Acta Cryst. (2007). E63, o3716 [ doi:10.1107/S1600536807037877 ]
The crystal structure of the title compound, C13H23ClN5O+·Cl-, is stabilized by intermolecular N-H
Cl hydrogen bonds which help to establish the crystal packing. The piperidine ring adopts a chair conformation.
The title compound was obtained according to the method of Kaiser & Thurston (1951). 2,4,6-Trichloro-1,3,5-triazine (40.0 g, 0.217 mol) was dissolved in toluene (120 ml) and then cooled to 278 K. With stirring, a solution of 2,2,6,6-tetramethylpiperidin-4-amine(33.23 g, 0.213 mol) in toluene (50 ml) was then added dropwise to the mixture over a period of 0.5 h. Then a solution of Na2CO3 (23.02 g, 0.217 mol) in water (50 ml) was then added dropwise for 0.5 h. The mixture was stirred at 273–278 K for further 3 h. The organic layer was washed with water and then concentrated in vacuo. 4,6-dichloro-N-(2,2,6,6-tetramethylpiperidin-4-yl)-1,3,5-triazin-2-amine (60.88 g) was obtained in powder form in a yield of 85.0%. Crystals were obtained by slow evaporation of a solution of methanol.
H atoms bonded to C were positioned geometrically (C—H=0.96–0.97 Å), and refined as riding with Uiso(H)=1.2Ueq(C) or 1.5eq(Cmethyl). The methyl groups were allowed to rotate but not to tip. H atoms bonded to N were freely refined.
Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
![[Figure 1]](./bt2461fig1thm.gif)
| Fig. 1. A view of the molecular structure of the title compound. Displacement ellopsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii. |
| C13H23ClN5O+·Cl– | F000 = 712 |
| Mr = 336.26 | Dx = 1.309 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation λ = 0.71073 Å |
| a = 7.7987 (16) Å | Cell parameters from 2231 reflections |
| b = 8.9425 (18) Å | θ = 2.3–25.0º |
| c = 24.472 (5) Å | µ = 0.39 mm−1 |
| β = 90.36 (3)º | T = 113 (2) K |
| V = 1706.7 (6) Å3 | Block, colorless |
| Z = 4 | 0.30 × 0.26 × 0.22 mm |
| Rigaku Saturn diffractometer | 3338 independent reflections |
| Radiation source: rotating anode | 3184 reflections with I > 2σ(I) |
| Monochromator: confocal | Rint = 0.026 |
| T = 113(2) K | θmax = 26.0º |
| ω and φ scans | θmin = 1.7º |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | h = −9→9 |
| Tmin = 0.893, Tmax = 0.920 | k = −11→10 |
| 13533 measured reflections | l = −30→30 |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.041 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0422P)2 + 1.4811P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.08 | (Δ/σ)max = 0.003 |
| 3338 reflections | Δρmax = 0.73 e Å−3 |
