organic compounds
(3R,4S)-3-Methyl-4-phenyl-2-[(R)-1-phenylethyl]-3,4-dihydroisoquinolin-2-ium tetrafluoridoborate
aAcadémie Militaire, Fondouk Jedid, 8012 Nabeul, Tunisia, and bCentre de Recherche de Gif sur Yvette, ICSN-CNRS, 1 avenue de la Terrasse, 91198 Gif sur Yvette, France
*Correspondence e-mail: pascal.retailleau@cnrs.fr
The title salt, C24H24N+·BF4−, is one of two possible diastereoisomers having a different configuration of the in the α-phenylethyl substituent, whose was established to be R. The two phenyl substituents of the cation have a cofacial orientation, albeit with a long centroid–centroid separation of 4.129 (3) Å. The exhibits numerous C—H⋯F contacts between counter-ions, with the tetrafluoridoborate anion surrounded by five iminium cations.
CCDC reference: 984464
Related literature
For related literature, see: Adam et al. (2001); Bohé et al. (1999); Cremer & Pople (1975); Davies & Coote (1988)
Experimental
Crystal data
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Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell CAD-4 Software; data reduction: NONIUS (Riche, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP (Johnson, 1965), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
CCDC reference: 984464
10.1107/S160053681400230X/ld2119sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681400230X/ld2119Isup2.hkl
Title compound was prepared by reaction of (3R,4S)-3-methyl-4-phenyl-3,4-dihydroisoquinoleine (1.990 g, 9 mmol) and rac-(1-bromoethyl) benzene (6.2 ml, 45 mmol). The mixture was heated at 318 K for 36 h. The reaction was monitored by TLC.
Two
were obtained in 1:1 ratio. These were separated by Each compound was treated by 1 equiv of AgBF4 in acetonitrile. Filtration and concentration in vacuo afforded a white solid.Only one diastereoisomer (the title compound) was successfully recrystallized. Crystals were grown by placing a solution of this dastereoisomer (45mg) in CH3COCH3 (0.5 ml) at the bottom of a test tube, then carefully covering it with pure hexane (50 ml).The test tube was covered and left undisturbed.
Colorless crystals of the title compound appeared after several days. [α]D24 = -16.1 (c 0.4; CHCl3), m.p. 447 K.
All H atoms were positioned geometrically and treated as riding, with C—H = 0.93 (aromatic), 0.96 (methyl), or 0.98 Å (methine), with Uiso(H) = xUeq(C) where x = 1.5 for methyl H and 1.2 for all other H atoms.
The
permitted P41212 and P43212 as possible space groups, but in the absence of significant it was not possible to distinguish between these enantiomeric space groups and the Friedel-equivalent reflections were merged. P41212 was selected because the has been assigned by reference to unchanging chiral centres in the synthetic procedure.Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell
CAD-4 Software (Enraf–Nonius, 1989); data reduction: NONIUS (Riche, 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP (Johnson, 1965), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. An ORTEP view of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. | |
Fig. 2. Environment of the BF4- anion in the crystal of the title compound. Geometric parameters for the non-conventional C–H···F hydrogen bonds shown as cyan dotted lines are provided in supplementary material section. |
C24H24N+·BF4− | Dx = 1.273 Mg m−3 |
Mr = 413.25 | Cu Kα radiation, λ = 1.5418 Å |
Tetragonal, P41212 | Cell parameters from 25 reflections |
Hall symbol: P 4abw 2nw | θ = 7.9–13.4° |
a = 9.367 (4) Å | µ = 0.81 mm−1 |
c = 49.137 (14) Å | T = 293 K |
V = 4311 (3) Å3 | Prism, colourless |
Z = 8 | 0.33 × 0.26 × 0.26 mm |
F(000) = 1728 |
Nonius CAD-4 diffractometer | Rint = 0.092 |
Radiation source: X-ray tube | θmax = 67.0°, θmin = 3.6° |
Graphite monochromator | h = −11→10 |
θ/2θ scans | k = −3→11 |
10992 measured reflections | l = 0→58 |
2353 independent reflections | 3 standard reflections every 60 min |
1192 reflections with I > 2σ(I) | intensity decay: 1% |
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)] = 0.065 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.1069P)2 + 0.3684P] where P = (Fo2 + 2Fc2)/3 |
2353 reflections | (Δ/σ)max = 0.001 |
273 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C24H24N+·BF4− | Z = 8 |
Mr = 413.25 | Cu Kα radiation |
Tetragonal, P41212 | µ = 0.81 mm−1 |
a = 9.367 (4) Å | T = 293 K |
c = 49.137 (14) Å | 0.33 × 0.26 × 0.26 mm |
V = 4311 (3) Å3 |
Nonius CAD-4 diffractometer | Rint = 0.092 |
10992 measured reflections | 3 standard reflections every 60 min |
2353 independent reflections | intensity decay: 1% |
1192 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.065 | 0 restraints |
wR(F2) = 0.215 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.30 e Å−3 |
2353 reflections | Δρmin = −0.18 e Å−3 |
273 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 | 0.5567 (6) | 0.4341 (7) | 0.05389 (13) | 0.0603 (17) | |
H1 | 0.5550 | 0.5320 | 0.0507 | 0.068* | |
N2 | 0.5135 (5) | 0.3893 (5) | 0.07701 (9) | 0.0529 (13) | |
C3 | 0.5210 (7) | 0.2316 (6) | 0.08264 (11) | 0.0539 (16) | |
H3 | 0.4509 | 0.2086 | 0.0968 | 0.060* | |
C4 | 0.4824 (6) | 0.1472 (6) | 0.05687 (10) | 0.0517 (15) | |
H4 | 0.5096 | 0.0477 | 0.0602 | 0.058* | |
C5 | 0.6173 (8) | 0.1095 (8) | 0.01273 (13) | 0.0717 (19) | |
