 | Acta Crystallographica Section E Acta Crystallographica Section E CRYSTALLOGRAPHIC COMMUNICATIONS |
journal menu
organic compounds
| CRYSTALLOGRAPHIC COMMUNICATIONS |
accessrac-(rel-1R,2R,4S)-Spiro[bicyclo[2.2.1]heptane-2,3′-indol]-2′-amine
aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, Johannesburg, PO Wits 2050, South Africa
*Correspondence e-mail: andreas.lemmerer@wits.ac.za
In the racemic title compound, C14H16N2, the aromatic ring component of the aminoindoline system occupies the endo cavity of the norbornane component. The aromatic ring lies at an angle of 74.12 (5)° to the plane defined by the four C atoms that comprises the rigid part of the boat-shaped six-membered ring of the norbornane unit. Pairs of molecules assemble in the forming centrosymmetric hydrogen-bonded dimers via pairs of N—H⋯N hydrogen bonds through the syn H atom of the amine group.
Related literature
For the synthesis, see: Fleming et al. (1986![[Fleming, I., Loreto, M. A., Wallace, I. H. M. & Michael, J. P. (1986). J. Chem. Soc. Perkin Trans. 1, pp. 349-359.]](../../../../../../logos/arrows/e_arr.gif "Fleming, I., Loreto, M. A., Wallace, I. H. M. & Michael, J. P. (1986). J. Chem. Soc. Perkin Trans. 1, pp. 349-359.")
). For related compounds, see: Lemmerer & Michael (2010).
![[Scheme 1]](ng5096scheme1.gif)
Experimental
Crystal data
|
Refinement
|
| |||||||||||||||||
Data collection: SMART-NT (Bruker, 1998); cell SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536811001048/ng5096sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811001048/ng5096Isup2.hkl
The compound was prepared as described previously (Fleming et al., 1986). Crystals of (I) were grown by slow evaporation at ambient conditions of a hexane–chloroform solution (1:1 v/v).
The C-bound H atoms were geometrically placed (C—H bond lengths of 0.95 (aromatic CH), 0.99 (methylene CH2) and 1.00 (methine CH) Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The N-bound H atoms were located in the difference map and coordinates refined freely, with Uiso(H) = 1.5Ueq(N).
Data collection: SMART-NT (Bruker, 1998); cell SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
![[Figure 1]](./ng5096fig1thm.gif) | Fig. 1. The asymmetric unit of (I) showing the atomic numbering scheme. Displacement ellipsoids are shown at the 50% probability level. |
![[Figure 2]](./ng5096fig2thm.gif) | Fig. 2. Packing diagram of (I). Intermolecular N—H···N hydrogen bonds are shown as dashed red lines forming dimers. Note that the anti H2 is not used in any hydrogen bonding interactions. |
| C14H16N2 | F(000) = 912 |
| Mr = 212.29 | Dx = 1.252 Mg m−3 |
| Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2n 2ab | Cell parameters from 876 reflections |
| a = 19.2145 (14) Å | θ = 2.9–25.5° |
| b = 11.3371 (8) Å | µ = 0.08 mm−1 |
