Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100014724/gs1106sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100014724/gs1106IVsup2.hkl |
CCDC reference: 158270
The absolute configuration was determined by refinement of the Flack (1983) parameter, based on 1143 Friedel pairs. The reported configuration yielded x = 0.01 (14) while the inverse configuration yielded x = 1.01 (14). The NH and CH H atoms were included in the observed positions and refined. Other H atoms were placed in calculated positions with C—H distances of 0.93 (Csp2), 0.97 (CH2) and 0.96 Å (CH3). All hydrogen atoms were assigned an isotropic displacement parameter corresponding to 1.2Ueq of the attached parent atom.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. View of C17H23NO2 showing the labelling of the non-H atoms. Displacement ellipsoids are shown at the 30% probability level; H atoms are drawn as small circles of arbitrary radius. |
C17H23NO2 | F(000) = 296 |
Mr = 273.36 | Dx = 1.191 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6653 (6) Å | Cell parameters from 5338 reflections |
b = 5.0767 (4) Å | θ = 4.4–25.3° |
c = 22.615 (2) Å | µ = 0.08 mm−1 |
β = 95.262 (2)° | T = 293 K |
V = 762.0 (2) Å3 | Needle, colourless |
Z = 2 | 0.20 × 0.18 × 0.08 mm |
Bruker SMART-CCD diffractometer | 2422 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 25.3°, θmin = 2.7° |
ω scans | h = −7→7 |
9999 measured reflections | k = −6→6 |
2673 independent reflections | l = −27→27 |
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0703P)2 + 0.0399P] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.036 | (Δ/σ)max = 0.001 |
wR(F2) = 0.107 | Δρmax = 0.18 e Å−3 |
S = 1.06 | Δρmin = −0.16 e Å−3 |
2673 reflections | Absolute structure: Flack (1983) |
191 parameters | Absolute structure parameter: 0.01 (14) |
1 restraint |
C17H23NO2 | V = 762.0 (2) Å3 |
Mr = 273.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.6653 (6) Å | µ = 0.08 mm−1 |
b = 5.0767 (4) Å | T = 293 K |
c = 22.615 (2) Å | 0.20 × 0.18 × 0.08 mm |
β = 95.262 (2)° |
Bruker SMART-CCD diffractometer | 2422 reflections with I > 2σ(I) |
9999 measured reflections | Rint = 0.023 |
2673 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.107 | Δρmax = 0.18 e Å−3 |
S = 1.06 | Δρmin = −0.16 e Å−3 |
2673 reflections | Absolute structure: Flack (1983) |
191 parameters | Absolute structure parameter: 0.01 (14) |
1 restraint |
Experimental. The crystal was positioned at a distance of 45 mm from the CCD area- detector entry. 3600 frames were recorded as an ω scan of 0.3 degees. The integration (Lorentz and polarization correction, data reduction and processing) was carried out using the SAINT program of the SMART CCD software package (Bruker, 1998). The structure was solved by direct methods (SIR92, (Altomare et al., 1993)) and refined by a full-matrix least-squares procedure (SHELXL97 (Sheldrick, 1997)). |