H5 | 0.5933 | 0.0131 | 0.0129 | 0.080* | |
C6 | 0.6996 (9) | 0.1639 (10) | −0.00821 (14) | 0.085 (2) | |
H6 | 0.7334 | 0.1031 | −0.0217 | 0.095* | |
C7 | 0.7322 (8) | 0.3084 (10) | −0.00929 (14) | 0.083 (2) | |
H7 | 0.7864 | 0.3444 | −0.0236 | 0.093* | |
C8 | 0.6845 (8) | 0.3968 (8) | 0.01059 (12) | 0.072 (2) | |
H8 | 0.7032 | 0.4941 | 0.0096 | 0.081* | |
C9 | 0.6083 (6) | 0.3428 (7) | 0.03230 (11) | 0.0565 (16) | |
C10 | 0.5708 (6) | 0.1985 (7) | 0.03335 (12) | 0.0552 (16) | |
C11 | 0.6686 (7) | 0.1929 (8) | 0.09325 (14) | 0.077 (2) | |
H11A | 0.6783 | 0.0909 | 0.0938 | 0.088* | |
H11B | 0.6806 | 0.2311 | 0.1112 | 0.088* | |
H11C | 0.7399 | 0.2321 | 0.0814 | 0.088* | |
C12 | 0.3215 (7) | 0.1476 (7) | 0.05072 (12) | 0.0581 (17) | |
C13 | 0.2383 (8) | 0.0355 (8) | 0.05968 (13) | 0.074 (2) | |
H13 | 0.2807 | −0.0381 | 0.0695 | 0.083* | |
C14 | 0.0943 (8) | 0.0300 (9) | 0.05445 (14) | 0.085 (2) | |
H14 | 0.0411 | −0.0479 | 0.0604 | 0.095* | |
C15 | 0.0293 (8) | 0.1376 (11) | 0.04074 (16) | 0.090 (3) | |
H15 | −0.0683 | 0.1350 | 0.0373 | 0.100* | |
C16 | 0.1104 (9) | 0.2492 (10) | 0.03213 (16) | 0.100 (3) | |
H16 | 0.0672 | 0.3234 | 0.0226 | 0.113* | |
C17 | 0.2526 (8) | 0.2549 (9) | 0.03710 (15) | 0.087 (2) | |
H17 | 0.3046 | 0.3334 | 0.0311 | 0.097* | |
C18 | 0.4575 (7) | 0.4894 (7) | 0.09788 (11) | 0.0611 (17) | |
H18 | 0.4812 | 0.5856 | 0.0915 | 0.068* | |
C19 | 0.5320 (8) | 0.4718 (8) | 0.12507 (14) | 0.087 (2) | |
H19A | 0.5069 | 0.5500 | 0.1368 | 0.100* | |
H19B | 0.6335 | 0.4708 | 0.1223 | 0.100* | |
H19C | 0.5027 | 0.3836 | 0.1333 | 0.100* | |
C20 | 0.2977 (7) | 0.4823 (7) | 0.09907 (12) | 0.0562 (16) | |
C21 | 0.2243 (8) | 0.3923 (8) | 0.11650 (14) | 0.079 (2) | |
H21 | 0.2736 | 0.3317 | 0.1282 | 0.088* | |
C22 | 0.0726 (9) | 0.3937 (11) | 0.1163 (2) | 0.102 (3) | |
H22 | 0.0220 | 0.3337 | 0.1279 | 0.115* | |
C23 | 0.0022 (10) | 0.4820 (12) | 0.09934 (19) | 0.102 (3) | |
H23 | −0.0971 | 0.4827 | 0.0996 | 0.114* | |
C24 | 0.0700 (10) | 0.5679 (12) | 0.08225 (19) | 0.114 (3) | |
H24 | 0.0190 | 0.6258 | 0.0703 | 0.128* | |
C25 | 0.2198 (9) | 0.5703 (9) | 0.08234 (15) | 0.089 (2) | |
H25 | 0.2675 | 0.6330 | 0.0708 | 0.100* | |
B26 | 0.7073 (11) | 0.7827 (9) | 0.0634 (2) | 0.078 (3) | |
F27 | 0.5714 (5) | 0.7850 (5) | 0.05584 (14) | 0.151 (3) | |
F28 | 0.7744 (6) | 0.9020 (6) | 0.06260 (15) | 0.160 (3) | |
F29 | 0.7185 (7) | 0.7172 (11) | 0.08622 (15) | 0.248 (5) | |
F30 | 0.7760 (9) | 0.6905 (9) | 0.0478 (2) | 0.237 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.051 (4) | 0.063 (4) | 0.066 (4) | −0.017 (3) | 0.004 (3) | 0.003 (3) |