| 207 parameters | Δρmin = −0.38 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C13H23ClN5O+·Cl– | V = 1706.7 (6) Å3 |
| Mr = 336.26 | Z = 4 |
| Monoclinic, P21/n | Mo Kα |
| a = 7.7987 (16) Å | µ = 0.39 mm−1 |
| b = 8.9425 (18) Å | T = 113 (2) K |
| c = 24.472 (5) Å | 0.30 × 0.26 × 0.22 mm |
| β = 90.36 (3)º |
| Rigaku Saturn diffractometer | 3338 independent reflections |
| Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005) | 3184 reflections with I > 2σ(I) |
| Tmin = 0.893, Tmax = 0.920 | Rint = 0.026 |
| 13533 measured reflections |
| R[F2 > 2σ(F2)] = 0.041 | 207 parameters |
| wR(F2) = 0.100 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.08 | Δρmax = 0.73 e Å−3 |
| 3338 reflections | Δρmin = −0.38 e Å−3 |
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 > 2sigma(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 | ||
| Cl1 | 0.81987 (7) | 1.44507 (5) | 0.04206 (2) | 0.02810 (15) | |
| O1 | 0.8043 (2) | 0.94806 (17) | −0.03288 (6) | 0.0332 (4) | |
| C1 | 0.7679 (3) | 0.7961 (3) | −0.03155 (10) | 0.0363 (5) | |
| H1A | 0.8330 | 0.7497 | −0.0028 | 0.054* | |
| H1B | 0.7979 | 0.7517 | −0.0659 | 0.054* | |
| H1C | 0.6477 | 0.7818 | −0.0251 | 0.054* | |
| Cl2 | 0.39494 (7) | 0.25965 (5) | 0.22079 (2) | 0.02840 (15) | |
| N1 | 0.6796 (2) | 1.21886 (18) | 0.09038 (7) | 0.0225 (4) | |
| N2 | 0.8057 (2) | 1.17694 (19) | 0.00360 (7) | 0.0248 (4) | |
| N3 | 0.6822 (2) | 0.97133 (19) | 0.05197 (7) | 0.0232 (4) | |
| N4 | 0.5635 (2) | 1.02010 (19) | 0.13604 (7) | 0.0225 (4) | |
| H4 | 0.533 (3) | 1.085 (3) | 0.1578 (10) | 0.031 (6)* | |
| N5 | 0.3789 (2) | 0.61101 (18) | 0.20083 (6) | 0.0158 (3) | |
| C2 | 0.7615 (3) | 1.0330 (2) | 0.00984 (8) | 0.0239 (4) | |
| C3 | 0.7600 (2) | 1.2577 (2) | 0.04591 (8) | 0.0219 (4) | |
| C4 | 0.6431 (2) | 1.0695 (2) | 0.09169 (8) | 0.0215 (4) | |
| C5 | 0.5324 (2) | 0.8625 (2) | 0.14724 (7) | 0.0189 (4) | |
| H5 | 0.6095 | 0.8027 | 0.1245 | 0.023* | |
| C6 | 0.5720 (2) | 0.8292 (2) | 0.20701 (8) | 0.0203 (4) | |
| H6A | 0.4947 | 0.8863 | 0.2298 | 0.024* | |
| H6B | 0.6881 | 0.8612 | 0.2153 | 0.024* | |
| C7 | 0.5540 (2) | 0.6633 (2) | 0.22059 (7) | 0.0178 (4) | |
| C8 | 0.6969 (2) | 0.5703 (2) | 0.19527 (8) | 0.0236 (4) | |
| H8A | 0.6676 | 0.4661 | 0.1972 | 0.035* | |
| H8B | 0.8021 | 0.5875 | 0.2149 | 0.035* | |
| H8C | 0.7111 | 0.5986 | 0.1577 | 0.035* | |
| C9 | 0.5543 (3) | 0.6403 (2) | 0.28253 (8) | 0.0254 (4) | |
| H9A | 0.4610 | 0.6952 | 0.2983 | 0.038* | |
| H9B | 0.6608 | 0.6756 | 0.2976 | 0.038* | |
| H9C | 0.5413 | 0.5359 | 0.2905 | 0.038* | |
| C10 | 0.3192 (2) | 0.6498 (2) | 0.14307 (7) | 0.0187 (4) | |
| C11 | 0.4114 (3) | 0.5538 (2) | 0.10096 (8) | 0.0259 (4) | |
