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Acta Crystallogr Sect E Struct Rep Online. 2009 May 1; 65(Pt 5): o1115.
Published online 2009 April 25. doi:  10.1107/S160053680901455X
PMCID: PMC2977791

N-Benzyl-2-propynamide

Abstract

Pale-yellow crystals of the title compound, C10H9NO, have been obtained by the reaction of benzyl­amine and methyl propiolate. Weak inter­molecular hydrogen bonding is observed between acetyl­enic H and carbonyl O atoms. The crystal packing is stabilized by these C—H(...)O and by N—H(...)O inter­molecular hydrogen-bonding inter­actions.

Related literature

The title compound was synthesized using a similar synthetic method to that described by Williamson et al. (1994 [triangle]). For the synthesis of triazole derivatives, see: Katritzky & Singh (2002 [triangle]). For the structure of the methyl analogue of the title compound, see: Leiserowitz & Tuval (1978 [triangle]). For the program ROTAX, used to investigate possible pseudo-merohedral twinning, see: Parsons & Gould (2003 [triangle]).

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Object name is e-65-o1115-scheme1.jpg

Experimental

Crystal data

  • C10H9NO
  • M r = 159.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1115-efi1.jpg
  • a = 9.495 (2) Å
  • b = 10.703 (2) Å
  • c = 8.9120 (19) Å
  • β = 101.637 (3)°
  • V = 887.1 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.08 mm−1
  • T = 173 K
  • 0.57 × 0.30 × 0.30 mm

Data collection

  • Bruker SMART APEX area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2001 [triangle]) T min = 0.848, T max = 1.000 (expected range = 0.828–0.977)
  • 5825 measured reflections
  • 1550 independent reflections
  • 1510 reflections with I > 2σ(I)
  • R int = 0.030

Refinement

  • R[F 2 > 2σ(F 2)] = 0.070
  • wR(F 2) = 0.221
  • S = 1.26
  • 1550 reflections
  • 113 parameters
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.45 e Å−3
  • Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2001 [triangle]); cell refinement: SAINT (Bruker, 2001 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680901455X/zl2187sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901455X/zl2187Isup2.hkl

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

Acknowledgments

The authors thank the National Science Foundation of China (grant No. 40706043) and the Science Foundation of Xiamen University (grant No. Z03120) for supporting this work. We also thank Mr Z.-B. Wei for technical assistance.

supplementary crystallographic information

Comment

The title compound is a terminal alkyne, which is an intermediate in the synthesis of triazole derivatives (Katritzky et al., 2002).

The molecular structure of the title compound is shown in Fig. 1. The bond lengths and bond angles in the compound are comparable to those in the structure of the methyl analogue (Leiserowitz et al., 1978). The atoms C1, C2, C3, O1, N1 and C4 of the title compound are nearly in a plane, and the r.m.s. deviation of these atoms from their mean plane is 0.007 Å. The dihedral angle between the plane of C5 and the phenyl ring and the mean plane of C1 to C4 and N1 is 76.8 (2)°. Hydrogen bonding plays a significant role in stabilizing the crystal structure; see Table 1 for geometric parameters and symmetry operations. The most prominent link occurs between the acylamide O and the N atoms, to form chains along the b axis. Weak intermolecular hydrogen bonding is observed between the alkyne H and the carbonyl O atoms (table 1). Molecules are connected into a double chain by C—H···O and N—H···O intermolecular hydrogen-bonding interactions (Figure 2).

Experimental

The title compound was synthesized using a similar synthetic method as for the preparation of 1-(pyrrolidin-1-yl)prop-2-yn-1-one (Williamson et al., 1994). To a solution of benzyl amine (1.07 g, 10 mmol) in methanol (4 ml) was slowly added methyl propiolate (0.84 g, 10 mmol) at 195 K with stirring. After addition of the propiolate, the stirring was continued for 10 h and then the mixture warmed to 248 K for 5 h. The reaction was quenched with a saturated NH4Cl solution (12 ml) and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous MgSO4, concentrated under vacuum and the crude product was purified by column chromatography (petroleum ether: ethyl acetate, 2:1) to give the title compound as a pale yellow solid in 72% yield. Single crystals of the title compound were grown in a petroleum ether/ethyl acetate solution (v/v = 5:1) by slow evaporation.

