organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

N-Methyl-N-styrylcinnamamide (lansamide) from Clausena lansium in Vietnam

aInstitut für Chemie und Biochemie-Kristallographie, Fachbereich Biologie-Chemie-Pharmazie der Freien Universität, Fabeckstrasse 36a, 14195 Berlin, Germany, bFaculty of Chemistry, Vinh University, 182-Le Duan, Vinh City, Nghean Province, Vietnam, and cFaculty of Chemistry, College of Natural Sciences, Hanoi National University, 19-Le Thanh Tong Street, 10 000 Hanoi, Vietnam
*Correspondence e-mail: luger@chemie.fu-berlin.de

(Received 13 March 2009; accepted 16 March 2009; online 19 March 2009)

The title compound, C18H17NO, was isolated from the seeds of Clausena lansium (wampee) (Rutaceae). The X-ray crystal structure analysis confirmed its chemical identity and revealed that it is solvent-free, in contrast to the previously reported monohydrate [Huang, Ou & Tang (2006[Huang, X.-S., Ou, S.-Y. & Tang, S.-Z. (2006). Acta Cryst. E62, o1987-o1988.]). Acta Cryst. E62, o1987–o1988]. The mol­ecular structures are practically identical but the mol­ecules pack differently. In contrast to the monohydrate in which the water molecule generates two hydrogen bonds, no such intermolecular contacts are present in the title compound. The dihedral angle between the cinnamamide and the styryl group is 53.1 (1)°.

Related literature

For the structure of the monohydrate, see: Huang et al. (2006[Huang, X.-S., Ou, S.-Y. & Tang, S.-Z. (2006). Acta Cryst. E62, o1987-o1988.]). For medicinal applications, see: Loi (2001[Loi, D. T. (2001). In Glossary of Vietnamese Medical Plants. Hanoi: Science and Technology Publishers.]).

[Scheme 1]

Experimental

Crystal data
  • C18H17NO

  • Mr = 263.33

  • Triclinic, [P \overline 1]

  • a = 6.356 (1) Å

  • b = 9.265 (2) Å

  • c = 13.073 (3) Å

  • α = 80.45 (3)°

  • β = 77.22 (3)°

  • γ = 78.13 (3)°

  • V = 728.9 (3) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 298 K

  • 0.60 × 0.60 × 0.55 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: none

  • 25654 measured reflections

  • 5327 independent reflections

  • 3962 reflections with I > 2σ(I)

  • Rint = 0.023

Refinement
  • R[F2 > 2σ(F2)] = 0.060

  • wR(F2) = 0.190

  • S = 1.02

  • 5327 reflections

  • 182 parameters

  • H-atom parameters constrained

  • Δρmax = 0.36 e Å−3

  • Δρmin = −0.14 e Å−3

Data collection: SMART (Bruker, 2004[Bruker (2004). SMART and SAINT. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2004[Bruker (2004). SMART and SAINT. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEPIII (Burnett & Johnson, 1996[Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.]) and SCHAKAL99 (Keller & Pierrard, 1999[Keller, E. & Pierrard, J.-S. (1999). SCHAKAL99. University of Freiburg, Germany.]); software used to prepare material for publication: SHELXL97.

Supporting information


Comment top

The title compound N-methyl-N-styrylcinnamamide [N-methyl-3-phenyl-N-(2-phenylethenyl)-2-propenamide] (I) was isolated from the seeds of Clausena lansium (wampee) (Rutaceae). The leaves have been used as a folk medicine for the treatment of coughs, asthma and gastrointestinal diseases. The fruit is used for digestive disorders and the seeds are used for gastro-intestinal diseases such as acute and chronic gastrointestinal, ulcers, etc. (Loi, 2001).

The X-ray structure of the monohydrate of (I) was reported recently (Huang et al., 2006) wherein it was reported that "the corresponding anhydrous compound is a pale-yellow liquid at room temperature". Surprisingly, we could grow pale-yellow crystals of the water-free form from n-hexane and its X-ray structure, which is subject of this study, was carried out to confirm its chemical identity.

The molecular structure of (I) is shown in Fig. 1 and its superposition with the molecule found in the monohydrate structure is shown in Fig. 2. Both structures are practically identical with a small difference of 10° in the rotation of the styryl phenyl ring along the bond C11—C12: torsion angle C10—C11—C12—C13= 148.7 (1)° for (I) and 139.0 (3)° for the monohydrate. Bond lengths and angles, which are all in the expected ranges, have an average difference of 0.007 Å and 0.4° between (I) and the monohydrate.

