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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o361.
Published online 2008 January 4. doi:  10.1107/S1600536807066020
PMCID: PMC2960416

cis-(9S,10S)-Methyl 1-propyl-1,2,3,4-tetra­hydro-β-carboline-3-carboxyl­ate

Abstract

The title compound, C16H20N2O2, was synthesized from (S)-tryptophan methyl ester hydro­chloride and butyraldehyde. The absolute configuration 9S,10S was assigned on the basis of the unchanging chirality of the C9 centre. The NH group of the indole ring is involved in inter­molecular N—H(...)O hydrogen bonding, while the NH group of the six-membered ring is not. This latter ring has a half-chair conformation.

Related literature

For related literature, see: Agurell et al. (1969 [triangle]); Bein (1953 [triangle]); Herraiz (2000 [triangle]); Johnson et al. (1963 [triangle]); Petter & Engelmann (1974 [triangle]). For synthetic details, see: Greenstein & Winiz (1961 [triangle]); Snyder et al. (1948 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o361-scheme1.jpg

Experimental

Crystal data

  • C16H20N2O2
  • M r = 272.34
  • Tetragonal, An external file that holds a picture, illustration, etc.
Object name is e-64-0o361-efi1.jpg
  • a = 9.3410 (11) Å
  • c = 36.125 (5) Å
  • V = 3152.1 (7) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 298 K
  • 0.30 × 0.30 × 0.30 mm

Data collection

  • Bruker–Nonius KappaCCD diffractometer
  • Absorption correction: none
  • 10764 measured reflections
  • 1778 independent reflections
  • 1285 reflections with I > 2σ(I)
  • R int = 0.043

Refinement

  • R[F 2 > 2σ(F 2)] = 0.048
  • wR(F 2) = 0.116
  • S = 1.08
  • 1778 reflections
  • 189 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.18 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: COLLECT (Nonius, 1999 [triangle]); cell refinement: DIRAX (Duisenberg, 1992 [triangle]); data reduction: EVALCCD (Duisenberg et al., 2003 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: DIAMOND (Brandenburg, 2007 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2008 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807066020/bi2260sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807066020/bi2260Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

MH is grateful to the Alexander von Humboldt Foundation, Germany, and AF thanks the Swedish Research Council for financial assistance.

supplementary crystallographic information

Comment

Keeping in mind the diverse biological activities of alkaloids containing an indole or indoline nucleus (Agurell et al., 1969; Bein, 1953; Johnson et al., 1963; Herraiz, 2000), we have designed and synthesized some optically active compounds containing the tetrahydro-β-carboline nucleus. We report here the crystal structure of the title compound.

Experimental

The title compound was prepared by condensation of (S)-tryptophan methyl ester hydrochloride with an aldehyde under polar protic conditions (Greenstein & Winiz, 1961; Snyder et al., 1948). (S)-tryptophan methyl ester hydrochloride (1.5 g, 0.0059 mol) and butyraldehyde (1.50 ml, 0.0059 mol) were dissolved in methanol/water solution (50 ml, 75/25%, v/v). The mixture was refluxed for 48 h, cooled and the solvent evaporated under vacuum. The residue was dissolved in 14% ammonium hydroxide, extracted with chloroform and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure to yield an oily residue which was subjected to column chromatography. The purified oil was crystallized from benzene/pet. ether (b.p. 373–393 K) to give the title compound: yield 1.2 g, 74.8%, m.p. 413 K, Rf 0.84 methanol / chloroform (3:7). [a]D28-132.8 (c = 0.00348, acetonitrile). The product after purification was subjected to different spectroscopic techniques. This data together with the result of elemental analysis confirmed the formation of a pure stereoisomer.

Refinement

In the absence of significant anomalous scattering effects, Friedel pairs were merged prior to refinement. All C-bonded H atoms were placed at calculated positions. The two N-bonded H atoms were located from the Fourier map and were refined with the restraint N—H = 0.89 (1) Å. The isotropic displacement parameters of the H atoms were fixed at Uiso(H) = 1.2Ueq(C/N) (1.5Ueq(C) for the methyl groups).

Figures

Fig. 1.
The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms.
Fig. 2.
The intermolecular N—H···O hydrogen bond (dashed line). H atoms not involved in hydrogen bonding are omitted.

Crystal data

C16H20N2O2Z = 8
Mr = 272.34F000 = 1168
Tetragonal, P43212Dx = 1.148 Mg m3
Hall symbol: P 4nw 2abwMo Kα radiation λ = 0.71073 Å
a = 9.3410 (11) ÅCell parameters from 87 reflections
b = 9.3410 (11) Åθ = 3.8–15.5º
c = 36.125 (5) ŵ = 0.08 mm1
α = 90ºT = 298 K
β = 90ºBlock, colourless
γ = 90º0.30 × 0.30 × 0.30 mm
V = 3152.1 (7) Å3

Data collection

Bruker–Nonius KappaCCD diffractometerRint = 0.043
Radiation source: fine-focus sealed tubeθmax = 25.5º
[var phi] & ω scansθmin = 4.5º
Absorption correction: noneh = −10→11
10764 measured reflectionsk = −10→11
1778 independent reflectionsl = −42→43
1285 reflections with I > 2σ(I)