| H11A | 0.3499 | 0.5574 | 0.0669 | 0.039* | |
| H11B | 0.4167 | 0.4523 | 0.1136 | 0.039* | |
| H11C | 0.5255 | 0.5912 | 0.0959 | 0.039* | |
| C12 | 0.1282 (3) | 0.6144 (2) | 0.14119 (9) | 0.0301 (5) | |
| H12A | 0.0703 | 0.6708 | 0.1689 | 0.045* | |
| H12B | 0.1113 | 0.5095 | 0.1475 | 0.045* | |
| H12C | 0.0826 | 0.6405 | 0.1059 | 0.045* | |
| C13 | 0.3487 (2) | 0.8168 (2) | 0.13443 (8) | 0.0199 (4) | |
| H13A | 0.3221 | 0.8421 | 0.0968 | 0.024* | |
| H13B | 0.2715 | 0.8727 | 0.1577 | 0.024* | |
| H5A | 0.375 (3) | 0.516 (3) | 0.2050 (8) | 0.020 (5)* | |
| H5B | 0.307 (3) | 0.649 (3) | 0.2227 (10) | 0.030 (6)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Cl1 | 0.0336 (3) | 0.0207 (3) | 0.0301 (3) | −0.00790 (19) | 0.0058 (2) | 0.00253 (18) |
| O1 | 0.0408 (9) | 0.0347 (9) | 0.0240 (7) | 0.0047 (7) | 0.0050 (6) | 0.0038 (6) |
| C1 | 0.0308 (12) | 0.0306 (12) | 0.0474 (14) | 0.0022 (9) | −0.0033 (10) | −0.0169 (10) |
| Cl2 | 0.0318 (3) | 0.0169 (2) | 0.0367 (3) | −0.00237 (18) | 0.0135 (2) | 0.00176 (19) |
| N1 | 0.0243 (8) | 0.0185 (8) | 0.0247 (8) | −0.0038 (6) | 0.0008 (7) | 0.0033 (6) |
| N2 | 0.0283 (9) | 0.0219 (8) | 0.0243 (8) | −0.0009 (7) | 0.0002 (7) | 0.0019 (7) |
| N3 | 0.0235 (8) | 0.0236 (8) | 0.0225 (8) | −0.0002 (7) | −0.0005 (7) | 0.0036 (7) |
| N4 | 0.0292 (9) | 0.0151 (8) | 0.0233 (8) | −0.0030 (7) | 0.0054 (7) | 0.0011 (7) |
| N5 | 0.0155 (7) | 0.0135 (8) | 0.0183 (8) | −0.0011 (6) | 0.0021 (6) | 0.0013 (6) |
| C2 | 0.0261 (10) | 0.0256 (10) | 0.0199 (9) | 0.0036 (8) | −0.0035 (8) | −0.0008 (8) |
| C3 | 0.0210 (9) | 0.0217 (10) | 0.0230 (10) | −0.0031 (7) | −0.0023 (8) | 0.0040 (7) |
| C4 | 0.0192 (9) | 0.0223 (10) | 0.0230 (9) | −0.0017 (7) | −0.0015 (7) | 0.0042 (8) |
| C5 | 0.0212 (9) | 0.0146 (9) | 0.0209 (9) | −0.0018 (7) | 0.0020 (7) | 0.0026 (7) |
| C6 | 0.0208 (9) | 0.0180 (9) | 0.0222 (9) | −0.0048 (7) | −0.0042 (7) | −0.0002 (7) |
| C7 | 0.0148 (8) | 0.0186 (9) | 0.0200 (9) | −0.0029 (7) | −0.0024 (7) | 0.0008 (7) |
| C8 | 0.0177 (9) | 0.0234 (10) | 0.0298 (10) | 0.0020 (7) | 0.0013 (8) | 0.0048 (8) |
| C9 | 0.0292 (10) | 0.0259 (10) | 0.0210 (10) | 0.0000 (8) | −0.0049 (8) | 0.0031 (8) |
| C10 | 0.0181 (9) | 0.0201 (9) | 0.0180 (9) | −0.0031 (7) | −0.0030 (7) | 0.0005 (7) |
| C11 | 0.0342 (11) | 0.0228 (10) | 0.0208 (9) | −0.0035 (8) | −0.0005 (8) | −0.0055 (8) |
| C12 | 0.0205 (10) | 0.0339 (11) | 0.0357 (12) | −0.0081 (9) | −0.0062 (9) | 0.0021 (9) |
| C13 | 0.0208 (9) | 0.0191 (9) | 0.0197 (9) | 0.0005 (7) | −0.0032 (7) | 0.0034 (7) |
| Cl1—C3 | 1.742 (2) | C6—C7 | 1.527 (3) |
| O1—C2 | 1.336 (2) | C6—H6A | 0.9700 |