Refinement

All non-hydrogen atoms were refined anisotropically. The acetylenic H atom was located from a difference Fourier map and both the position and isotropic thermal parameter were freely refined. The remaining H atoms were placed in ideal positions and refined via a riding model with N-H distances of 0.88, C-Hmethyelene = 0.99 and C-Haromatic = 0.95 Å and Uiso = 1.2 Ueq(C,N). Torsion angles were refined to fit the electron density. The metric parameters suggest the possibility of pseudo-merohedral twinning by a two fold rotation around either the a or the c axis. Application of the respective twin law of (-1 0 - 0.43, 0 1 0, 0 0 1), obtained using the program Rotax (Parsons & Gould, 2003)) however indicated that the crystal at hand was not twinned.

Figures

Fig. 1.
The molecular structure of the compound with 50% probability displacement ellipsoids (arbitrary spheres for H atoms).
Fig. 2.
Part of the packing of the title compound. Intermolecular hydrogen bonds are represented by dashed lines.

Crystal data

C10H9NOF(000) = 336
Mr = 159.18Dx = 1.192 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 4373 reflections
a = 9.495 (2) Åθ = 2.2–28.3°
b = 10.703 (2) ŵ = 0.08 mm1
c = 8.9120 (19) ÅT = 173 K
β = 101.637 (3)°Chunk, pale yellow
V = 887.1 (3) Å30.57 × 0.30 × 0.30 mm
Z = 4

Data collection

Bruker APEX area-detector diffractometer1550 independent reflections
Radiation source: fine-focus sealed tube1510 reflections with I > 2σ(I)
graphiteRint = 0.030
[var phi] and ω scansθmax = 25.0°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)h = −11→11
Tmin = 0.848, Tmax = 1.000k = −12→12
5825 measured reflectionsl = −10→10

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)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.221H atoms treated by a mixture of independent and constrained refinement
S = 1.26w = 1/[σ2(Fo2) + (0.0874P)2 + 1.0844P] where P = (Fo2 + 2Fc2)/3
1550 reflections(Δ/σ)max < 0.001
113 parametersΔρmax = 0.45 e Å3
0 restraintsΔρmin = −0.23 e Å3

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
O10.8163 (2)0.3454 (2)0.1877 (2)0.0356 (6)
N10.7947 (3)0.3179 (2)0.4330 (3)0.0323 (7)
H1A0.82030.27280.51660.039*
C11.0048 (4)0.0859 (3)0.3289 (4)0.0401 (8)
C20.9317 (3)0.1756 (3)0.3242 (3)0.0317 (7)
C30.8422 (3)0.2867 (3)0.3095 (3)0.0290 (7)
C40.7008 (4)0.4254 (3)0.4350 (4)0.0365 (8)
H4A0.73890.49710.38550.044*
H4B0.70150.44870.54270.044*
C50.5485 (3)0.4009 (3)0.3545 (3)0.0323 (7)
C60.4870 (4)0.4688 (3)0.2258 (4)0.0413 (8)
H6A0.54180.53090.18730.050*
C70.3471 (4)0.4469 (4)0.1532 (4)0.0483 (9)
H7A0.30580.49430.06530.058*
C80.2665 (4)0.3569 (4)0.2069 (4)0.0466 (9)
H8A0.17020.34150.15590.056*
C90.3268 (4)0.2895 (3)0.3353 (4)0.0464 (9)
H9A0.27150.22770.37360.056*
C100.4673 (4)0.3113 (3)0.4089 (4)0.0411 (8)
H10A0.50810.26430.49740.049*
H11.061 (4)0.014 (4)0.328 (4)0.050 (11)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0461 (13)0.0335 (12)0.0286 (12)−0.0005 (10)0.0112 (9)0.0028 (9)
N10.0378 (14)0.0352 (14)0.0246 (13)0.0058 (11)0.0076 (10)0.0010 (10)
C10.0344 (17)0.0376 (19)0.049 (2)0.0016 (16)0.0091 (14)−0.0036 (15)
C20.0313 (16)0.0355 (17)0.0297 (16)−0.0050 (13)0.0091 (12)−0.0018 (12)
C30.0285 (15)0.0301 (15)0.0275 (15)−0.0076 (12)0.0038 (11)−0.0021 (12)
C40.0432 (18)0.0323 (16)0.0342 (17)0.0031 (14)0.0086 (13)−0.0064 (13)
C50.0406 (17)0.0284 (15)0.0292 (15)0.0061 (13)0.0104 (12)−0.0050 (12)
C60.050 (2)0.0380 (18)0.0368 (18)0.0070 (15)0.0116 (15)0.0024 (14)
C70.051 (2)0.054 (2)0.0379 (19)0.0174 (18)0.0061 (16)0.0028 (16)
C80.0387 (18)0.053 (2)0.046 (2)0.0078 (16)0.0040 (15)−0.0089 (16)
C90.043 (2)0.0391 (19)0.057 (2)−0.0032 (15)0.0112 (16)−0.0014 (16)
C100.0459 (19)0.0358 (17)0.0412 (18)0.0040 (14)0.0080 (15)0.0049 (14)