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.116  w = 1/[σ2(Fo2) + (0.0441P)2 + 0.674P] where P = (Fo2 + 2Fc2)/3
S = 1.08(Δ/σ)max < 0.001
1778 reflectionsΔρmax = 0.18 e Å3
189 parametersΔρmin = −0.14 e Å3
2 restraintsExtinction correction: none

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
C11.0247 (3)1.1462 (3)0.13466 (8)0.0614 (8)
C21.0963 (4)1.2716 (4)0.12461 (10)0.0795 (10)
C31.0883 (4)1.3850 (4)0.14882 (13)0.0947 (12)
C41.0138 (5)1.3760 (4)0.18233 (12)0.0943 (12)
C50.9434 (4)1.2512 (4)0.19235 (10)0.0787 (10)
C60.9480 (3)1.1324 (3)0.16848 (8)0.0600 (8)
C70.8933 (3)0.9871 (3)0.16950 (7)0.0570 (7)
C80.9361 (3)0.9219 (3)0.13770 (7)0.0559 (7)
C90.9096 (3)0.7685 (3)0.12739 (8)0.0618 (8)
C100.8291 (3)0.7477 (3)0.19244 (7)0.0607 (8)
C110.8098 (4)0.9089 (3)0.19896 (7)0.0654 (8)
C120.8563 (4)0.7499 (3)0.08743 (7)0.0733 (9)
C130.8352 (5)0.5956 (4)0.07535 (9)0.0947 (12)
C140.7879 (7)0.5844 (6)0.03549 (11)0.156 (2)
C150.7327 (3)0.6573 (4)0.21666 (7)0.0668 (8)
C160.6592 (6)0.6136 (5)0.27900 (9)0.140 (2)
O10.6595 (3)0.5587 (3)0.20643 (5)0.0843 (7)
O20.7402 (3)0.6986 (3)0.25177 (6)0.1103 (10)
N11.0152 (3)1.0167 (3)0.11634 (7)0.0639 (7)
N20.7998 (3)0.7132 (3)0.15343 (7)0.0660 (7)
H21.14721.27810.10250.095*
H31.13391.47030.14270.114*
H41.01141.45470.19810.113*
H50.89361.24610.21460.094*
H90.99830.71390.13060.074*
H100.92880.72260.19790.073*
H11A0.70930.93420.19750.078*
H11B0.84490.93490.22330.078*
H12A0.76600.80010.08480.088*
H12B0.92450.79490.07090.088*
H13A0.92440.54380.07850.114*
H13B0.76400.55090.09110.114*
H14A0.70470.64290.03170.235*
H14B0.76530.48660.02980.235*
H14C0.86370.61660.01960.235*
H16A0.55890.61860.27340.211*
H16B0.67570.65110.30340.211*
H16C0.69030.51570.27800.211*
H1N1.052 (3)0.996 (3)0.0958 (9)0.077*
H2N0.799 (3)0.620 (4)0.1515 (9)0.079*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.0602 (19)0.0582 (19)0.0658 (18)0.0029 (14)−0.0028 (15)0.0070 (15)
C20.084 (2)0.067 (2)0.087 (2)−0.0118 (18)−0.0036 (18)0.0132 (19)
C30.094 (3)0.068 (2)0.121 (3)−0.015 (2)−0.010 (3)0.017 (2)
C40.105 (3)0.055 (2)0.123 (3)−0.001 (2)−0.019 (3)−0.012 (2)
C50.087 (3)0.068 (2)0.081 (2)0.0092 (19)−0.0023 (19)−0.0071 (19)
C60.0579 (18)0.0541 (17)0.0679 (18)0.0069 (14)−0.0079 (15)−0.0013 (15)
C70.0585 (18)0.0534 (17)0.0590 (16)0.0006 (13)0.0017 (13)0.0011 (14)
C80.0575 (17)0.0558 (17)0.0542 (15)−0.0043 (14)0.0037 (14)0.0027 (14)
C90.0640 (19)0.0601 (18)0.0614 (16)−0.0018 (15)0.0041 (14)−0.0013 (14)
C100.0611 (19)0.068 (2)0.0535 (15)−0.0128 (15)−0.0004 (14)0.0025 (14)
C110.072 (2)0.069 (2)0.0553 (16)−0.0053 (16)0.0071 (15)−0.0030 (15)
C120.086 (2)0.076 (2)0.0581 (17)−0.0049 (18)0.0105 (17)−0.0059 (16)
C130.122 (3)0.084 (3)0.078 (2)−0.008 (2)0.005 (2)−0.018 (2)
C140.239 (7)0.143 (5)0.087 (3)−0.011 (5)−0.025 (4)−0.042 (3)
C150.070 (2)0.079 (2)0.0511 (17)−0.0185 (17)−0.0037 (15)0.0033 (16)
C160.208 (6)0.148 (4)0.065 (2)−0.090 (4)0.027 (3)0.006 (2)
O10.0951 (17)0.0920 (17)0.0658 (13)−0.0389 (15)−0.0028 (12)0.0037 (12)
O20.150 (2)0.127 (2)0.0542 (12)−0.0739 (18)0.0075 (14)0.0014 (14)
N10.0699 (17)0.0634 (16)0.0583 (14)−0.0033 (13)0.0096 (13)0.0024 (13)
N20.0749 (17)0.0676 (17)0.0555 (14)−0.0187 (14)0.0069 (12)−0.0051 (13)