N2 | 0.053 (3) | 0.054 (3) | 0.052 (3) | 0.002 (3) | 0.007 (2) | −0.005 (2) |
C3 | 0.056 (4) | 0.054 (4) | 0.051 (3) | 0.004 (3) | −0.006 (3) | 0.007 (3) |
C4 | 0.050 (4) | 0.051 (4) | 0.054 (3) | −0.006 (3) | −0.002 (3) | 0.002 (3) |
C5 | 0.072 (5) | 0.079 (5) | 0.064 (4) | 0.000 (4) | −0.002 (4) | −0.013 (4) |
C6 | 0.088 (6) | 0.105 (7) | 0.062 (4) | 0.003 (5) | 0.016 (4) | −0.013 (5) |
C7 | 0.075 (5) | 0.109 (7) | 0.065 (4) | −0.006 (5) | 0.021 (4) | −0.001 (5) |
C8 | 0.072 (5) | 0.082 (5) | 0.063 (4) | −0.013 (4) | 0.008 (4) | 0.004 (4) |
C9 | 0.052 (4) | 0.068 (4) | 0.050 (3) | −0.008 (3) | 0.010 (3) | 0.001 (3) |
C10 | 0.052 (4) | 0.061 (4) | 0.053 (3) | −0.006 (3) | −0.008 (3) | −0.001 (3) |
C11 | 0.063 (5) | 0.095 (6) | 0.072 (4) | 0.009 (4) | −0.016 (4) | −0.004 (4) |
C12 | 0.054 (4) | 0.066 (4) | 0.054 (3) | −0.016 (4) | −0.010 (3) | −0.004 (3) |
C13 | 0.074 (5) | 0.082 (5) | 0.066 (4) | −0.026 (4) | −0.004 (4) | 0.004 (4) |
C14 | 0.068 (5) | 0.107 (7) | 0.079 (5) | −0.043 (5) | 0.014 (4) | −0.018 (5) |
C15 | 0.043 (4) | 0.135 (8) | 0.090 (5) | −0.009 (5) | −0.001 (4) | 0.002 (6) |
C16 | 0.067 (6) | 0.115 (7) | 0.119 (7) | −0.003 (5) | −0.018 (5) | 0.024 (6) |
C17 | 0.053 (5) | 0.100 (6) | 0.107 (5) | −0.014 (4) | −0.012 (4) | 0.023 (5) |
C18 | 0.065 (4) | 0.060 (4) | 0.058 (3) | 0.001 (3) | 0.007 (3) | −0.007 (3) |
C19 | 0.078 (5) | 0.111 (7) | 0.072 (4) | 0.003 (5) | −0.006 (4) | −0.023 (5) |
C20 | 0.058 (4) | 0.050 (4) | 0.060 (4) | −0.001 (3) | 0.007 (3) | −0.004 (3) |
C21 | 0.075 (5) | 0.074 (5) | 0.087 (5) | 0.005 (4) | 0.008 (4) | 0.022 (4) |
C22 | 0.066 (6) | 0.106 (7) | 0.135 (8) | −0.011 (5) | 0.030 (5) | 0.008 (6) |
C23 | 0.062 (5) | 0.133 (9) | 0.110 (7) | 0.021 (6) | 0.008 (5) | −0.015 (6) |
C24 | 0.076 (7) | 0.164 (11) | 0.103 (7) | 0.029 (6) | −0.003 (5) | 0.003 (7) |
C25 | 0.088 (6) | 0.100 (7) | 0.080 (5) | 0.008 (5) | 0.015 (5) | 0.014 (5) |
B26 | 0.078 (7) | 0.047 (5) | 0.108 (7) | −0.003 (5) | −0.021 (6) | −0.003 (5) |
F27 | 0.085 (4) | 0.079 (3) | 0.287 (7) | −0.014 (3) | −0.087 (4) | 0.040 (4) |
F28 | 0.098 (4) | 0.106 (4) | 0.277 (7) | −0.051 (3) | −0.015 (4) | −0.001 (5) |
F29 | 0.135 (6) | 0.415 (15) | 0.194 (6) | −0.101 (7) | −0.062 (5) | 0.166 (9) |
F30 | 0.176 (8) | 0.193 (8) | 0.343 (11) | 0.014 (6) | 0.014 (7) | −0.147 (8) |
C1—N2 | 1.277 (7) | C14—C15 | 1.356 (10) |
C1—C9 | 1.446 (8) | C14—H14 | 0.9300 |
C1—H1 | 0.9300 | C15—C16 | 1.360 (11) |
N2—C18 | 1.485 (7) | C15—H15 | 0.9300 |
N2—C3 | 1.505 (7) | C16—C17 | 1.356 (10) |
C3—C11 | 1.521 (8) | C16—H16 | 0.9300 |
C3—C4 | 1.536 (8) | C17—H17 | 0.9300 |
C3—H3 | 0.9800 | C18—C20 | 1.500 (9) |
C4—C10 | 1.500 (8) | C18—C19 | 1.516 (9) |