| O1—C1 | 1.389 (3) | C6—H6B | 0.9700 |
| C1—H1A | 0.9600 | C7—C8 | 1.525 (3) |
| C1—H1B | 0.9600 | C7—C9 | 1.530 (3) |
| C1—H1C | 0.9600 | C8—H8A | 0.9600 |
| N1—C3 | 1.307 (3) | C8—H8B | 0.9600 |
| N1—C4 | 1.366 (2) | C8—H8C | 0.9600 |
| N2—C3 | 1.313 (3) | C9—H9A | 0.9600 |
| N2—C2 | 1.341 (3) | C9—H9B | 0.9600 |
| N3—C2 | 1.326 (3) | C9—H9C | 0.9600 |
| N3—C4 | 1.346 (3) | C10—C12 | 1.523 (3) |
| N4—C4 | 1.329 (2) | C10—C11 | 1.525 (3) |
| N4—C5 | 1.456 (2) | C10—C13 | 1.526 (3) |
| N4—H4 | 0.82 (3) | C11—H11A | 0.9600 |
| N5—C7 | 1.520 (2) | C11—H11B | 0.9600 |
| N5—C10 | 1.525 (2) | C11—H11C | 0.9600 |
| N5—H5A | 0.86 (2) | C12—H12A | 0.9600 |
| N5—H5B | 0.85 (3) | C12—H12B | 0.9600 |
| C5—C13 | 1.521 (3) | C12—H12C | 0.9600 |
| C5—C6 | 1.522 (3) | C13—H13A | 0.9700 |
| C5—H5 | 0.9800 | C13—H13B | 0.9700 |
| C2—O1—C1 | 119.09 (17) | N5—C7—C6 | 108.24 (14) |
| O1—C1—H1A | 109.5 | C8—C7—C6 | 111.90 (15) |
| O1—C1—H1B | 109.5 | N5—C7—C9 | 105.65 (14) |
| H1A—C1—H1B | 109.5 | C8—C7—C9 | 109.46 (16) |
| O1—C1—H1C | 109.5 | C6—C7—C9 | 110.26 (15) |
| H1A—C1—H1C | 109.5 | C7—C8—H8A | 109.5 |
| H1B—C1—H1C | 109.5 | C7—C8—H8B | 109.5 |
| C3—N1—C4 | 112.36 (17) | H8A—C8—H8B | 109.5 |
| C3—N2—C2 | 111.51 (17) | C7—C8—H8C | 109.5 |
| C2—N3—C4 | 113.51 (17) | H8A—C8—H8C | 109.5 |
| C4—N4—C5 | 123.67 (17) | H8B—C8—H8C | 109.5 |
| C4—N4—H4 | 115.7 (17) | C7—C9—H9A | 109.5 |
| C5—N4—H4 | 120.6 (17) | C7—C9—H9B | 109.5 |
| C7—N5—C10 | 119.56 (14) | H9A—C9—H9B | 109.5 |
| C7—N5—H5A | 107.6 (14) | C7—C9—H9C | 109.5 |
| C10—N5—H5A | 108.8 (14) | H9A—C9—H9C | 109.5 |
| C7—N5—H5B | 105.8 (16) | H9B—C9—H9C | 109.5 |
| C10—N5—H5B | 107.0 (16) | C12—C10—C11 | 109.14 (16) |
| H5A—N5—H5B | 107 (2) | C12—C10—N5 | 105.87 (15) |
| N3—C2—O1 | 119.45 (18) | C11—C10—N5 | 110.86 (15) |
| N3—C2—N2 | 127.54 (18) | C12—C10—C13 | 110.33 (16) |
| O1—C2—N2 | 113.02 (17) | C11—C10—C13 | 112.65 (15) |
| N1—C3—N2 | 130.13 (18) | N5—C10—C13 | 107.78 (14) |
| N1—C3—Cl1 | 115.52 (15) | C10—C11—H11A | 109.5 |
| N2—C3—Cl1 | 114.34 (14) | C10—C11—H11B | 109.5 |
| N4—C4—N3 | 118.80 (17) | H11A—C11—H11B | 109.5 |
| N4—C4—N1 | 116.26 (18) | C10—C11—H11C | 109.5 |
| N3—C4—N1 | 124.94 (17) | H11A—C11—H11C | 109.5 |
| N4—C5—C13 | 112.27 (15) | H11B—C11—H11C | 109.5 |
| N4—C5—C6 | 109.68 (15) | C10—C12—H12A | 109.5 |
| C13—C5—C6 | 109.31 (15) | C10—C12—H12B | 109.5 |
| N4—C5—H5 | 108.5 | H12A—C12—H12B | 109.5 |
| C13—C5—H5 | 108.5 | C10—C12—H12C | 109.5 |
| C6—C5—H5 | 108.5 | H12A—C12—H12C | 109.5 |
| C5—C6—C7 | 112.37 (15) | H12B—C12—H12C | 109.5 |
| C5—C6—H6A | 109.1 | C5—C13—C10 | 112.14 (15) |