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 | ||
C1 | 0.0510 (3) | 0.0142 (5) | 0.43540 (9) | 0.0689 (5) | |
H1A | 0.1216 | −0.1472 | 0.4296 | 0.083* | |
H1B | −0.0268 | 0.0622 | 0.3992 | 0.083* | |
H1C | −0.0372 | −0.0094 | 0.4663 | 0.082* | |
O1 | 0.1917 (2) | 0.2164 (3) | 0.45189 (5) | 0.0686 (4) | |
C2 | 0.3333 (2) | 0.2774 (4) | 0.41389 (7) | 0.0524 (4) | |
C3 | 0.4720 (3) | 0.4662 (4) | 0.43405 (8) | 0.0628 (5) | |
H3 | 0.4653 | 0.5432 | 0.4711 | 0.075* | |
C4 | 0.6200 (3) | 0.5396 (4) | 0.39895 (9) | 0.0659 (5) | |
H4 | 0.7133 | 0.6663 | 0.413 | 0.079* | |
C5 | 0.6351 (2) | 0.4312 (4) | 0.34327 (8) | 0.0525 (4) | |
C6 | 0.8037 (3) | 0.5158 (4) | 0.30655 (10) | 0.0666 (5) | |
H6A | 0.9275 | 0.4282 | 0.3215 | 0.08* | |
H6B | 0.8246 | 0.7041 | 0.311 | 0.08* | |
C7 | 0.7580 (3) | 0.4509 (5) | 0.24100 (10) | 0.0698 (6) | |
H7A | 0.6507 | 0.5639 | 0.2238 | 0.084* | |
H7B | 0.8767 | 0.4826 | 0.2202 | 0.084* | |
C8 | 0.6952 (3) | 0.1655 (4) | 0.23386 (10) | 0.0671 (5) | |
H8A | 0.8014 | 0.0538 | 0.2522 | 0.08* | |
H8B | 0.6767 | 0.1222 | 0.1919 | 0.08* | |
C9 | 0.4988 (3) | 0.1104 (4) | 0.26230 (8) | 0.0510 (4) | |
H9 | 0.490 (3) | −0.069 (5) | 0.2689 (9) | 0.061* | |
C10 | 0.4954 (2) | 0.2413 (3) | 0.32264 (7) | 0.0456 (4) | |
C11 | 0.3448 (2) | 0.1651 (3) | 0.35862 (7) | 0.0480 (4) | |
H11 | 0.2516 | 0.0373 | 0.3451 | 0.057* | |
C12 | 0.3096 (3) | 0.1760 (3) | 0.22112 (7) | 0.0546 (4) | |
H12A | 0.1951 | 0.1878 | 0.2445 | 0.065* | |
H12B | 0.3271 | 0.3467 | 0.203 | 0.065* | |
C13 | 0.2662 (4) | −0.0230 (6) | 0.17362 (11) | 0.0880 (8) | |
H13A | 0.382 | −0.0356 | 0.1507 | 0.105* | |
H13B | 0.2488 | −0.1931 | 0.192 | 0.105* | |
N1 | 0.0893 (3) | 0.0323 (3) | 0.13336 (6) | 0.0584 (4) | |
H1 | 0.067 (3) | 0.190 (6) | 0.1252 (10) | 0.07* | |
C14 | −0.0154 (3) | −0.1599 (4) | 0.10576 (7) | 0.0538 (4) | |
O2 | 0.0279 (2) | −0.3937 (3) | 0.11287 (7) | 0.0752 (5) | |
C15 | −0.1913 (3) | −0.0772 (4) | 0.06503 (9) | 0.0638 (5) | |
H15 | −0.217 (3) | 0.104 (6) | 0.0602 (10) | 0.076* | |
C16 | −0.3728 (3) | −0.2522 (6) | 0.05985 (11) | 0.0849 (7) | |
H16A | −0.3687 | −0.4099 | 0.0841 | 0.102* | |
H16B | −0.504 | −0.1691 | 0.0536 | 0.102* | |
C17 | −0.2417 (4) | −0.2429 (6) | 0.01076 (9) | 0.0804 (7) | |
H17A | −0.2927 | −0.1539 | −0.0255 | 0.096* | |
H17B | −0.1573 | −0.3948 | 0.0051 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0669 (12) | 0.0803 (14) | 0.0622 (10) | −0.0126 (11) | 0.0201 (9) | 0.0040 (11) |
O1 | 0.0665 (8) | 0.0902 (10) | 0.0509 (6) | −0.0134 (8) | 0.0149 (6) | −0.0109 (7) |