C4—C12 | 1.537 (8) | C18—H18 | 0.9800 |
C4—H4 | 0.9800 | C19—H19A | 0.9600 |
C5—C10 | 1.383 (9) | C19—H19B | 0.9600 |
C5—C6 | 1.383 (9) | C19—H19C | 0.9600 |
C5—H5 | 0.9300 | C20—C25 | 1.374 (9) |
C6—C7 | 1.389 (10) | C20—C21 | 1.385 (9) |
C6—H6 | 0.9300 | C21—C22 | 1.421 (11) |
C7—C8 | 1.356 (9) | C21—H21 | 0.9300 |
C7—H7 | 0.9300 | C22—C23 | 1.347 (11) |
C8—C9 | 1.379 (8) | C22—H22 | 0.9300 |
C8—H8 | 0.9300 | C23—C24 | 1.325 (12) |
C9—C10 | 1.398 (8) | C23—H23 | 0.9300 |
C11—H11A | 0.9600 | C24—C25 | 1.403 (11) |
C11—H11B | 0.9600 | C24—H24 | 0.9300 |
C11—H11C | 0.9600 | C25—H25 | 0.9300 |
C12—C17 | 1.369 (10) | B26—F29 | 1.281 (10) |
C12—C13 | 1.380 (9) | B26—F28 | 1.283 (9) |
C13—C14 | 1.374 (10) | B26—F30 | 1.323 (11) |
C13—H13 | 0.9300 | B26—F27 | 1.327 (10) |
N2—C1—C9 | 124.4 (6) | C15—C14—C13 | 120.4 (8) |
N2—C1—H1 | 117.8 | C15—C14—H14 | 119.8 |
C9—C1—H1 | 117.8 | C13—C14—H14 | 119.8 |
C1—N2—C18 | 121.3 (5) | C14—C15—C16 | 118.3 (7) |
C1—N2—C3 | 118.1 (5) | C14—C15—H15 | 120.8 |
C18—N2—C3 | 120.6 (5) | C16—C15—H15 | 120.8 |
N2—C3—C11 | 109.9 (5) | C17—C16—C15 | 121.5 (8) |
N2—C3—C4 | 110.0 (4) | C17—C16—H16 | 119.2 |
C11—C3—C4 | 112.0 (5) | C15—C16—H16 | 119.2 |
N2—C3—H3 | 108.3 | C16—C17—C12 | 121.5 (8) |
C11—C3—H3 | 108.3 | C16—C17—H17 | 119.2 |
C4—C3—H3 | 108.3 | C12—C17—H17 | 119.2 |
C10—C4—C3 | 109.9 (5) | N2—C18—C20 | 110.6 (5) |
C10—C4—C12 | 112.9 (5) | N2—C18—C19 | 112.2 (5) |
C3—C4—C12 | 113.1 (5) | C20—C18—C19 | 114.8 (5) |
C10—C4—H4 | 106.9 | N2—C18—H18 | 106.2 |
C3—C4—H4 | 106.9 | C20—C18—H18 | 106.2 |
C12—C4—H4 | 106.9 | C19—C18—H18 | 106.2 |
C10—C5—C6 | 119.9 (7) | C18—C19—H19A | 109.5 |
C10—C5—H5 | 120.0 | C18—C19—H19B | 109.5 |
C6—C5—H5 | 120.0 | H19A—C19—H19B | 109.5 |
C5—C6—C7 | 120.7 (7) | C18—C19—H19C | 109.5 |
C5—C6—H6 | 119.7 | H19A—C19—H19C | 109.5 |
C7—C6—H6 | 119.7 | H19B—C19—H19C | 109.5 |
C8—C7—C6 | 119.7 (7) | C25—C20—C21 | 118.2 (7) |
C8—C7—H7 | 120.2 | C25—C20—C18 | 118.7 (6) |
C6—C7—H7 | 120.2 | C21—C20—C18 | 123.1 (6) |
C7—C8—C9 | 120.2 (7) | C20—C21—C22 | 119.1 (7) |
C7—C8—H8 | 119.9 | C20—C21—H21 | 120.4 |
C9—C8—H8 | 119.9 | C22—C21—H21 | 120.4 |
C8—C9—C10 | 120.9 (6) | C23—C22—C21 | 120.0 (8) |
C8—C9—C1 | 121.6 (6) | C23—C22—H22 | 120.0 |
C10—C9—C1 | 117.4 (5) | C21—C22—H22 | 120.0 |
C5—C10—C9 | 118.5 (6) | C24—C23—C22 | 122.0 (9) |
C5—C10—C4 | 123.0 (6) | C24—C23—H23 | 119.0 |
C9—C10—C4 | 118.5 (5) | C22—C23—H23 | 119.0 |
C3—C11—H11A | 109.5 | C23—C24—C25 | 119.2 (9) |
C3—C11—H11B | 109.5 | C23—C24—H24 | 120.4 |
H11A—C11—H11B | 109.5 | C25—C24—H24 | 120.4 |
C3—C11—H11C | 109.5 | C20—C25—C24 | 121.5 (8) |
