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Acta Cryst. (2008). E64, o361    [ doi:10.1107/S1600536807066020 ]

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

S. Alam, M. Hasan, S. Saeed, A. Fischer and N. Khan

Abstract top

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.

Comment top

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.

Related literature top

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

Experimental top

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 top

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).

Computing details top

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

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level for non-H atoms.
[Figure 2] Fig. 2. The intermolecular N—H···O hydrogen bond (dashed line). H atoms not involved in hydrogen bonding are omitted.
cis-(9S,10S)-Methyl 1-propyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylate top
Crystal data top
C16H20N2O2Z = 8
Mr = 272.34F000 = 1168
Tetragonal, P43212Dx = 1.148 Mg m−3
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 mm−1
α = 90ºT = 298 K
β = 90ºBlock, colourless
γ = 90º0.30 × 0.30 × 0.30 mm
V = 3152.1 (7) Å3
Data collection top
Bruker–Nonius KappaCCD diffractometerRint = 0.043
Radiation source: fine-focus sealed tubeθmax = 25.5º
φ & 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 top
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 Å−3
189 parametersΔρmin = −0.14 e Å−3
2 restraintsExtinction correction: none
Crystal data top
C16H20N2O2γ = 90º
Mr = 272.34V = 3152.1 (7) Å3
Tetragonal, P43212Z = 8
a = 9.3410 (11) ÅMo Kα
b = 9.3410 (11) ŵ = 0.08 mm−1
c = 36.125 (5) ÅT = 298 K
α = 90º0.30 × 0.30 × 0.30 mm
β = 90º
Data collection top
Bruker–Nonius KappaCCD diffractometer1778 independent reflections
Absorption correction: none1285 reflections with I > 2σ(I)
10764 measured reflectionsRint = 0.043
Refinement top
R[F2 > 2σ(F2)] = 0.048H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.116Δρmax = 0.18 e Å−3
S = 1.08Δρmin = −0.14 e Å−3
1778 reflectionsAbsolute structure: ?
189 parametersFlack parameter: ?
2 restraintsRogers parameter: ?
Special details top

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) top
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) top
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, °) top
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, °) top
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.
Table 1
Hydrogen-bond geometry (Å, °) top
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.
Acknowledgements top

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

references
References top

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