| c = 10.3399 (7) Å | T = 173 K |
| V = 2252.4 (3) Å3 | Needle, colourless |
| Z = 8 | 0.4 × 0.12 × 0.08 mm |
| Bruker SMART 1K CCD area-detector diffractometer | 2728 independent reflections |
| Radiation source: sealed tube | 1842 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.078 |
| ω scans | θmax = 28.0°, θmin = 2.1° |
| Absorption correction: integration (XPREP; Bruker, 1999) | h = −22→25 |
| Tmin = 0.980, Tmax = 0.994 | k = −14→14 |
| 16382 measured reflections | l = −13→13 |
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.046 | w = 1/[σ2(Fo2) + (0.0594P)2 + 0.0604P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.118 | (Δ/σ)max = 0.005 |
| S = 1.04 | Δρmax = 0.22 e Å−3 |
| 2728 reflections | Δρmin = −0.20 e Å−3 |
| 151 parameters |
| C14H16N2 | V = 2252.4 (3) Å3 |
| Mr = 212.29 | Z = 8 |
| Orthorhombic, Pbcn | Mo Kα radiation |
| a = 19.2145 (14) Å | µ = 0.08 mm−1 |
| b = 11.3371 (8) Å | T = 173 K |
| c = 10.3399 (7) Å | 0.4 × 0.12 × 0.08 mm |
| Bruker SMART 1K CCD area-detector diffractometer | 2728 independent reflections |
| Absorption correction: integration (XPREP; Bruker, 1999) | 1842 reflections with I > 2σ(I) |
| Tmin = 0.980, Tmax = 0.994 | Rint = 0.078 |
| 16382 measured reflections |
| R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
| wR(F2) = 0.118 | H atoms treated by a mixture of independent and constrained refinement |
| S = 1.04 | Δρmax = 0.22 e Å−3 |
| 2728 reflections | Δρmin = −0.20 e Å−3 |
| 151 parameters |
Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 1999) |
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. |
| x | y | z | Uiso*/Ueq | ||
| C2 | 0.08033 (7) | 0.08297 (13) | 0.39207 (14) | 0.0269 (3) | |
| C3 | 0.12640 (7) | 0.16703 (11) | 0.31300 (13) | 0.0221 (3) | |
| C4 | 0.11622 (7) | 0.27794 (12) | 0.39302 (13) | 0.0239 (3) | |
| C5 | 0.13484 (8) | 0.39471 (13) | 0.37348 (14) | 0.0299 (3) | |
| H5 | 0.16 | 0.417 | 0.2983 | 0.036* | |
| C6 | 0.11627 (8) | 0.47945 (14) | 0.46537 (16) | 0.0394 (4) | |
| H6 | 0.1289 | 0.5597 | 0.4527 | 0.047* | |
| C7 | 0.07970 (9) | 0.44686 (16) | 0.57446 (17) | 0.0484 (5) | |
| H7 | 0.0676 | 0.5051 | 0.6366 | 0.058* | |
| C8 | 0.06029 (9) | 0.33061 (16) | 0.59495 (18) | 0.0481 (5) | |
| H8 | 0.0356 | 0.3086 | 0.6708 | 0.058* | |
| C9 | 0.07762 (7) | 0.24683 (14) | 0.50236 (14) | 0.0311 (3) | |
| C10 | 0.20345 (7) | 0.11810 (12) | 0.30821 (13) | 0.0250 (3) | |
| H10 | 0.2183 | 0.0743 | 0.3874 | 0.03* | |
| C11 | 0.25299 (7) | 0.21793 (13) | 0.26686 (14) | 0.0287 (3) | |
| H11A | 0.3022 | 0.1927 | 0.2727 | 0.034* | |
| H11B | 0.2462 | 0.2892 | 0.3208 | 0.034* | |
| C12 | 0.23141 (8) | 0.24110 (13) | 0.12412 (14) | 0.0302 (3) | |
| H12A | 0.211 | 0.3208 | 0.114 | 0.036* | |
| H12B | 0.2718 | 0.2333 | 0.0652 | 0.036* | |
| C13 | 0.17676 (7) | 0.14452 (12) | 0.09730 (14) | 0.0286 (3) | |