The triclinic lattice of (I) is illustrated in Fig. 3. In contrast to the monohydrate where the water molecule generates two hydrogen bonds in a body centered tetragonal lattice, no such intermolecular contacts are present in (I). Nevertheless, the packing in the triclinic lattice shows some characteristic features. The molecule consists of two planar fragments, the cinnamamide and the styryl group, forming an interplanar angle of 53.1 (1)°. In molecular pairs related by the inversion centre at (1/2, 1/2, 1), the cinnamamide fragments are aligned in parallel planes with a shortest contact distance of C atoms of adjacent planes being C1···C8 = 3.664 (3) Å. Such an arrangement of cinnamamide groups was also observed in the monohydrate structure. The styryl groups also form co-planar planes for molecules related by the inversion centre at (1/2, 1/2, 1/2), the shortest distance between C atoms of adjacent planes is C11···C17 = 3.730 (3) Å (see dashed lines in Fig. 3). This arrangement of styryl groups was not observed in the monohydrate structure.

Related literature top

For related literature, see: Huang et al. (2006); Loi (2001).

Experimental top

The dried seeds of C. lansium (3,0 kg) were powdered and extracted with MeOH at room temperature, and the combined extracts were concentrated under reduced pressure to give a deep-brown syrup (160 g). This was partitioned between H2O and n-hexane. The n-hexane-soluble residue (85 g) was chromatographed over a silica gel column, which developed by gradient elution with n-hexane and increasing concentrations of Me2CO to afford forty fractions. Fractions were combined on their TLC. After standing for several day, fractions 9–11 recrystallized from n-hexane to afford pale-yellow lansamide (2554 mg).

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and SCHAKAL99 (Keller & Pierrard, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) with atom numbering scheme, displacement ellipsoids are shown at the 50% probability level.
[Figure 2] Fig. 2. Superposition of (I) (red) and the monohydrate (blue) forms of lansamide.
[Figure 3] Fig. 3. Stereo drawing of packing in (I) shown in projection onto the yz-plane. The C1···C8 and C11···C17 contacts are shown by dashed lines.
N-Methyl-N-styrylcinnamamide top
Crystal data top
C18H17NOZ = 2
Mr = 263.33F(000) = 280
Triclinic, P1Dx = 1.200 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.356 (1) ÅCell parameters from 5327 reflections
b = 9.265 (2) Åθ = 2.3–33.3°
c = 13.073 (3) ŵ = 0.07 mm1
α = 80.45 (3)°T = 298 K
β = 77.22 (3)°Block, yellow
γ = 78.13 (3)°0.60 × 0.60 × 0.55 mm
V = 728.9 (3) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
3962 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.023
Graphite monochromatorθmax = 33.3°, θmin = 2.3°
ω scansh = 99
25654 measured reflectionsk = 1314
5327 independent reflectionsl = 020
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)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.190H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.0892P)2 + 0.1313P]
where P = (Fo2 + 2Fc2)/3
5327 reflections(Δ/σ)max < 0.001
182 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = 0.14 e Å3
Crystal data top
C18H17NOγ = 78.13 (3)°
Mr = 263.33V = 728.9 (3) Å3
Triclinic, P1Z = 2
a = 6.356 (1) ÅMo Kα radiation
b = 9.265 (2) ŵ = 0.07 mm1
c = 13.073 (3) ÅT = 298 K
α = 80.45 (3)°0.60 × 0.60 × 0.55 mm
β = 77.22 (3)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3962 reflections with I > 2σ(I)
25654 measured reflectionsRint = 0.023
5327 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.190H-atom parameters constrained
S = 1.02Δρmax = 0.36 e Å3
5327 reflectionsΔρmin = 0.14 e Å3
182 parameters
Special details top

Experimental. Bruker AXS APEX CCD area detector on Huber four circle diffractometer is used

