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The title compound, C7H13N5, a tetrazole analogue of betaines, exists as a zwitterion, with the H atom of the tetrazole ring being transferred to the piperidine ring N atom. The tetrazole ring symmetry is close to C2v, which suggests strong charge delocalization in the N-C-N fragment of the ring. There are classical hydrogen bonds in the structure which are responsible for the formation of two-membered aggregates.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102020905/av1125sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102020905/av1125Isup2.hkl
Contains datablock I

CCDC reference: 204044

Comment top

Tetrazole and its 5-substituted derivatives attract research attention in the field of bioorganic and medicinal chemistry, due to the isosterity and acidity of the N-unsubstituted tetrazole ring being comparable with those of the carboxylic acid group (Butler, 1996). 5-Monosubstituted tetrazoles with an aminomethyl substituent represent an interesting class of tetrazole analogues of α-aminoacids. One should expect that such compounds may exist in the form of a zwitterion. In this paper, we report the molecular and crystal structures of the title compound, (I) (Fig. 1). No crystal data were found for 5-(α-aminomethyl)tetrazoles (Cambridge Structural Database, Version 5.23 of September 2002; Allen, 2002). \sch

As was expected, compound (I) exists as a zwitterion, with the H atom of the tetrazole ring being transferred to the piperidine ring N atom. The main geometrical features of (I) are given in Table 1.

As can be seen in Fig. 1, the tetrazole ring in (I) is rather symmetrical. The C5—N1 and C5—N4 bond lengths are practically the same, and the N1—N2 bond length is equal to the value for N3—N4. The N2—N3 bond is the shortest in the ring. Bond symmetry is supported by angle symmetry (Table 1). Moreover, the tetrazole ring is essentially planar to within 0.0019 (6) Å. Thus, the ring symmetry is close to C2v. Taking into account the essential difference between the C5—N1 and C5—N4 bond lengths in 5-substituted tetrazoles, one can conclude that there is strong charge delocalization in the N1—C5—N4 fragment of (I).

The protonation at the N7 atom leads to an increase in the N7—C distances and to the angles at N7 being close to tetrahedral (Table 1). The piperidine ring adopts a chair conformation, with the H atom at N7 in the axial position, whereas the bulky substituent is located in the equatorial position.

Inspection of the packing structure of (I) reveals classical N7—H7···N4 hydrogen bonds (Table 2). These are responsible for the formation of two-membered aggregates (Fig.2), additionally stabilized by weak C9—H9B···N3 interactions (Table 2). Only non-classical hydrogen bonds (Table 2), together with van der Waals interactions, exist between the above aggregates in the structure of (I).

It should be noted that the title compound is the second structurally characterized tetrazole analogue of betaines after 5-(2'-dimethylaminoethyl)tetrazole (Chertanova et al., 1988). The main features of the tetrazole ring geometry of the latter compound are close to those found for (I).

Experimental top

The title compound was synthesized by the aminomethylation of tetrazole with piperidine and formaldehyde, according to the method described by Karavai & Gaponik (1991). The compound decomposes at 528 K. Single crystals of (I) were grown by slow evaporation in air of an ethyl alcohol solution of the title compound. Spectroscopic analysis: 1H NMR [100 MHz, (CD3)2SO, δ, p.p.m.]: 1.30–1.82 (m, 6H, 3CH2), 3.00 (t, 4H, 2CH2), 4.25 (s, 2H, CH2).

Refinement top

H-atom positions were found from the difference Fourier map and all associated parameters were refined freely. Refined C—H distances were in the range 0.95 (2)–1.01 (2) Å.

Computing details top

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) and PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The crystal structure of (I) viewed along the a axis. Dashed lines indicate classical N—H···N hydrogen bonds.
1-(1-piperidiniomethyl)-1H-tetrazolide top
Crystal data top
C7H13N5Z = 2
Mr = 167.22F(000) = 180
Triclinic, P1Dx = 1.321 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71069 Å
a = 6.1664 (10) ÅCell parameters from 25 reflections
b = 8.3913 (18) Åθ = 20.4–23.3°
c = 8.6842 (17) ŵ = 0.09 mm1
α = 90.062 (17)°T = 293 K
β = 110.351 (15)°Prism, colourless
γ = 93.176 (16)°0.50 × 0.40 × 0.38 mm
V = 420.56 (14) Å3
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.018
Radiation source: fine-focus sealed tubeθmax = 30.0°, θmin = 2.4°
Graphite monochromatorh = 08
ω/2θ scansk = 1111
2761 measured reflectionsl = 1211
2467 independent reflections3 standard reflections every 100 reflections
2118 reflections with I > 2σ(I) intensity decay: 1.7%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040Hydrogen site location: difference Fourier map
wR(F2) = 0.118All H-atom parameters refined
S = 1.06 w = 1/[σ2(Fo2) + (0.069P)2 + 0.0378P]
where P = (Fo2 + 2Fc2)/3
2467 reflections(Δ/σ)max < 0.001
161 parametersΔρmax = 0.17 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C7H13N5γ = 93.176 (16)°
Mr = 167.22V = 420.56 (14) Å3
Triclinic, P1Z = 2
a = 6.1664 (10) ÅMo Kα radiation
b = 8.3913 (18) ŵ = 0.09 mm1
c = 8.6842 (17) ÅT = 293 K
α = 90.062 (17)°0.50 × 0.40 × 0.38 mm
β = 110.351 (15)°
Data collection top
Nicolet R3m four-circle
diffractometer
Rint = 0.018
2761 measured reflections3 standard reflections every 100 reflections
2467 independent reflections intensity decay: 1.7%
2118 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0400 restraints
wR(F2) = 0.118All H-atom parameters refined
S = 1.06Δρmax = 0.17 e Å3
2467 reflectionsΔρmin = 0.26 e Å3
161 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
N10.23825 (15)0.61929 (11)0.80123 (10)0.0448 (2)
N20.41908 (15)0.68757 (11)0.69104 (11)0.0479 (2)
N30.38644 (14)0.69921 (10)0.55060 (10)0.0438 (2)
N40.18145 (13)0.63976 (9)0.56555 (9)0.03756 (19)
C50.09640 (14)0.59166 (10)0.71974 (9)0.03267 (18)
C60.12905 (14)0.51840 (11)0.79597 (10)0.03540 (19)
H6A0.252 (2)0.5757 (14)0.7671 (15)0.045 (3)*
H6B0.172 (2)0.5195 (14)0.9139 (15)0.039 (3)*
N70.12534 (11)0.34779 (9)0.74078 (8)0.03126 (17)
H70.120 (2)0.3488 (16)0.6309 (17)0.050 (3)*
C80.35021 (15)0.27820 (12)0.83978 (11)0.0392 (2)
H8A0.363 (2)0.2864 (14)0.9580 (15)0.045 (3)*
H8B0.474 (2)0.3495 (16)0.8234 (16)0.051 (3)*
C90.35742 (17)0.10701 (13)0.78682 (13)0.0464 (2)
H9A0.507 (2)0.0668 (18)0.8596 (18)0.062 (4)*
H9B0.363 (2)0.1039 (15)0.6761 (16)0.050 (3)*
C100.1508 (2)0.00404 (14)0.79440 (17)0.0559 (3)
H10A0.162 (3)0.0057 (19)0.914 (2)0.068 (4)*
H10B0.150 (3)0.106 (2)0.758 (2)0.075 (5)*
C110.07294 (18)0.07791 (13)0.69544 (15)0.0495 (2)
H11A0.094 (2)0.0780 (17)0.5764 (19)0.058 (4)*
H11B0.208 (3)0.0136 (19)0.7034 (19)0.067 (4)*
C120.07836 (14)0.24810 (11)0.75148 (12)0.0377 (2)
H12A0.071 (2)0.2549 (15)0.8652 (16)0.045 (3)*
H12B0.216 (2)0.2989 (14)0.6819 (15)0.041 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0507 (5)0.0569 (5)0.0382 (4)0.0096 (4)0.0290 (4)0.0065 (3)
N20.0469 (4)0.0559 (5)0.0523 (5)0.0098 (4)0.0306 (4)0.0087 (4)
N30.0402 (4)0.0527 (5)0.0424 (4)0.0060 (3)0.0189 (3)0.0074 (3)
N40.0381 (4)0.0491 (4)0.0300 (3)0.0030 (3)0.0174 (3)0.0039 (3)