| H13 | 0.1715 | 0.1232 | 0.004 | 0.034* | |
| C14 | 0.10853 (7) | 0.17663 (12) | 0.16523 (13) | 0.0263 (3) | |
| H14A | 0.071 | 0.1209 | 0.1414 | 0.032* | |
| H14B | 0.0938 | 0.2577 | 0.1426 | 0.032* | |
| C15 | 0.20324 (8) | 0.04395 (12) | 0.18327 (14) | 0.0312 (4) | |
| H15A | 0.2503 | 0.0163 | 0.1584 | 0.037* | |
| H15B | 0.1705 | −0.0234 | 0.1873 | 0.037* | |
| N1 | 0.05733 (6) | 0.12635 (12) | 0.50174 (12) | 0.0341 (3) | |
| N2 | 0.06590 (7) | −0.02770 (11) | 0.35451 (14) | 0.0334 (3) | |
| H1 | 0.0310 (10) | −0.0677 (15) | 0.3982 (17) | 0.05* | |
| H2 | 0.0746 (9) | −0.0498 (16) | 0.2725 (18) | 0.05* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C2 | 0.0181 (6) | 0.0322 (8) | 0.0303 (8) | −0.0025 (6) | −0.0042 (6) | 0.0085 (6) |
| C3 | 0.0195 (6) | 0.0246 (7) | 0.0223 (7) | −0.0020 (5) | −0.0009 (5) | 0.0028 (5) |
| C4 | 0.0185 (6) | 0.0306 (7) | 0.0226 (7) | −0.0003 (5) | −0.0014 (5) | 0.0012 (6) |
| C5 | 0.0304 (8) | 0.0306 (7) | 0.0287 (8) | −0.0010 (6) | 0.0003 (6) | −0.0016 (6) |
| C6 | 0.0383 (9) | 0.0367 (9) | 0.0432 (10) | −0.0013 (7) | −0.0016 (7) | −0.0111 (7) |
| C7 | 0.0422 (10) | 0.0553 (11) | 0.0476 (11) | −0.0032 (8) | 0.0076 (8) | −0.0249 (9) |
| C8 | 0.0388 (10) | 0.0679 (12) | 0.0375 (10) | −0.0101 (9) | 0.0170 (8) | −0.0137 (9) |
| C9 | 0.0223 (7) | 0.0430 (8) | 0.0278 (8) | −0.0042 (6) | 0.0026 (6) | −0.0007 (6) |
| C10 | 0.0197 (6) | 0.0281 (7) | 0.0272 (8) | 0.0004 (6) | −0.0008 (6) | 0.0045 (6) |
| C11 | 0.0222 (7) | 0.0357 (8) | 0.0282 (8) | −0.0035 (6) | 0.0017 (6) | −0.0012 (6) |
| C12 | 0.0306 (8) | 0.0347 (8) | 0.0254 (8) | −0.0075 (6) | 0.0058 (6) | −0.0014 (6) |
| C13 | 0.0330 (8) | 0.0318 (8) | 0.0211 (7) | −0.0055 (6) | 0.0002 (6) | −0.0038 (6) |
| C14 | 0.0271 (7) | 0.0274 (7) | 0.0243 (7) | −0.0032 (6) | −0.0048 (6) | 0.0015 (6) |
| C15 | 0.0269 (7) | 0.0273 (7) | 0.0394 (9) | 0.0012 (6) | 0.0052 (7) | −0.0028 (6) |
| N1 | 0.0267 (6) | 0.0434 (7) | 0.0321 (7) | −0.0086 (6) | 0.0057 (5) | 0.0052 (6) |
| N2 | 0.0302 (7) | 0.0309 (7) | 0.0390 (8) | −0.0092 (5) | 0.0000 (6) | 0.0082 (6) |
| C2—N1 | 1.3126 (19) | C10—C15 | 1.5413 (19) |
| C2—N2 | 1.3424 (19) | C10—H10 | 1 |
| C2—C3 | 1.5362 (18) | C11—C12 | 1.555 (2) |
| C3—C4 | 1.5178 (19) | C11—H11A | 0.99 |
| C3—C14 | 1.5698 (18) | C11—H11B | 0.99 |
| C3—C10 | 1.5819 (19) | C12—C13 | 1.5423 (19) |
| C4—C5 | 1.386 (2) | C12—H12A | 0.99 |
| C4—C9 | 1.3974 (19) | C12—H12B | 0.99 |
| C5—C6 | 1.398 (2) | C13—C14 | 1.531 (2) |
| C5—H5 | 0.95 | C13—C15 | 1.533 (2) |
| C6—C7 | 1.379 (2) | C13—H13 | 1 |
| C6—H6 | 0.95 | C14—H14A | 0.99 |
| C7—C8 | 1.386 (2) | C14—H14B | 0.99 |
| C7—H7 | 0.95 | C15—H15A | 0.99 |
| C8—C9 | 1.389 (2) | C15—H15B | 0.99 |
| C8—H8 | 0.95 | N2—H1 | 0.927 (19) |
| C9—N1 | 1.420 (2) | N2—H2 | 0.900 (18) |
| C10—C11 | 1.5394 (19) | ||
