organic compounds
Piperidine-1-carboximidamide
aFakultät Chemie/Organische Chemie, Hochschule Aalen, Beethovenstrasse 1, D-73430 Aalen, Germany
*Correspondence e-mail: Ioannis.Tiritiris@htw-aalen.de
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 ). For the of bis(piperidin-1-yl)methanone, see: Betz et al. (2011).
of 4-morpholinecarboxamidine, see: Tiritiris (2012Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; 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.
Supporting information
10.1107/S1600536812044467/go2073sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812044467/go2073Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812044467/go2073Isup3.cml
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 (C═N).
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
in the riding model approximation, with U(H) set to 1.2 Ueq(C).Data collection: APEX2 (Bruker, 2008); cell
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).C6H13N3 | F(000) = 280 |
Mr = 127.19 | Dx = 1.182 Mg m−3 |
Monoclinic, P21/c | Melting point: 409 K |
Hall symbol: -P 2ybc | Cu Kα radiation, λ = 1.54178 Å |
a = 12.2193 (9) Å | Cell parameters from 4190 reflections |
b = 5.5784 (5) Å | θ = 3.6–73.5° |
c = 10.4885 (7) Å | µ = 0.60 mm−1 |
β = 91.887 (4)° | T = 100 K |
V = 714.55 (10) Å3 | Plate, colorless |
Z = 4 | 0.45 × 0.26 × 0.06 mm |
Bruker Kappa APEXII DUO diffractometer | 1413 independent reflections |
Radiation source: sealed tube | 1116 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.049 |
ϕ scans, and ω scans | θmax = 73.5°, θmin = 3.6° |
Absorption correction: multi-scan (Blessing, 1995) | h = −15→15 |
Tmin = 0.830, Tmax = 0.965 | k = −6→6 |
4190 measured reflections | l = −12→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.045 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.112 | H 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 parameters | Δρmax = 0.19 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C6H13N3 | V = 714.55 (10) Å3 |
Mr = 127.19 | Z = 4 |
Monoclinic, P21/c | Cu Kα radiation |
a = 12.2193 (9) Å | µ = 0.60 mm−1 |
b = 5.5784 (5) Å | T = 100 K |
c = 10.4885 (7) Å | 0.45 × 0.26 × 0.06 mm |
β = 91.887 (4)° |
Bruker Kappa APEXII DUO diffractometer | 1413 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 1116 reflections with I > 2σ(I) |
Tmin = 0.830, Tmax = 0.965 | Rint = 0.049 |
4190 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.19 e Å−3 |
1413 reflections | Δρmin = −0.21 e Å−3 |
94 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.38570 (11) | 0.2272 (2) | 0.20721 (12) | 0.0194 (3) | |
N1 | 0.41982 (10) | 0.26476 (18) | 0.32513 (11) | 0.0229 (3) | |
H11 | 0.4665 (14) | 0.393 (3) | 0.3256 (16) | 0.031 (4)* | |
N2 | 0.40843 (11) | 0.37432 (19) | 0.10763 (12) | 0.0248 (3) | |
H21 | 0.4040 (14) | 0.315 (3) | 0.0240 (18) | 0.037 (4)* | |
H22 | 0.4598 (14) | 0.497 (3) | 0.1251 (15) | 0.035 (4)* | |
N3 | 0.32466 (10) | 0.02529 (17) | 0.17918 (10) | 0.0225 (3) | |
C2 | 0.25890 (12) | −0.0007 (2) | 0.06138 (13) | 0.0270 (4) | |
H2A | 0.2591 | −0.1706 | 0.0341 | 0.032* | |
H2B | 0.2915 | 0.0964 | −0.0067 | 0.032* | |
C3 | 0.14128 (12) | 0.0807 (2) | 0.08029 (14) | 0.0279 (4) | |
H3A | 0.1403 | 0.2540 | 0.1006 | 0.034* | |
H3B | 0.0972 | 0.0553 | 0.0005 | 0.034* | |
C4 | 0.09150 (13) | −0.0602 (2) | 0.18847 (14) | 0.0275 (3) | |
H4A | 0.0179 | 0.0040 | 0.2054 | 0.033* | |
H4B | 0.0833 | −0.2304 | 0.1631 | 0.033* | |
C5 | 0.16364 (12) | −0.0434 (2) | 0.30906 (14) | 0.0273 (4) | |
H5A | 0.1341 | −0.1493 | 0.3754 | 0.033* | |
H5B | 0.1629 | 0.1231 | 0.3416 | 0.033* | |
C6 | 0.28172 (12) | −0.1171 (2) | 0.28289 (13) | 0.0246 (3) | |
H6A | 0.3282 | −0.0937 | 0.3610 | 0.030* | |
H6B | 0.2837 | −0.2892 | 0.2600 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0203 (7) | 0.0167 (6) | 0.0211 (7) | 0.0021 (4) | 0.0004 (5) | −0.0011 (4) |