C50.0365 (4)0.0378 (4)0.0284 (3)0.0021 (3)0.0180 (3)0.0001 (3)
C60.0340 (4)0.0430 (4)0.0298 (4)0.0030 (3)0.0127 (3)0.0015 (3)
N70.0283 (3)0.0436 (4)0.0241 (3)0.0011 (3)0.0121 (2)0.0016 (2)
C80.0285 (4)0.0571 (5)0.0324 (4)0.0046 (3)0.0107 (3)0.0056 (3)
C90.0413 (5)0.0565 (6)0.0460 (5)0.0150 (4)0.0192 (4)0.0118 (4)
C100.0563 (6)0.0474 (6)0.0697 (7)0.0086 (5)0.0284 (6)0.0137 (5)
C110.0430 (5)0.0452 (5)0.0607 (6)0.0031 (4)0.0196 (5)0.0053 (4)
C120.0299 (4)0.0449 (4)0.0408 (4)0.0020 (3)0.0162 (3)0.0006 (3)
Geometric parameters (Å, º) top
N1—C51.3313 (11)C8—H8A1.004 (13)
N1—N21.3480 (13)C8—H8B0.994 (14)
N2—N31.3062 (12)C9—C101.5203 (16)
N3—N41.3489 (11)C9—H9A0.995 (15)
N4—C51.3293 (11)C9—H9B0.975 (14)
C5—C61.4847 (12)C10—C111.5156 (16)
C6—N71.5058 (12)C10—H10A1.018 (17)
C6—H6A0.979 (13)C10—H10B0.978 (17)
C6—H6B0.965 (12)C11—C121.5141 (14)
N7—C121.5003 (11)C11—H11A0.996 (15)
N7—C81.5048 (11)C11—H11B0.988 (16)
N7—H70.943 (14)C12—H12A0.974 (13)
C8—C91.5156 (15)C12—H12B0.975 (12)
C5—N1—N2104.73 (7)C8—C9—C10111.64 (9)
N3—N2—N1109.69 (8)C8—C9—H9A107.3 (9)
N2—N3—N4108.96 (8)C10—C9—H9A111.7 (9)
C5—N4—N3105.17 (7)C8—C9—H9B109.9 (8)
N4—C5—N1111.45 (8)C10—C9—H9B110.3 (8)
N4—C5—C6125.48 (7)H9A—C9—H9B105.9 (11)
N1—C5—C6123.06 (7)C11—C10—C9110.14 (9)
C5—C6—N7113.13 (7)C11—C10—H10A110.1 (9)
C5—C6—H6A111.2 (7)C9—C10—H10A109.1 (9)
N7—C6—H6A105.7 (7)C11—C10—H10B110.6 (10)
C5—C6—H6B110.0 (7)C9—C10—H10B112.8 (10)
N7—C6—H6B107.5 (7)H10A—C10—H10B104.1 (13)
H6A—C6—H6B109.1 (10)C12—C11—C10111.69 (9)
C12—N7—C8111.25 (7)C12—C11—H11A108.4 (8)
C12—N7—C6112.71 (7)C10—C11—H11A110.9 (8)
C8—N7—C6109.07 (7)C12—C11—H11B109.6 (9)
C12—N7—H7109.4 (8)C10—C11—H11B110.5 (9)
C8—N7—H7106.6 (8)H11A—C11—H11B105.6 (12)
C6—N7—H7107.6 (8)N7—C12—C11110.50 (8)
N7—C8—C9111.24 (8)N7—C12—H12A106.9 (7)
N7—C8—H8A106.5 (7)C11—C12—H12A112.3 (7)
C9—C8—H8A111.7 (7)N7—C12—H12B106.1 (7)
N7—C8—H8B105.8 (7)C11—C12—H12B111.8 (7)
C9—C8—H8B112.5 (8)H12A—C12—H12B109.0 (10)
H8A—C8—H8B108.7 (10)
C5—N1—N2—N30.27 (11)C5—C6—N7—C8173.00 (6)
N1—N2—N3—N40.50 (11)C12—N7—C8—C956.12 (9)
N2—N3—N4—C50.51 (10)C6—N7—C8—C9178.94 (7)
N3—N4—C5—N10.35 (10)N7—C8—C9—C1055.01 (11)
N3—N4—C5—C6179.44 (8)C8—C9—C10—C1154.36 (13)
N2—N1—C5—N40.06 (11)C9—C10—C11—C1255.55 (13)
N2—N1—C5—C6179.18 (8)C8—N7—C12—C1156.86 (10)
N4—C5—C6—N774.86 (10)C6—N7—C12—C11179.73 (7)
N1—C5—C6—N7106.15 (9)C10—C11—C12—N757.06 (12)
C5—C6—N7—C1248.92 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7—H7···N4i0.943 (14)1.874 (14)2.8007 (11)166.9 (11)
C9—H9B···N3i0.975 (14)2.608 (13)3.4067 (15)139.3 (10)
C6—H6A···N2ii0.979 (13)2.482 (13)3.4555 (13)172.9 (10)
C12—H12B···N3iii0.975 (12)2.579 (12)3.4801 (14)153.7 (9)
C8—H8A···N1iv1.004 (13)2.602 (13)3.5345 (13)154.5 (9)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z; (iii) x1, y+1, z+1; (iv) x, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC7H13N5
Mr167.22
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)6.1664 (10), 8.3913 (18), 8.6842 (17)
α, β, γ (°)90.062 (17), 110.351 (15), 93.176 (16)
V3)420.56 (14)
Z2
Radiation typeMo Kα
µ (mm1)0.09
Crystal size (mm)0.50 × 0.40 × 0.38
Data collection
DiffractometerNicolet R3m four-circle
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2761, 2467, 2118
Rint0.018
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.118, 1.06
No. of reflections2467
No. of parameters161
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.17, 0.26