| C7—C6—H6A | 109.1 | C5—C13—H13A | 109.2 |
| C5—C6—H6B | 109.1 | C10—C13—H13A | 109.2 |
| C7—C6—H6B | 109.1 | C5—C13—H13B | 109.2 |
| H6A—C6—H6B | 107.9 | C10—C13—H13B | 109.2 |
| N5—C7—C8 | 111.14 (15) | H13A—C13—H13B | 107.9 |
| C4—N3—C2—O1 | −178.66 (17) | C4—N4—C5—C6 | 136.65 (19) |
| C4—N3—C2—N2 | 0.6 (3) | N4—C5—C6—C7 | −176.00 (15) |
| C1—O1—C2—N3 | −1.4 (3) | C13—C5—C6—C7 | 60.5 (2) |
| C1—O1—C2—N2 | 179.17 (18) | C10—N5—C7—C8 | −74.9 (2) |
| C3—N2—C2—N3 | −0.1 (3) | C10—N5—C7—C6 | 48.4 (2) |
| C3—N2—C2—O1 | 179.19 (17) | C10—N5—C7—C9 | 166.45 (15) |
| C4—N1—C3—N2 | 1.5 (3) | C5—C6—C7—N5 | −52.0 (2) |
| C4—N1—C3—Cl1 | −177.39 (13) | C5—C6—C7—C8 | 70.9 (2) |
| C2—N2—C3—N1 | −1.1 (3) | C5—C6—C7—C9 | −167.06 (15) |
| C2—N2—C3—Cl1 | 177.82 (14) | C7—N5—C10—C12 | −167.06 (16) |
| C5—N4—C4—N3 | 7.1 (3) | C7—N5—C10—C11 | 74.7 (2) |
| C5—N4—C4—N1 | −172.68 (17) | C7—N5—C10—C13 | −49.0 (2) |
| C2—N3—C4—N4 | −179.88 (18) | N4—C5—C13—C10 | 176.70 (15) |
| C2—N3—C4—N1 | −0.1 (3) | C6—C5—C13—C10 | −61.3 (2) |
| C3—N1—C4—N4 | 178.98 (17) | C12—C10—C13—C5 | 168.49 (16) |
| C3—N1—C4—N3 | −0.8 (3) | C11—C10—C13—C5 | −69.3 (2) |
| C4—N4—C5—C13 | −101.6 (2) | N5—C10—C13—C5 | 53.34 (19) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4···Cl2i | 0.82 (3) | 2.45 (3) | 3.2639 (19) | 171 (2) |
| N5—H5A···Cl2 | 0.86 (2) | 2.33 (2) | 3.1821 (17) | 173.2 (19) |
| N5—H5B···Cl2ii | 0.85 (3) | 2.32 (3) | 3.1714 (18) | 177 (2) |
| Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y+1/2, −z+1/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N4—H4···Cl2i | 0.82 (3) | 2.45 (3) | 3.2639 (19) | 171 (2) |
| N5—H5A···Cl2 | 0.86 (2) | 2.33 (2) | 3.1821 (17) | 173.2 (19) |
| N5—H5B···Cl2ii | 0.85 (3) | 2.32 (3) | 3.1714 (18) | 177 (2) |
| Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, y+1/2, −z+1/2. |
Borzatta, V. & Carrozza, P. (1991). Eur. Patent EP 0 462 069.
Bruker (1997). SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
Deng, Y., Wang, X.-J., Wen, F., Wang, L. & Zhang, Y. (2006). Acta Cryst. E62, o5207–o5208.
Kaiser, D. W. & Thurston, J. T. (1951). J. Am. Chem. Soc. 73, 2984–2986.
Rigaku/MSC (2005). CrystalClear. Rigaku/MSC, The Woodlands, Texas, USA.
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.
The title compound is an intermediate for the synthesis of hindered light stabilizers (Borzatta & Carrozza, 1991). Its derivatives have many applications in organic chemistry (Deng et al., 2006).
The triazine ring is essentially planar with an r.m.s. deviation from the mean plane of 0.0038 Å. The molecules are linked by intermolecular N—H···Cl hydrogen bonds (Table 1) forming zigzag chains.