| N1—C2—N2 | 122.04 (13) | C10—C11—H11A | 111.2 |
| N1—C2—C3 | 114.92 (12) | C12—C11—H11A | 111.2 |
| N2—C2—C3 | 123.02 (13) | C10—C11—H11B | 111.2 |
| C4—C3—C2 | 98.60 (11) | C12—C11—H11B | 111.2 |
| C4—C3—C14 | 116.42 (11) | H11A—C11—H11B | 109.1 |
| C2—C3—C14 | 115.78 (11) | C13—C12—C11 | 103.43 (11) |
| C4—C3—C10 | 115.35 (10) | C13—C12—H12A | 111.1 |
| C2—C3—C10 | 109.78 (10) | C11—C12—H12A | 111.1 |
| C14—C3—C10 | 101.45 (10) | C13—C12—H12B | 111.1 |
| C5—C4—C9 | 119.74 (13) | C11—C12—H12B | 111.1 |
| C5—C4—C3 | 132.72 (12) | H12A—C12—H12B | 109 |
| C9—C4—C3 | 107.47 (12) | C14—C13—C15 | 101.24 (11) |
| C4—C5—C6 | 119.44 (14) | C14—C13—C12 | 109.37 (11) |
| C4—C5—H5 | 120.3 | C15—C13—C12 | 101.41 (12) |
| C6—C5—H5 | 120.3 | C14—C13—H13 | 114.4 |
| C7—C6—C5 | 120.13 (15) | C15—C13—H13 | 114.4 |
| C7—C6—H6 | 119.9 | C12—C13—H13 | 114.4 |
| C5—C6—H6 | 119.9 | C13—C14—C3 | 104.05 (11) |
| C6—C7—C8 | 121.12 (15) | C13—C14—H14A | 110.9 |
| C6—C7—H7 | 119.4 | C3—C14—H14A | 110.9 |
| C8—C7—H7 | 119.4 | C13—C14—H14B | 110.9 |
| C7—C8—C9 | 118.71 (16) | C3—C14—H14B | 110.9 |
| C7—C8—H8 | 120.6 | H14A—C14—H14B | 109 |
| C9—C8—H8 | 120.6 | C13—C15—C10 | 94.67 (10) |
| C8—C9—C4 | 120.81 (14) | C13—C15—H15A | 112.8 |
| C8—C9—N1 | 126.50 (14) | C10—C15—H15A | 112.8 |
| C4—C9—N1 | 112.63 (13) | C13—C15—H15B | 112.8 |
| C11—C10—C15 | 99.78 (11) | C10—C15—H15B | 112.8 |
| C11—C10—C3 | 109.24 (11) | H15A—C15—H15B | 110.3 |
| C15—C10—C3 | 102.41 (10) | C2—N1—C9 | 105.77 (11) |
| C11—C10—H10 | 114.6 | C2—N2—H1 | 117.8 (11) |
| C15—C10—H10 | 114.6 | C2—N2—H2 | 119.7 (12) |
| C3—C10—H10 | 114.6 | H1—N2—H2 | 117.2 (16) |
| C10—C11—C12 | 102.88 (11) | ||
| N1—C2—C3—C4 | −8.15 (14) | C2—C3—C10—C11 | −162.78 (11) |
| N2—C2—C3—C4 | 173.58 (13) | C14—C3—C10—C11 | 74.23 (13) |
| N1—C2—C3—C14 | −133.10 (13) | C4—C3—C10—C15 | −157.66 (11) |
| N2—C2—C3—C14 | 48.64 (18) | C2—C3—C10—C15 | 92.08 (12) |
| N1—C2—C3—C10 | 112.82 (13) | C14—C3—C10—C15 | −30.90 (12) |
| N2—C2—C3—C10 | −65.45 (16) | C15—C10—C11—C12 | 39.45 (13) |
| C2—C3—C4—C5 | −170.93 (15) | C3—C10—C11—C12 | −67.48 (13) |
| C14—C3—C4—C5 | −46.4 (2) | C10—C11—C12—C13 | −4.84 (14) |
| C10—C3—C4—C5 | 72.31 (19) | C11—C12—C13—C14 | 74.58 (14) |
| C2—C3—C4—C9 | 6.05 (13) | C11—C12—C13—C15 | −31.79 (14) |
| C14—C3—C4—C9 | 130.55 (12) | C15—C13—C14—C3 | 39.32 (13) |
| C10—C3—C4—C9 | −110.72 (13) | C12—C13—C14—C3 | −67.16 (14) |
| C9—C4—C5—C6 | 1.7 (2) | C4—C3—C14—C13 | 121.15 (12) |
| C3—C4—C5—C6 | 178.34 (14) | C2—C3—C14—C13 | −123.67 (12) |
| C4—C5—C6—C7 | 0.0 (2) | C10—C3—C14—C13 | −4.90 (13) |
| C5—C6—C7—C8 | −0.4 (3) | C14—C13—C15—C10 | −57.33 (12) |
| C6—C7—C8—C9 | −0.8 (3) | C12—C13—C15—C10 | 55.32 (12) |
| C7—C8—C9—C4 | 2.5 (3) | C11—C10—C15—C13 | −58.27 (12) |
| C7—C8—C9—N1 | −174.52 (15) | C3—C10—C15—C13 | 54.09 (12) |
| C5—C4—C9—C8 | −2.9 (2) | N2—C2—N1—C9 | −174.97 (13) |