C2 | 0.0509 (9) | 0.0614 (11) | 0.0447 (8) | −0.0007 (8) | 0.0022 (7) | 0.0024 (8) |
C3 | 0.0686 (11) | 0.0688 (13) | 0.0493 (9) | −0.0085 (10) | −0.0043 (8) | −0.0078 (9) |
C4 | 0.0636 (11) | 0.0653 (12) | 0.0660 (11) | −0.0164 (10) | −0.0094 (9) | −0.0008 (10) |
C5 | 0.0463 (9) | 0.0508 (9) | 0.0590 (9) | −0.0028 (8) | −0.0028 (7) | 0.0132 (8) |
C6 | 0.0498 (10) | 0.0658 (11) | 0.0839 (13) | −0.0084 (9) | 0.0037 (9) | 0.0212 (11) |
C7 | 0.0655 (11) | 0.0676 (13) | 0.0805 (13) | 0.0043 (10) | 0.0291 (10) | 0.0174 (10) |
C8 | 0.0648 (11) | 0.0610 (13) | 0.0795 (13) | 0.0114 (9) | 0.0282 (9) | 0.0094 (10) |
C9 | 0.0502 (9) | 0.0492 (9) | 0.0547 (9) | 0.0063 (8) | 0.0117 (7) | 0.0034 (8) |
C10 | 0.0403 (8) | 0.0470 (9) | 0.0490 (8) | 0.0053 (7) | 0.0018 (6) | 0.0068 (7) |
C11 | 0.0442 (8) | 0.0518 (10) | 0.0474 (8) | −0.0043 (7) | 0.0018 (6) | −0.0020 (7) |
C12 | 0.0632 (10) | 0.0527 (11) | 0.0481 (9) | 0.0123 (8) | 0.0062 (7) | −0.0010 (7) |
C13 | 0.0869 (15) | 0.0886 (16) | 0.0836 (15) | 0.0345 (13) | −0.0181 (12) | −0.0322 (13) |
N1 | 0.0742 (10) | 0.0482 (8) | 0.0516 (8) | 0.0114 (7) | −0.0001 (7) | −0.0032 (7) |
C14 | 0.0743 (11) | 0.0468 (10) | 0.0415 (8) | 0.0092 (8) | 0.0121 (8) | 0.0002 (7) |
O2 | 0.1026 (11) | 0.0475 (8) | 0.0731 (9) | 0.0135 (7) | −0.0046 (8) | −0.0004 (6) |
C15 | 0.0804 (13) | 0.0538 (10) | 0.0562 (10) | 0.0132 (10) | 0.0000 (9) | −0.0037 (8) |
C16 | 0.0696 (13) | 0.0979 (18) | 0.0870 (15) | 0.0044 (13) | 0.0060 (11) | −0.0184 (14) |
C17 | 0.0901 (14) | 0.0907 (17) | 0.0584 (11) | 0.0111 (13) | −0.0048 (10) | −0.0155 (12) |
C1—O1 | 1.417 (3) | C9—C10 | 1.520 (3) |
O1—C2 | 1.369 (2) | C9—C12 | 1.534 (3) |
C2—C3 | 1.380 (3) | C10—C11 | 1.403 (2) |
C2—C11 | 1.383 (2) | C12—C13 | 1.484 (3) |
C3—C4 | 1.373 (3) | C13—N1 | 1.450 (3) |
C4—C5 | 1.386 (3) | N1—C14 | 1.322 (3) |
C5—C10 | 1.391 (2) | C14—O2 | 1.228 (2) |
C5—C6 | 1.519 (3) | C14—C15 | 1.484 (3) |
C6—C7 | 1.522 (3) | C15—C16 | 1.496 (4) |
C7—C8 | 1.513 (3) | C15—C17 | 1.500 (3) |
C8—C9 | 1.537 (3) | C16—C17 | 1.475 (3) |
C2—O1—C1 | 118.43 (14) | C5—C10—C11 | 119.28 (15) |
O1—C2—C3 | 115.41 (15) | C5—C10—C9 | 122.68 (15) |
O1—C2—C11 | 125.00 (16) | C11—C10—C9 | 118.04 (15) |
C3—C2—C11 | 119.59 (15) | C2—C11—C10 | 120.85 (15) |
C4—C3—C2 | 119.51 (16) | C13—C12—C9 | 112.75 (15) |
C3—C4—C5 | 122.23 (17) | N1—C13—C12 | 114.60 (18) |
C4—C5—C10 | 118.53 (16) | C14—N1—C13 | 121.12 (19) |
C4—C5—C6 | 120.22 (17) | O2—C14—N1 | 122.95 (19) |
C10—C5—C6 | 121.23 (17) | O2—C14—C15 | 121.15 (18) |
C5—C6—C7 | 112.28 (16) | N1—C14—C15 | 115.91 (18) |
C8—C7—C6 | 109.87 (18) | C14—C15—C16 | 117.9 (2) |
C7—C8—C9 | 111.58 (15) | C14—C15—C17 | 117.01 (18) |
C10—C9—C12 | 111.79 (14) | C16—C15—C17 | 58.97 (16) |
C10—C9—C8 | 112.29 (16) | C17—C16—C15 | 60.65 (16) |
C12—C9—C8 | 113.01 (15) | C16—C17—C15 | 60.38 (16) |
C1—O1—C2—C3 | −176.73 (17) | C12—C9—C10—C11 | 64.4 (2) |
C1—O1—C2—C11 | 3.3 (3) | C8—C9—C10—C11 | −167.39 (15) |
O1—C2—C3—C4 | 179.87 (18) | O1—C2—C11—C10 | 179.74 (16) |
C11—C2—C3—C4 | −0.1 (3) | C3—C2—C11—C10 | −0.2 (3) |
C2—C3—C4—C5 | 0.4 (3) | C5—C10—C11—C2 | 0.4 (2) |
C3—C4—C5—C10 | −0.2 (3) | C9—C10—C11—C2 | −179.79 (16) |
C3—C4—C5—C6 | −179.00 (18) | C10—C9—C12—C13 | −156.68 (19) |
C4—C5—C6—C7 | −160.80 (17) | C8—C9—C12—C13 | 75.5 (2) |
C10—C5—C6—C7 | 20.4 (2) | C9—C12—C13—N1 | −179.57 (19) |
C5—C6—C7—C8 | −50.6 (2) | C12—C13—N1—C14 | −152.2 (2) |
C6—C7—C8—C9 | 63.4 (2) | C13—N1—C14—O2 | 1.0 (3) |
C7—C8—C9—C10 | −43.2 (2) | C13—N1—C14—C15 | −179.08 (19) |
C7—C8—C9—C12 | 84.4 (2) | O2—C14—C15—C16 | 34.0 (3) |
C4—C5—C10—C11 | −0.2 (2) | N1—C14—C15—C16 | −145.88 (19) |
C6—C5—C10—C11 | 178.60 (15) | O2—C14—C15—C17 | −33.3 (3) |
C4—C5—C10—C9 | −179.98 (17) | N1—C14—C15—C17 | 146.8 (2) |
C6—C5—C10—C9 | −1.2 (2) | C14—C15—C16—C17 | −106.3 (2) |
C12—C9—C10—C5 | −115.82 (17) | C14—C15—C17—C16 | 107.8 (2) |
C8—C9—C10—C5 | 12.4 (2) |
Experimental details
Crystal data | |
Chemical formula | C17H23NO2 |
Mr | 273.36 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.6653 (6), 5.0767 (4), 22.615 (2) |
β (°) | 95.262 (2) |
V (Å3) | 762.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.20 × 0.18 × 0.08 |
Data collection | |
Diffractometer | Bruker SMART-CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9999, 2673, 2422 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.600 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.107, 1.06 |
No. of reflections | 2673 |
No. of parameters | 191 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.16 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.01 (14) |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C1—O1 | 1.417 (3) | C14—C15 | 1.484 (3) |
O1—C2 | 1.369 (2) | C15—C16 | 1.496 (4) |
C13—N1 | 1.450 (3) | C15—C17 | 1.500 (3) |
N1—C14 | 1.322 (3) | C16—C17 | 1.475 (3) |
C14—O2 | 1.228 (2) | ||
C2—O1—C1 | 118.43 (14) | N1—C14—C15 | 115.91 (18) |
O1—C2—C3 | 115.41 (15) | C14—C15—C16 | 117.9 (2) |
O1—C2—C11 | 125.00 (16) | C14—C15—C17 | 117.01 (18) |
C14—N1—C13 | 121.12 (19) | C16—C15—C17 | 58.97 (16) |
O2—C14—N1 | 122.95 (19) | C17—C16—C15 | 60.65 (16) |
O2—C14—C15 | 121.15 (18) | C16—C17—C15 | 60.38 (16) |
C1—O1—C2—C3 | −176.73 (17) | C9—C12—C13—N1 | −179.57 (19) |
C1—O1—C2—C11 | 3.3 (3) | C12—C13—N1—C14 | −152.2 (2) |
C10—C9—C12—C13 | −156.68 (19) | C13—N1—C14—O2 | 1.0 (3) |
C8—C9—C12—C13 | 75.5 (2) | C13—N1—C14—C15 | −179.08 (19) |
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Melatonin (N-acetyl-5-methoxytryptamine), (I), is a hormone synthesized and secreted primarily by the pineal gland during darkness, by all mammalian species (Reiter, 1991). The hormone has been the focus of considerable clinical interest in recent years. It is now well recognized that it regulates circadian rhythms in humans and in different animal species (Arendt & Deacon, 1997). Melatonin's effects seem to be mediated through membrane receptors, recently classified as MT1, MT2 and MT3. \sch
This interest prompted us to develop new melatonin receptor ligands and led us to the synthesis (Yous et al., 1992) and crystallographic studies of naphthalenic bioisosteres (II) and (III) (Tinant et al., 1993, 1994). Recently we have synthesized a tetrahydronaphtalenic analog, (IV) (Fourmaitraux et al., 1998). The presence of a chiral centre in this compound together with the pharmacological studies which showed enantiomers of many drugs differ in activity, metabolism, toxicity, trigger the investigation of the racemic mixture (IV). Chiral direct HPLC has been recognized as a useful methodology for the resolution of racemates (Francotte & Junker-Buchheit, 1992). We obtain the two enantiomers of (4) (Belloli et al., 2000), by preparative chiral HPLc to investigate their biochemical stereoselective affinity. Preliminary results show that the (-) form is the most affin enantiomer. Therefore, our pronounced interest was focused on the elucidation of the absolute configuration of the tetrahydronaphthalenic analogues of melatonin. A view of the molecule (4) with the atomic numbering is given in Fig. 1. The chiral center is found to have the R configuration. The nonaromatic nucleus shows a half-chair conformation. Methylene atoms C7 and C8 are located at -0.475 (5) and 0.278 (5) Å, respectively, from the mean molecular plane (C5,C6,C9,C10). The amide and the naphthalene moieties are practically perpendicular: the dihedral angle between the two mean planes was 87.6 (1)°. This conformation is different from that of one of the two independant molecules of N-cyclopropylcarbonyl-2-(7-methoxy-1-naphthyl)ethylamine (Tinant et al., 1993) in which the amide and the naphthalene planes are approximately parallel. The methoxy group is close to the plane of the aromatic ring and the conformation about C2—O1 bond is staggered (sp) with a torsion angle C11—C2—O1—C1 of 3.3 (3)°. The distance between the methoxy O atom O1 and the amide H atom H1, i.e. the two presumed polar anchoring points on the receptor (Lesieur, 1992), is 7.36 Å. By comparison, this distance is 7.34 Å in melatonin (Mostad & Romming, 1974) and 6.98 Å in molecule (A) of N-cyclopropylcarbonyl-2-(7-methoxy-1-naphthyl)ethylamine (Tinant et al., 1993).