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
C10.6509 (2)0.21826 (15)0.99509 (11)0.0553 (3)
H10.52920.23280.96360.066*
C20.6807 (3)0.10113 (17)1.07380 (11)0.0650 (4)
H20.57940.03731.09490.078*
C30.8605 (3)0.07815 (17)1.12150 (11)0.0653 (4)
H30.88070.00141.17420.078*
C41.0085 (3)0.17266 (18)1.09103 (12)0.0671 (4)
H41.12830.15851.12380.080*
C50.9801 (2)0.28959 (16)1.01128 (11)0.0581 (3)
H51.08300.35230.99020.070*
C60.80051 (19)0.31483 (12)0.96224 (9)0.0447 (2)
C70.77651 (19)0.44124 (13)0.87988 (9)0.0469 (2)
H70.89470.49110.85720.056*
C80.60545 (19)0.49270 (12)0.83399 (9)0.0447 (2)
H80.48310.44670.85410.054*
C90.60632 (18)0.62255 (12)0.75108 (9)0.0439 (2)
O10.74616 (16)0.70168 (10)0.73318 (8)0.0600 (2)
N10.44089 (16)0.65399 (10)0.69570 (8)0.0474 (2)
C100.2872 (2)0.56144 (15)0.69998 (10)0.0537 (3)
H100.13980.60400.71550.064*
C110.3327 (2)0.41992 (15)0.68402 (10)0.0545 (3)
H110.21240.37290.69410.065*
C120.5480 (2)0.32715 (12)0.65251 (9)0.0472 (3)
C130.5818 (3)0.17475 (15)0.68682 (12)0.0663 (4)
H130.46780.13270.73090.080*
C140.7817 (4)0.08498 (16)0.65648 (15)0.0781 (5)
H140.80160.01600.68110.094*
C150.9499 (3)0.14446 (17)0.59047 (15)0.0727 (4)
H151.08470.08430.57070.087*
C160.9191 (3)0.29425 (15)0.55317 (12)0.0622 (3)
H161.03250.33450.50710.075*
C170.7205 (2)0.38448 (12)0.58411 (10)0.0512 (3)
H170.70190.48530.55880.061*
C180.4179 (3)0.79342 (14)0.62545 (12)0.0628 (4)
H1810.46710.86740.65330.094*
H1820.26690.82590.62010.094*
H1830.50480.77880.55670.094*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0516 (7)0.0576 (7)0.0575 (7)0.0127 (5)0.0159 (5)0.0013 (5)
C20.0691 (9)0.0633 (8)0.0597 (7)0.0183 (7)0.0113 (6)0.0071 (6)
C30.0761 (10)0.0640 (8)0.0494 (6)0.0032 (7)0.0156 (6)0.0042 (5)
C40.0658 (9)0.0725 (9)0.0631 (8)0.0005 (7)0.0303 (7)0.0012 (6)
C50.0509 (7)0.0600 (7)0.0658 (7)0.0082 (5)0.0226 (6)0.0014 (6)
C60.0418 (5)0.0463 (5)0.0444 (5)0.0025 (4)0.0094 (4)0.0067 (4)
C70.0399 (5)0.0485 (5)0.0513 (6)0.0071 (4)0.0105 (4)0.0027 (4)
C80.0412 (5)0.0477 (5)0.0451 (5)0.0077 (4)0.0099 (4)0.0039 (4)
C90.0391 (5)0.0432 (5)0.0478 (5)0.0020 (4)0.0096 (4)0.0061 (4)
O10.0524 (5)0.0530 (5)0.0762 (6)0.0151 (4)0.0203 (4)0.0048 (4)
N10.0443 (5)0.0433 (4)0.0536 (5)0.0013 (4)0.0153 (4)0.0032 (4)
C100.0359 (5)0.0669 (7)0.0574 (6)0.0076 (5)0.0133 (4)0.0011 (5)
C110.0476 (6)0.0678 (7)0.0541 (6)0.0262 (5)0.0145 (5)0.0017 (5)
C120.0575 (7)0.0446 (5)0.0454 (5)0.0206 (4)0.0164 (5)0.0005 (4)
C130.0903 (11)0.0509 (7)0.0635 (8)0.0319 (7)0.0235 (7)0.0119 (6)
C140.1117 (14)0.0410 (6)0.0849 (11)0.0077 (7)0.0405 (10)0.0048 (6)
C150.0796 (11)0.0546 (7)0.0865 (11)0.0040 (7)0.0314 (9)0.0155 (7)
C160.0612 (8)0.0542 (7)0.0714 (8)0.0118 (6)0.0074 (6)0.0135 (6)
C170.0578 (7)0.0398 (5)0.0557 (6)0.0146 (4)0.0066 (5)0.0036 (4)
C180.0745 (9)0.0452 (6)0.0685 (8)0.0004 (6)0.0289 (7)0.0005 (5)
Geometric parameters (Å, º) top
C1—C21.3798 (19)N1—C181.4566 (16)
C1—C61.3896 (18)C10—C111.3245 (19)
C1—H10.9300C10—H100.9300
C2—C31.383 (2)C11—C121.471 (2)
C2—H20.9300C11—H110.9300
C3—C41.366 (2)C12—C171.3902 (18)
C3—H30.9300C12—C131.3960 (17)
C4—C51.386 (2)C13—C141.384 (3)
C4—H40.9300C13—H130.9300
C5—C61.3902 (17)C14—C151.367 (3)
C5—H50.9300C14—H140.9300
C6—C71.4611 (16)C15—C161.381 (2)
C7—C81.3228 (16)C15—H150.9300
C7—H70.9300C16—C171.381 (2)
C8—C91.4797 (16)C16—H160.9300
C8—H80.9300C17—H170.9300
C9—O11.2254 (15)C18—H1810.9600
C9—N11.3621 (15)C18—H1820.9600
N1—C101.4133 (17)C18—H1830.9600
C2—C1—C6120.79 (13)C11—C10—N1126.33 (11)
C2—C1—H1119.6C11—C10—H10116.8
C6—C1—H1119.6N1—C10—H10116.8
C1—C2—C3120.35 (14)C10—C11—C12128.68 (11)
C1—C2—H2119.8C10—C11—H11115.7
C3—C2—H2119.8C12—C11—H11115.7
C4—C3—C2119.77 (13)C17—C12—C13117.46 (13)
C4—C3—H3120.1C17—C12—C11122.16 (11)
C2—C3—H3120.1C13—C12—C11120.30 (12)
C3—C4—C5120.01 (13)C14—C13—C12121.25 (14)
C3—C4—H4120.0C14—C13—H13119.4
C5—C4—H4120.0C12—C13—H13119.4
C4—C5—C6121.19 (14)C15—C14—C13120.15 (13)
C4—C5—H5119.4C15—C14—H14119.9
C6—C5—H5119.4C13—C14—H14119.9
C1—C6—C5117.88 (11)C14—C15—C16119.79 (16)
C1—C6—C7123.17 (11)C14—C15—H15120.1
C5—C6—C7118.95 (11)C16—C15—H15120.1
C8—C7—C6127.28 (11)C15—C16—C17120.21 (15)
C8—C7—H7116.4C15—C16—H16119.9
C6—C7—H7116.4C17—C16—H16119.9
C7—C8—C9120.86 (11)C16—C17—C12121.10 (12)
C7—C8—H8119.6C16—C17—H17119.5
C9—C8—H8119.6C12—C17—H17119.5
O1—C9—N1120.39 (11)N1—C18—H181109.5
O1—C9—C8122.32 (10)N1—C18—H182109.5
N1—C9—C8117.28 (10)H181—C18—H182109.5
C9—N1—C10125.32 (10)N1—C18—H183109.5
C9—N1—C18118.41 (11)H181—C18—H183109.5
C10—N1—C18116.27 (10)H182—C18—H183109.5
C6—C1—C2—C30.1 (2)O1—C9—N1—C187.99 (17)
C1—C2—C3—C40.5 (2)C8—C9—N1—C18170.62 (10)
C2—C3—C4—C51.1 (2)C9—N1—C10—C1153.69 (19)
C3—C4—C5—C61.1 (2)C18—N1—C10—C11126.00 (14)
C2—C1—C6—C50.1 (2)N1—C10—C11—C123.9 (2)
C2—C1—C6—C7179.54 (12)C10—C11—C12—C1734.6 (2)
C4—C5—C6—C10.5 (2)C10—C11—C12—C13148.71 (14)
C4—C5—C6—C7178.95 (12)C17—C12—C13—C141.9 (2)
C1—C6—C7—C88.2 (2)C11—C12—C13—C14178.75 (13)
C5—C6—C7—C8171.22 (12)C12—C13—C14—C151.0 (2)
C6—C7—C8—C9179.88 (10)C13—C14—C15—C160.7 (3)
C7—C8—C9—O111.86 (18)C14—C15—C16—C171.3 (2)
C7—C8—C9—N1169.57 (11)C15—C16—C17—C120.3 (2)
O1—C9—N1—C10171.70 (11)C13—C12—C17—C161.29 (19)
C8—C9—N1—C109.70 (17)C11—C12—C17—C16178.04 (12)