Geometric parameters (Å, °)

C1—N11.382 (4)C16—O21.473 (4)
C1—C21.397 (4)C2—H20.930
C1—C61.422 (4)C3—H30.930
C2—C31.376 (5)C4—H40.930
C3—C41.399 (5)C5—H50.930
C4—C51.386 (5)C9—H90.980
C5—C61.406 (4)C10—H100.980
C6—C71.452 (4)C11—H11A0.970
C7—C81.360 (4)C11—H11B0.970
C7—C111.508 (4)C12—H12A0.970
C8—N11.388 (3)C12—H12B0.970
C8—C91.501 (4)C13—H13A0.970
C9—N21.484 (4)C13—H13B0.970
C9—C121.537 (4)C14—H14A0.960
C10—N21.471 (4)C14—H14B0.960
C10—C151.513 (4)C14—H14C0.960
C10—C111.535 (4)C16—H16A0.960
C12—C131.519 (5)C16—H16B0.960
C13—C141.510 (5)C16—H16C0.960
C15—O11.206 (3)N1—H1N0.84 (3)
C15—O21.327 (3)N2—H2N0.87 (3)
N1—C1—C2129.8 (3)C6—C5—H5120.4
N1—C1—C6107.5 (3)N2—C9—H9109.1
C2—C1—C6122.7 (3)C8—C9—H9109.1
C3—C2—C1117.0 (3)C12—C9—H9109.1
C2—C3—C4122.0 (3)N2—C10—H10108.4
C5—C4—C3120.9 (4)C15—C10—H10108.4
C4—C5—C6119.2 (3)C11—C10—H10108.4
C5—C6—C1118.1 (3)C7—C11—H11A110.1
C5—C6—C7135.4 (3)C10—C11—H11A110.1
C1—C6—C7106.5 (2)C7—C11—H11B110.1
C8—C7—C6107.1 (2)C10—C11—H11B110.1
C8—C7—C11122.1 (3)H11A—C11—H11B108.5
C6—C7—C11130.8 (3)C13—C12—H12A108.6
C7—C8—N1109.9 (3)C9—C12—H12A108.6
C7—C8—C9126.0 (3)C13—C12—H12B108.6
N1—C8—C9124.0 (2)C9—C12—H12B108.6
N2—C9—C8106.8 (2)H12A—C12—H12B107.5
N2—C9—C12109.4 (2)C14—C13—H13A109.2
C8—C9—C12113.2 (3)C12—C13—H13A109.2
N2—C10—C15108.7 (2)C14—C13—H13B109.2
N2—C10—C11109.9 (2)C12—C13—H13B109.2
C15—C10—C11112.9 (3)H13A—C13—H13B107.9
C7—C11—C10107.8 (2)C13—C14—H14A109.5
C13—C12—C9114.8 (3)C13—C14—H14B109.5
C14—C13—C12112.2 (3)H14A—C14—H14B109.5
O1—C15—O2123.0 (3)C13—C14—H14C109.5
O1—C15—C10125.9 (3)H14A—C14—H14C109.5
O2—C15—C10111.0 (3)H14B—C14—H14C109.5
C15—O2—C16117.0 (3)O2—C16—H16A109.5
C1—N1—C8109.1 (2)O2—C16—H16B109.5
C10—N2—C9113.7 (2)H16A—C16—H16B109.5
C3—C2—H2121.5O2—C16—H16C109.5
C1—C2—H2121.5H16A—C16—H16C109.5
C2—C3—H3119.0H16B—C16—H16C109.5
C4—C3—H3119.0C1—N1—H1N127 (2)
C5—C4—H4119.6C8—N1—H1N124 (2)
C3—C4—H4119.6C10—N2—H2N107 (2)
C4—C5—H5120.4C9—N2—H2N108 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.84 (3)2.20 (3)3.037 (3)177 (3)

Symmetry codes: (i) x+1/2, −y+3/2, −z+1/4.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BI2260).

References

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  • Bein, H. J. (1953). Experientia, 9, 107–110. [PubMed]
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  • Duisenberg, A. J. M., Kroon-Batenburg, L. M. J. & Schreurs, A. M. M. (2003). J. Appl. Cryst.36, 220–229.
  • Greenstein, J. P. & Winiz, M. (1961). Chemistry of Amino Acids, Vol. II, p. 926. Weinheim: John Wiley and Sons Inc.
  • Herraiz, T. (2000). J. Agric. Food Chem.48, 4900–4904. [PubMed]
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  • Westrip, S. (2008). publCIF In preparation.

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