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ISSN: 2056-9890

Piperidine-1-carboximidamide

aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: Ioannis.Tiritiris@htw-aalen.de

(Received 25 October 2012; accepted 26 October 2012; online 31 October 2012)

In the title compound, C6H13N3, the C=N and C—N bond lengths in the CN3 unit are 1.3090 (17), and 1.3640 (17) (C–NH2) and 1.3773 (16) Å, indicating double- and single-bond character, respectively. The N—C—N angles are 116.82 (12), 119.08 (11) and 124.09 (11)°, showing a deviation of the CN3 plane from an ideal trigonal–planar geometry. The piperidine ring is in a chair conformation. In the crystal, mol­ecules are linked by N—H⋯N hydrogen bonds, forming a two-dimensional network along the ac plane.

Related literature

For the crystal structure of 4-morpholine­carboxamidine, see: Tiritiris (2012[Tiritiris, I. (2012). Acta Cryst. E68, o3118.]). For the crystal structure of bis­(piperidin-1-yl)methanone, see: Betz et al. (2011[Betz, R., Gerber, T. & Schalekamp, H. (2011). Acta Cryst. E67, o397.]).

[Scheme 1]

Experimental

Crystal data
  • C6H13N3

  • Mr = 127.19

  • Monoclinic, P 21 /c

  • a = 12.2193 (9) Å

  • b = 5.5784 (5) Å

  • c = 10.4885 (7) Å

  • β = 91.887 (4)°

  • V = 714.55 (10) Å3

  • Z = 4

  • Cu Kα radiation

  • μ = 0.60 mm−1

  • T = 100 K

  • 0.45 × 0.26 × 0.06 mm

Data collection
  • Bruker Kappa APEXII DUO diffractometer

  • Absorption correction: multi-scan (Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]) Tmin = 0.830, Tmax = 0.965

  • 4190 measured reflections

  • 1413 independent reflections

  • 1116 reflections with I > 2σ(I)

  • Rint = 0.049

Refinement
  • R[F2 > 2σ(F2)] = 0.045

  • wR(F2) = 0.112

  • S = 1.03

  • 1413 reflections

  • 94 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.21 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N2—H21⋯N1i 0.94 (2) 2.15 (2) 3.071 (1) 168 (1)
N2—H22⋯N1ii 0.94 (2) 2.15 (2) 3.090 (1) 177 (1)
Symmetry codes: (i) [x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]; (ii) [-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg & Putz, 2005[Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

1-Piperidinecarboxamidine, a guanidine derivative bearing one piperidine moiety, is similar to the structurally known compound 4-morpholinecarboxamidine (Tiritiris, 2012). Our efforts to study guanidines for CO2 capturing, led to the preparation of the title compound. Because its crystal structure was previously unknown, it was decided to conduct an investigation. According to the structure analysis, the C1–N1 bond in the title compound is 1.3090 (17) Å, indicating double bond character. The bond lengths C1–N2 = 1.3640 (17) Å and C1–N3 = 1.3773 (16) Å are elongated and characteristic for a C–N amine single bond (Fig. 1). The N–C1–N angles are: 116.82 (12)° (N2–C1–N3), 119.08 (11)° (N1–C1–N3) and 124.09 (11)° (N1–C1–N2), showing a deviation of the CN3 plane from an ideal trigonal-planar geometry (Fig. 1). The structural parameters of the piperidine ring in the here presented title compound agree very well with the data obtained from the X-ray analysis of the urea bis(piperidin-1-yl)methanone (Betz et al., 2011). In both crystal structures the piperidine rings adopt a chair conformation. In contrast to the structure of 4-morpholinecarboxamidine (Tiritiris, 2012), only strong N—H···N hydrogen bonds between nitrogen atoms of neighboring molecules (Fig. 2 and 3) are present [d(H···N) = 2.15 (2) Å] (Tab. 1), forming an infinite two-dimensional network (base vectors [0 0 1] and [0 1 0]). Surprisingly, the imine hydrogen atom H11 is not involved in the hydrogen bonding system.

Related literature top

For the crystal structure of 4-morpholinecarboxamidine, see: Tiritiris (2012). For the crystal structure of bis(piperidin-1-yl)methanone, see: Betz et al. (2011).

Experimental top

1-Piperidine-carboxamidinium sulfate (I) was prepared by heating one equivalent O-methylisourea sulfate with two equivalents of piperidine under reflux. The methanol formed in the reaction was distilled off and (I) precipitated in nearly quantitative yield. To a solution of 5.0 g (14 mmol) (I) in 50 ml water, a solution of 1.2 g (30 mmol) sodium hydroxide dissolved in 25 ml water was added dropwise under ice cooling. After warming to room temperature the aqueous phase was extracted with diethyl ether. The organic phase was finally dried over sodium sulfate. After evaporation of the solvent, the title compound precipitated in form of a colorless solid. Yield: 1.5 g (84%). During the storage of a saturated acetonitrile solution at 0° C, colorless single crystals of the title compound suitable for X-ray analysis were obtained. 1H NMR (500 MHz, CD3CN/TMS): δ = 1.60–1.64 [m, 6 H, –CH2], 3.38–3.42 [m, 4 H,–CH2], 5.85 [s, 1 H, –NH], 6.19 [s, 2 H, –NH2]. 13C NMR (125 MHz, CD3CN/TMS): δ = 23.2 (–CH2), 24.7 (–CH2), 46.5 (–CH2), 157.4 (CN).