Experimental details

Crystal data
Chemical formulaC18H17NO
Mr263.33
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)6.356 (1), 9.265 (2), 13.073 (3)
α, β, γ (°)80.45 (3), 77.22 (3), 78.13 (3)
V3)728.9 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.60 × 0.60 × 0.55
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
25654, 5327, 3962
Rint0.023
(sin θ/λ)max1)0.772
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.190, 1.02
No. of reflections5327
No. of parameters182
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.36, 0.14

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and SCHAKAL99 (Keller & Pierrard, 1999).

 

Acknowledgements

The authors wish to thank Dau Thi Kim Quyen MSc, Faculty of Chemistry, Vinh University, for help in sample preparation. The help of Stefan Mebs Dipl. Chem. in X-ray data collection is gratefully acknowledged.

References

First citationBruker (2004). SMART and SAINT. Bruker Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.  Google Scholar
First citationBurnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.  Google Scholar
First citationHuang, X.-S., Ou, S.-Y. & Tang, S.-Z. (2006). Acta Cryst. E62, o1987–o1988.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationKeller, E. & Pierrard, J.-S. (1999). SCHAKAL99. University of Freiburg, Germany.  Google Scholar
First citationLoi, D. T. (2001). In Glossary of Vietnamese Medical Plants. Hanoi: Science and Technology Publishers.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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