| C3—C4—C9—C8 | 179.63 (14) | C3—C2—N1—C9 | 6.75 (16) |
| C5—C4—C9—N1 | 174.45 (12) | C8—C9—N1—C2 | 174.96 (16) |
| C3—C4—C9—N1 | −2.99 (16) | C4—C9—N1—C2 | −2.23 (16) |
| C4—C3—C10—C11 | −52.53 (15) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H1···N1i | 0.927 (19) | 2.10 (2) | 3.0112 (18) | 169 (2) |
| Symmetry code: (i) −x, −y, −z+1. |
Experimental details
| Crystal data | |
| Chemical formula | C14H16N2 |
| Mr | 212.29 |
| Crystal system, space group | Orthorhombic, Pbcn |
| Temperature (K) | 173 |
| a, b, c (Å) | 19.2145 (14), 11.3371 (8), 10.3399 (7) |
| V (Å3) | 2252.4 (3) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.08 |
| Crystal size (mm) | 0.4 × 0.12 × 0.08 |
| Data collection | |
| Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
| Absorption correction | Integration (XPREP; Bruker, 1999) |
| Tmin, Tmax | 0.980, 0.994 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 16382, 2728, 1842 |
| Rint | 0.078 |
| (sin θ/λ)max (Å−1) | 0.660 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.118, 1.04 |
| No. of reflections | 2728 |
| No. of parameters | 151 |
| H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
| Δρmax, Δρmin (e Å−3) | 0.22, −0.20 |
Computer programs: SMART-NT (Bruker, 1998), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H1···N1i | 0.927 (19) | 2.10 (2) | 3.0112 (18) | 169 (2) |
| Symmetry code: (i) −x, −y, −z+1. |
Acknowledgements
This material is based upon work supported financially by the National Research Foundation, Pretoria (GUN 2053652). This work was also supported by the University of the Witwatersrand, which is thanked for providing the required infrastructure.
References
Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1998). SMART-NT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Fleming, I., Loreto, M. A., Wallace, I. H. M. & Michael, J. P. (1986). J. Chem. Soc. Perkin Trans. 1, pp. 349–359. CrossRef Web of Science Google Scholar
Lemmerer, A. & Michael, J. P. (2010). S. Afr. J. Chem. 63, 186–191. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
| CRYSTALLOGRAPHIC COMMUNICATIONS |
The racemic compound (rac)-(rel-1R,2R,4S)-Spiro[bicyclo[2.2.1] heptane-2,3'-indol]-2'-amine (I) is an intermediate in the synthesis of a model oxindole prepared during the development of methodology aimed at the total synthesis of the complex spiro-oxindole alkaloid gelsemine (Fleming et al., 1986). The solid state packing of the title compound involves forming centrosymmetric hydrogen-bonded pairs of molecules, generated by interactions from the syn H1 of the amine to the N1 lone pair of the oxindole backbone (See Fig 2). Formation of dimeric pairs is seen in related oxindole compounds (Lemmerer & Michael, 2010). The anti H of the amine group is not involved in any hydrogen bonding interactions.