Refinement top

The N-bound H atoms were located in a difference Fourier map and were refined freely [N—H = 0.91 (2)–0.94 (2) Å]. The hydrogen atoms of the methylene groups were placed in calculated positions with d(C—H) = 0.99 Å. They were included in the refinement in the riding model approximation, with U(H) set to 1.2 Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with displacement ellipsoids at the 50% probability level.
[Figure 2] Fig. 2. N–H···N hydrogen bonds between neighboring molecules, ac-view. The hydrogen bonds are indicated by dashed lines.
[Figure 3] Fig. 3. N–H···N hydrogen bonds generating a two-dimensional network, ac-view. The hydrogen bonds are indicated by dashed lines.
Piperidine-1-carboximidamide top
Crystal data top
C6H13N3F(000) = 280
Mr = 127.19Dx = 1.182 Mg m3
Monoclinic, P21/cMelting point: 409 K
Hall symbol: -P 2ybcCu Kα radiation, λ = 1.54178 Å
a = 12.2193 (9) ÅCell parameters from 4190 reflections
b = 5.5784 (5) Åθ = 3.6–73.5°
c = 10.4885 (7) ŵ = 0.60 mm1
β = 91.887 (4)°T = 100 K
V = 714.55 (10) Å3Plate, colorless
Z = 40.45 × 0.26 × 0.06 mm
Data collection top
Bruker Kappa APEXII DUO
diffractometer
1413 independent reflections
Radiation source: sealed tube1116 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.049
ϕ scans, and ω scansθmax = 73.5°, θmin = 3.6°
Absorption correction: multi-scan
(Blessing, 1995)
h = 1515
Tmin = 0.830, Tmax = 0.965k = 66
4190 measured reflectionsl = 1212
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)] = 0.045Hydrogen site location: difference Fourier map
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.03 w = 1/[σ2(Fo2) + (0.0625P)2]
where P = (Fo2 + 2Fc2)/3
1413 reflections(Δ/σ)max < 0.001
94 parametersΔρmax = 0.19 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C6H13N3V = 714.55 (10) Å3
Mr = 127.19Z = 4
Monoclinic, P21/cCu Kα radiation
a = 12.2193 (9) ŵ = 0.60 mm1
b = 5.5784 (5) ÅT = 100 K
c = 10.4885 (7) Å0.45 × 0.26 × 0.06 mm
β = 91.887 (4)°
Data collection top
Bruker Kappa APEXII DUO
diffractometer
1413 independent reflections
Absorption correction: multi-scan
(Blessing, 1995)
1116 reflections with I > 2σ(I)
Tmin = 0.830, Tmax = 0.965Rint = 0.049
4190 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.03Δρmax = 0.19 e Å3
1413 reflectionsΔρmin = 0.21 e Å3
94 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
C10.38570 (11)0.2272 (2)0.20721 (12)0.0194 (3)
N10.41982 (10)0.26476 (18)0.32513 (11)0.0229 (3)
H110.4665 (14)0.393 (3)0.3256 (16)0.031 (4)*
N20.40843 (11)0.37432 (19)0.10763 (12)0.0248 (3)
H210.4040 (14)0.315 (3)0.0240 (18)0.037 (4)*
H220.4598 (14)0.497 (3)0.1251 (15)0.035 (4)*
N30.32466 (10)0.02529 (17)0.17918 (10)0.0225 (3)
C20.25890 (12)0.0007 (2)0.06138 (13)0.0270 (4)
H2A0.25910.17060.03410.032*
H2B0.29150.09640.00670.032*
C30.14128 (12)0.0807 (2)0.08029 (14)0.0279 (4)
H3A0.14030.25400.10060.034*
H3B0.09720.05530.00050.034*
C40.09150 (13)0.0602 (2)0.18847 (14)0.0275 (3)
H4A0.01790.00400.20540.033*
H4B0.08330.23040.16310.033*
C50.16364 (12)0.0434 (2)0.30906 (14)0.0273 (4)
H5A0.13410.14930.37540.033*
H5B0.16290.12310.34160.033*
C60.28172 (12)0.1171 (2)0.28289 (13)0.0246 (3)
H6A0.32820.09370.36100.030*
H6B0.28370.28920.26000.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0203 (7)0.0167 (6)0.0211 (7)0.0021 (4)0.0004 (5)0.0011 (4)
N10.0271 (7)0.0187 (5)0.0228 (6)0.0023 (4)0.0013 (5)0.0015 (4)
