4 (7)	C16—C17—H17B	109.1 (9)
C10—C11—H11	123.3 (7)	H17A—C17—H17B	108.7 (11)
N13—C12—C5	112.59 (9)	N13—C18—C17	112.25 (10)
N13—C12—H12A	107.7 (7)	N13—C18—H18A	109.4 (8)
C5—C12—H12A	108.8 (7)	C17—C18—H18A	109.4 (8)
N13—C12—H12B	111.8 (8)	N13—C18—H18B	105.0 (8)
C5—C12—H12B	107.4 (8)	C17—C18—H18B	113.6 (8)
H12A—C12—H12B	108.4 (11)	H18A—C18—H18B	106.9 (12)
C5—N1—N2—N3	−0.24 (12)	C7—C8—C9—C10	0.99 (19)
C6—N1—N2—N3	−175.69 (9)	C8—C9—C10—C11	−0.31 (19)
N1—N2—N3—N4	0.33 (13)	C7—C6—C11—C10	1.39 (17)
N2—N3—N4—C5	−0.30 (13)	N1—C6—C11—C10	−179.25 (10)
N3—N4—C5—N1	0.14 (12)	C9—C10—C11—C6	−0.86 (18)
N3—N4—C5—C12	178.92 (10)	N4—C5—C12—N13	91.94 (13)
N2—N1—C5—N4	0.06 (11)	N1—C5—C12—N13	−89.49 (12)
C6—N1—C5—N4	174.80 (10)	C5—C12—N13—C14	−69.67 (11)
N2—N1—C5—C12	−178.73 (9)	C5—C12—N13—C18	170.48 (9)
C6—N1—C5—C12	−3.99 (17)	C12—N13—C14—C15	−179.20 (9)
C5—N1—C6—C7	−133.92 (11)	C18—N13—C14—C15	−59.81 (12)
N2—N1—C6—C7	40.32 (13)	N13—C14—C15—C16	58.41 (14)
C5—N1—C6—C11	46.70 (15)	C14—C15—C16—C17	−53.38 (16)
N2—N1—C6—C11	−139.06 (10)	C15—C16—C17—C18	51.90 (15)
C11—C6—C7—C8	−0.73 (17)	C12—N13—C18—C17	179.29 (10)
N1—C6—C7—C8	179.90 (10)	C14—N13—C18—C17	58.77 (13)
C6—C7—C8—C9	−0.48 (18)	C16—C17—C18—N13	−55.59 (14)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···N13	0.978 (14)	2.648 (13)	3.4395 (15)	138.3 (10)