N1 | 0.0271 (7) | 0.0187 (5) | 0.0228 (6) | −0.0023 (4) | −0.0013 (5) | −0.0015 (4) |
N2 | 0.0335 (7) | 0.0211 (5) | 0.0196 (6) | −0.0053 (5) | −0.0011 (5) | −0.0009 (4) |
N3 | 0.0256 (7) | 0.0203 (5) | 0.0214 (6) | −0.0032 (4) | −0.0036 (5) | 0.0001 (4) |
C2 | 0.0329 (9) | 0.0261 (6) | 0.0218 (7) | −0.0065 (5) | −0.0021 (6) | −0.0037 (5) |
C3 | 0.0309 (9) | 0.0274 (6) | 0.0249 (8) | −0.0016 (6) | −0.0091 (6) | 0.0017 (5) |
C4 | 0.0261 (8) | 0.0268 (7) | 0.0295 (8) | 0.0009 (5) | −0.0013 (6) | −0.0002 (5) |
C5 | 0.0313 (9) | 0.0251 (6) | 0.0254 (8) | −0.0022 (5) | 0.0012 (6) | 0.0016 (5) |
C6 | 0.0292 (8) | 0.0197 (6) | 0.0247 (7) | −0.0019 (5) | −0.0040 (6) | 0.0048 (5) |
C1—N1 | 1.3090 (17) | C3—C4 | 1.5235 (19) |
C1—N2 | 1.3640 (17) | C3—H3A | 0.9900 |
C1—N3 | 1.3773 (16) | C3—H3B | 0.9900 |
N1—H11 | 0.913 (17) | C4—C5 | 1.521 (2) |
N2—H21 | 0.937 (18) | C4—H4A | 0.9900 |
N2—H22 | 0.943 (17) | C4—H4B | 0.9900 |
N3—C6 | 1.4585 (17) | C5—C6 | 1.534 (2) |
N3—C2 | 1.4587 (17) | C5—H5A | 0.9900 |
C2—C3 | 1.526 (2) | C5—H5B | 0.9900 |
C2—H2A | 0.9900 | C6—H6A | 0.9900 |
C2—H2B | 0.9900 | C6—H6B | 0.9900 |
N1—C1—N2 | 124.09 (11) | C2—C3—H3B | 109.6 |
N1—C1—N3 | 119.08 (11) | H3A—C3—H3B | 108.2 |
N2—C1—N3 | 116.82 (12) | C5—C4—C3 | 110.67 (12) |
C1—N1—H11 | 108.1 (11) | C5—C4—H4A | 109.5 |
C1—N2—H21 | 119.8 (10) | C3—C4—H4A | 109.5 |
C1—N2—H22 | 116.1 (10) | C5—C4—H4B | 109.5 |
H21—N2—H22 | 117.2 (14) | C3—C4—H4B | 109.5 |
C1—N3—C6 | 119.46 (11) | H4A—C4—H4B | 108.1 |
C1—N3—C2 | 122.78 (10) | C4—C5—C6 | 110.95 (12) |
C6—N3—C2 | 112.09 (10) | C4—C5—H5A | 109.4 |
N3—C2—C3 | 110.80 (11) | C6—C5—H5A | 109.4 |
N3—C2—H2A | 109.5 | C4—C5—H5B | 109.4 |
C3—C2—H2A | 109.5 | C6—C5—H5B | 109.4 |
N3—C2—H2B | 109.5 | H5A—C5—H5B | 108.0 |
C3—C2—H2B | 109.5 | N3—C6—C5 | 110.55 (11) |
H2A—C2—H2B | 108.1 | N3—C6—H6A | 109.5 |
C4—C3—C2 | 110.12 (11) | C5—C6—H6A | 109.5 |
C4—C3—H3A | 109.6 | N3—C6—H6B | 109.5 |
C2—C3—H3A | 109.6 | C5—C6—H6B | 109.5 |
C4—C3—H3B | 109.6 | H6A—C6—H6B | 108.1 |
N1—C1—N3—C6 | 11.63 (18) | N3—C2—C3—C4 | −56.89 (14) |
N2—C1—N3—C6 | −169.57 (11) | C2—C3—C4—C5 | 53.91 (15) |
N1—C1—N3—C2 | 162.94 (12) | C3—C4—C5—C6 | −53.30 (14) |
N2—C1—N3—C2 | −18.25 (18) | C1—N3—C6—C5 | 95.35 (14) |
C1—N3—C2—C3 | −93.09 (14) | C2—N3—C6—C5 | −58.83 (14) |
C6—N3—C2—C3 | 60.10 (13) | C4—C5—C6—N3 | 55.17 (13) |
D—H···A | D—H | H···A | D···A | 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+1/2, z−1/2; (ii) −x+1, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C6H13N3 |
Mr | 127.19 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 100 |
a, b, c (Å) | 12.2193 (9), 5.5784 (5), 10.4885 (7) |
β (°) | 91.887 (4) |
V (Å3) | 714.55 (10) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.60 |
Crystal size (mm) | 0.45 × 0.26 × 0.06 |
Data collection | |
Diffractometer | Bruker Kappa APEXII DUO diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.830, 0.965 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4190, 1413, 1116 |
Rint | 0.049 |
(sin θ/λ)max (Å−1) | 0.622 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.112, 1.03 |
No. of reflections | 1413 |
No. of parameters | 94 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.21 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2005).
D—H···A | D—H | H···A | D···A | 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+1/2, z−1/2; (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
Betz, R., Gerber, T. & Schalekamp, H. (2011). Acta Cryst. E67, o397. Web of Science CSD CrossRef IUCr Journals Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Brandenburg, K. & Putz, H. (2005). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tiritiris, I. (2012). Acta Cryst. E68, o3118. CSD CrossRef IUCr Journals Google Scholar
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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.