N20.0335 (7)0.0211 (5)0.0196 (6)0.0053 (5)0.0011 (5)0.0009 (4)
N30.0256 (7)0.0203 (5)0.0214 (6)0.0032 (4)0.0036 (5)0.0001 (4)
C20.0329 (9)0.0261 (6)0.0218 (7)0.0065 (5)0.0021 (6)0.0037 (5)
C30.0309 (9)0.0274 (6)0.0249 (8)0.0016 (6)0.0091 (6)0.0017 (5)
C40.0261 (8)0.0268 (7)0.0295 (8)0.0009 (5)0.0013 (6)0.0002 (5)
C50.0313 (9)0.0251 (6)0.0254 (8)0.0022 (5)0.0012 (6)0.0016 (5)
C60.0292 (8)0.0197 (6)0.0247 (7)0.0019 (5)0.0040 (6)0.0048 (5)
Geometric parameters (Å, º) top
C1—N11.3090 (17)C3—C41.5235 (19)
C1—N21.3640 (17)C3—H3A0.9900
C1—N31.3773 (16)C3—H3B0.9900
N1—H110.913 (17)C4—C51.521 (2)
N2—H210.937 (18)C4—H4A0.9900
N2—H220.943 (17)C4—H4B0.9900
N3—C61.4585 (17)C5—C61.534 (2)
N3—C21.4587 (17)C5—H5A0.9900
C2—C31.526 (2)C5—H5B0.9900
C2—H2A0.9900C6—H6A0.9900
C2—H2B0.9900C6—H6B0.9900
N1—C1—N2124.09 (11)C2—C3—H3B109.6
N1—C1—N3119.08 (11)H3A—C3—H3B108.2
N2—C1—N3116.82 (12)C5—C4—C3110.67 (12)
C1—N1—H11108.1 (11)C5—C4—H4A109.5
C1—N2—H21119.8 (10)C3—C4—H4A109.5
C1—N2—H22116.1 (10)C5—C4—H4B109.5
H21—N2—H22117.2 (14)C3—C4—H4B109.5
C1—N3—C6119.46 (11)H4A—C4—H4B108.1
C1—N3—C2122.78 (10)C4—C5—C6110.95 (12)
C6—N3—C2112.09 (10)C4—C5—H5A109.4
N3—C2—C3110.80 (11)C6—C5—H5A109.4
N3—C2—H2A109.5C4—C5—H5B109.4
C3—C2—H2A109.5C6—C5—H5B109.4
N3—C2—H2B109.5H5A—C5—H5B108.0
C3—C2—H2B109.5N3—C6—C5110.55 (11)
H2A—C2—H2B108.1N3—C6—H6A109.5
C4—C3—C2110.12 (11)C5—C6—H6A109.5
C4—C3—H3A109.6N3—C6—H6B109.5
C2—C3—H3A109.6C5—C6—H6B109.5
C4—C3—H3B109.6H6A—C6—H6B108.1
N1—C1—N3—C611.63 (18)N3—C2—C3—C456.89 (14)
N2—C1—N3—C6169.57 (11)C2—C3—C4—C553.91 (15)
N1—C1—N3—C2162.94 (12)C3—C4—C5—C653.30 (14)
N2—C1—N3—C218.25 (18)C1—N3—C6—C595.35 (14)
C1—N3—C2—C393.09 (14)C2—N3—C6—C558.83 (14)
C6—N3—C2—C360.10 (13)C4—C5—C6—N355.17 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H21···N1i0.94 (2)2.15 (2)3.071 (1)168 (1)
N2—H22···N1ii0.94 (2)2.15 (2)3.090 (1)177 (1)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC6H13N3
Mr127.19
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)12.2193 (9), 5.5784 (5), 10.4885 (7)
β (°) 91.887 (4)
V3)714.55 (10)
Z4
Radiation typeCu Kα
µ (mm1)0.60
Crystal size (mm)0.45 × 0.26 × 0.06
Data collection
DiffractometerBruker Kappa APEXII DUO
diffractometer
Absorption correctionMulti-scan
(Blessing, 1995)
Tmin, Tmax0.830, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
4190, 1413, 1116
Rint0.049
(sin θ/λ)max1)0.622
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.112, 1.03
No. of reflections1413
No. of parameters94
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.19, 0.21

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H21···N1i0.94 (2)2.15 (2)3.071 (1)168 (1)
N2—H22···N1ii0.94 (2)2.15 (2)3.090 (1)177 (1)
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x+1, y+1/2, z+1/2.
 

Acknowledgements

The author thanks Dr W. Frey (Institut für Organische Chemie, Universität Stuttgart) for measuring the crystal data.

References

First citationBetz, R., Gerber, T. & Schalekamp, H. (2011). Acta Cryst. E67, o397.  Web of Science CSD CrossRef IUCr Journals
First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals
First citationBrandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany.
First citationBruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationTiritiris, I. (2012). Acta Cryst. E68, o3118.  CSD CrossRef IUCr Journals

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ISSN: 2056-9890
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