H11A—C11—H11C | 109.5 | C20—C25—H25 | 119.2 |
H11B—C11—H11C | 109.5 | C24—C25—H25 | 119.2 |
C17—C12—C13 | 116.6 (6) | F29—B26—F28 | 113.9 (9) |
C17—C12—C4 | 124.1 (6) | F29—B26—F30 | 98.9 (9) |
C13—C12—C4 | 119.3 (6) | F28—B26—F30 | 108.2 (9) |
C14—C13—C12 | 121.5 (8) | F29—B26—F27 | 109.4 (9) |
C14—C13—H13 | 119.2 | F28—B26—F27 | 116.6 (8) |
C12—C13—H13 | 119.2 | F30—B26—F27 | 108.3 (8) |
C9—C1—N2—C18 | −178.0 (5) | C3—C4—C12—C17 | 83.7 (7) |
C9—C1—N2—C3 | 2.2 (9) | C10—C4—C12—C13 | 139.5 (6) |
C1—N2—C3—C11 | 85.5 (6) | C3—C4—C12—C13 | −95.0 (7) |
C18—N2—C3—C11 | −94.3 (6) | C17—C12—C13—C14 | 1.9 (10) |
C1—N2—C3—C4 | −38.2 (7) | C4—C12—C13—C14 | −179.3 (6) |
C18—N2—C3—C4 | 141.9 (5) | C12—C13—C14—C15 | −1.5 (11) |
N2—C3—C4—C10 | 51.8 (6) | C13—C14—C15—C16 | 0.7 (12) |
C11—C3—C4—C10 | −70.7 (6) | C14—C15—C16—C17 | −0.4 (13) |
N2—C3—C4—C12 | −75.3 (6) | C15—C16—C17—C12 | 0.8 (14) |
C11—C3—C4—C12 | 162.2 (6) | C13—C12—C17—C16 | −1.5 (11) |
C10—C5—C6—C7 | −2.2 (11) | C4—C12—C17—C16 | 179.7 (7) |
C5—C6—C7—C8 | 0.9 (12) | C1—N2—C18—C20 | 103.3 (7) |
C6—C7—C8—C9 | 2.3 (11) | C3—N2—C18—C20 | −76.9 (7) |
C7—C8—C9—C10 | −4.3 (10) | C1—N2—C18—C19 | −127.1 (6) |
C7—C8—C9—C1 | 179.6 (6) | C3—N2—C18—C19 | 52.7 (8) |
N2—C1—C9—C8 | −164.3 (6) | N2—C18—C20—C25 | −88.9 (7) |
N2—C1—C9—C10 | 19.5 (9) | C19—C18—C20—C25 | 142.9 (7) |
C6—C5—C10—C9 | 0.3 (10) | N2—C18—C20—C21 | 91.9 (7) |
C6—C5—C10—C4 | −179.4 (6) | C19—C18—C20—C21 | −36.3 (9) |
C8—C9—C10—C5 | 2.9 (9) | C25—C20—C21—C22 | 0.4 (11) |
C1—C9—C10—C5 | 179.2 (6) | C18—C20—C21—C22 | 179.6 (7) |
C8—C9—C10—C4 | −177.4 (6) | C20—C21—C22—C23 | −0.1 (13) |
C1—C9—C10—C4 | −1.1 (9) | C21—C22—C23—C24 | 0.9 (15) |
C3—C4—C10—C5 | 146.2 (6) | C22—C23—C24—C25 | −2.0 (16) |
C12—C4—C10—C5 | −86.6 (7) | C21—C20—C25—C24 | −1.5 (12) |
C3—C4—C10—C9 | −33.5 (8) | C18—C20—C25—C24 | 179.3 (7) |
C12—C4—C10—C9 | 93.7 (7) | C23—C24—C25—C20 | 2.3 (15) |
C10—C4—C12—C17 | −41.8 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···F27 | 0.93 | 2.39 | 3.292 (9) | 164 |
C1—H1···F30 | 0.93 | 2.55 | 3.170 (12) | 125 |
C18—H18···F29 | 0.98 | 2.55 | 3.292 (10) | 132 |
C24—H24···F30i | 0.93 | 2.60 | 3.430 (15) | 148 |
C4—H4···F27ii | 0.98 | 2.54 | 3.498 (8) | 165 |
C11—H11A···F28ii | 0.96 | 2.50 | 3.268 (11) | 137 |
C14—H14···F28iii | 0.93 | 2.54 | 3.249 (10) | 133 |
C7—H7···F27iv | 0.93 | 2.65 | 3.399 (10) | 138 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z; (iii) x−1, y−1, z; (iv) y, x, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···F27 | 0.93 | 2.39 | 3.292 (9) | 163.8 |
C1—H1···F30 | 0.93 | 2.55 | 3.170 (12) | 124.8 |
C18—H18···F29 | 0.98 | 2.55 | 3.292 (10) | 132.2 |
C24—H24···F30i | 0.93 | 2.60 | 3.430 (15) | 148.3 |
C4—H4···F27ii | 0.98 | 2.54 | 3.498 (8) | 165.2 |
C11—H11A···F28ii | 0.96 | 2.50 | 3.268 (11) | 136.8 |
C14—H14···F28iii | 0.93 | 2.54 | 3.249 (10) | 133.4 |
C7—H7···F27iv | 0.93 | 2.65 | 3.399 (10) | 137.8 |
Symmetry codes: (i) x−1, y, z; (ii) x, y−1, z; (iii) x−1, y−1, z; (iv) y, x, −z. |
Acknowledgements
The authors thank Dr Marie-Thérèse Martin for her help and advice in NMR spectroscopy.
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In recent years, much effort has been devoted to the development of organocatalytic processes that afford metal-free procedures (Adam et al., 2001), such as asymmetric epoxidation catalysed by chiral iminium salts. It has been proved that iminium salts are effective catalysts at low loadings for enantioselective epoxidation using Oxone® (2KHSO5.KHSO4.K2SO4) as the stoichiometric oxidant.
As a part of our interest in catalytic epoxidation by dihydroisoquinolinium-derived iminium salts (Bohé et al., 1999), we report herein the synthesis from the corresponding (3R,4S)-3-methyl-4-phenyl-3,4-dihydroisoquinoleine (Davies et al., 1988), by N-alkylation with (1-bromoethyl)benzene, and the crystal structure determination of the title compound. It was isolated as one of the two diastereoisomeric products; it is a new dihydroisoquinolinium-derived iminium salt containing an asymmetric centre in an exocyclic substituent at the nitrogen atom. The X-ray analyses confirmed the 2D NMR data and allowed us to define the absolute configuration of the exocyclic substituent at the nitrogen atom to be R (Fig. 1). The tetrahydroisoquinoline unit is substituted by methyl group in position 3, a phenyl substituent in position 4, both in axial conformation, and a (1-phenylethyl) group at the nitrogen atom (Fig.1). The six-heteromembered ring adopts a screw-boat conformation (rather than a half-chair one as previously described), as indicated by puckering analysis [Q = 0.474 (6) Å, θ = 113.8 (7)°, φ = 93.9 (8) °] (Cremer & Pople, 1975). The two phenyl rings in position C4 and C18 are almost facing each other with a dihedral angle of 19.3 (4)° but with a rather long centroid-centroid distance of 4.129 (3)Å. In the crystal of the iminium salt, significant contacts between cationic species are uniquely mediated by BF4- anions, each of them being surrounded by five cations (Fig. 2). The tetrafluoridoborate anions are involved in intensive thermal motion, thus some B–F bond lengths and angles [range from 1.281 (10) to 1.327 (10) Å and from 98.9 (9) to 116.6 (8)°, respectively] deviate significantly from their standard values.