Computer programs: R3m Software (Nicolet, 1980), R3m Software, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 1999), SHELXL97.

Selected geometric parameters (Å, º) top
N1—C51.3313 (11)N4—C51.3293 (11)
N1—N21.3480 (13)C6—N71.5058 (12)
N2—N31.3062 (12)N7—C121.5003 (11)
N3—N41.3489 (11)N7—C81.5048 (11)
C5—N1—N2104.73 (7)C12—N7—C8111.25 (7)
N3—N2—N1109.69 (8)C12—N7—C6112.71 (7)
N2—N3—N4108.96 (8)C8—N7—C6109.07 (7)
C5—N4—N3105.17 (7)C12—N7—H7109.4 (8)
N4—C5—N1111.45 (8)C8—N7—H7106.6 (8)
N4—C5—C6125.48 (7)C6—N7—H7107.6 (8)
N1—C5—C6123.06 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7—H7···N4i0.943 (14)1.874 (14)2.8007 (11)166.9 (11)
C9—H9B···N3i0.975 (14)2.608 (13)3.4067 (15)139.3 (10)
C6—H6A···N2ii0.979 (13)2.482 (13)3.4555 (13)172.9 (10)
C12—H12B···N3iii0.975 (12)2.579 (12)3.4801 (14)153.7 (9)
C8—H8A···N1iv1.004 (13)2.602 (13)3.5345 (13)154.5 (9)
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y, z; (iii) x1, y+1, z+1; (iv) x, y+1, z+2.
 

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