Geometric parameters (Å, °)

O1—C31.235 (4)C5—C61.384 (5)
N1—C31.314 (4)C6—C71.376 (5)
N1—C41.458 (4)C6—H6A0.9500
N1—H1A0.8800C7—C81.374 (6)
C1—C21.180 (5)C7—H7A0.9500
C1—H10.93 (4)C8—C91.376 (5)
C2—C31.453 (4)C8—H8A0.9500
C4—C51.502 (5)C9—C101.383 (5)
C4—H4A0.9900C9—H9A0.9500
C4—H4B0.9900C10—H10A0.9500
C5—C101.378 (5)
C3—N1—C4121.7 (3)C6—C5—C4120.6 (3)
C3—N1—H1A119.2C7—C6—C5120.4 (3)
C4—N1—H1A119.2C7—C6—H6A119.8
C2—C1—H1178 (2)C5—C6—H6A119.8
C1—C2—C3176.9 (3)C8—C7—C6120.6 (3)
O1—C3—N1124.5 (3)C8—C7—H7A119.7
O1—C3—C2120.3 (3)C6—C7—H7A119.7
N1—C3—C2115.2 (3)C7—C8—C9119.3 (3)
N1—C4—C5112.8 (2)C7—C8—H8A120.4
N1—C4—H4A109.0C9—C8—H8A120.4
C5—C4—H4A109.0C8—C9—C10120.4 (3)
N1—C4—H4B109.0C8—C9—H9A119.8
C5—C4—H4B109.0C10—C9—H9A119.8
H4A—C4—H4B107.8C5—C10—C9120.4 (3)
C10—C5—C6119.0 (3)C5—C10—H10A119.8
C10—C5—C4120.4 (3)C9—C10—H10A119.8
C4—N1—C3—O12.1 (5)C5—C6—C7—C8−0.3 (5)
C4—N1—C3—C2−178.4 (3)C6—C7—C8—C90.6 (5)
C3—N1—C4—C576.0 (4)C7—C8—C9—C10−0.5 (5)
N1—C4—C5—C1063.6 (4)C6—C5—C10—C90.3 (5)
N1—C4—C5—C6−117.3 (3)C4—C5—C10—C9179.4 (3)
C10—C5—C6—C7−0.2 (5)C8—C9—C10—C50.0 (5)
C4—C5—C6—C7−179.3 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.881.992.839 (3)163
C1—H1···O1ii0.93 (4)2.17 (4)3.105 (4)176 (3)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2187).

References

  • Bruker (2001). SAINT, SMART and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Katritzky, A. R. & Singh, K. (2002). J. Org. Chem.67, 9077–9079. [PubMed]
  • Leiserowitz, L. & Tuval, M. (1978). Acta Cryst. B34, 1230–1247.
  • Parsons, S. & Gould, B. (2003). ROTAX University of Edinburgh, Scotland.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Williamson, B. L., Tykwinski, R. R. & Stang, P. J. (1994). J. Am. Chem. Soc.116, 93–98.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography