N-Benzyl-2-propynamide

Chen, M.-M.; Gao, Y.-X.; Wang, H.-Y.; Han, D.-X.; Zhao, Y.-F.

doi:10.1107/S160053680901455X

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1115

doi:10.1107/S160053680901455X

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N-Benzyl-2-propynamide

Mei-Mei Chen,^a Yu-Xing Gao,^b Hai-Yan Wang,^c Da-Xiong Han ^a ^* and Yu-Fen Zhao ^a

^aDepartment of Pharmacy, Medical College of Xiamen University, Xiamen 361005, People's Republic of China, ^bDepartment of Chemistry and the Key Laboratory for Chemical Biology of Fujian Province, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China, and ^cThe Third Institute of Oceanography, State Oceanic Administration of China, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: daxiong@xmu.edu.cn

(Received 8 March 2009; accepted 19 April 2009; online 25 April 2009)

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 ). For the synthesis of triazole derivatives, see: Katritzky & Singh (2002 ). For the structure of the methyl analogue of the title compound, see: Leiserowitz & Tuval (1978 ). For the program ROTAX, used to investigate possible pseudo-merohedral twinning, see: Parsons & Gould (2003 ).

Experimental

Crystal data

C₁₀H₉NO
M_r = 159.18
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.070
wR(F²) = 0.221
S = 1.26
1550 reflections
113 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.88	1.99	2.839 (3)	163
C1—H1⋯O1ⁱⁱ	0.93 (4)	2.17 (4)	3.105 (4)	176 (3)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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.

N-benzyl-2-propynamide top

Crystal data top

C₁₀H₉NO	F(000) = 336
M_r = 159.18	D_x = 1.192 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4373 reflections
a = 9.495 (2) Å	θ = 2.2–28.3°
b = 10.703 (2) Å	µ = 0.08 mm⁻¹
c = 8.9120 (19) Å	T = 173 K
β = 101.637 (3)°	Chunk, pale yellow
V = 887.1 (3) Å³	0.57 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker APEX area-detector diffractometer	1550 independent reflections
Radiation source: fine-focus sealed tube	1510 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.848, T_max = 1.000	k = −12→12
5825 measured reflections	l = −10→10

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.070	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.221	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	w = 1/[σ²(F_o²) + (0.0874P)² + 1.0844P] where P = (F_o² + 2F_c²)/3
1550 reflections	(Δ/σ)_max < 0.001
113 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₀H₉NO	V = 887.1 (3) Å³
M_r = 159.18	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.495 (2) Å	µ = 0.08 mm⁻¹
b = 10.703 (2) Å	T = 173 K
c = 8.9120 (19) Å	0.57 × 0.30 × 0.30 mm
β = 101.637 (3)°

Data collection top

Bruker APEX area-detector diffractometer	1550 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1510 reflections with I > 2σ(I)
T_min = 0.848, T_max = 1.000	R_int = 0.030
5825 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	0 restraints
wR(F²) = 0.221	H atoms treated by a mixture of independent and constrained refinement
S = 1.26	Δρ_max = 0.45 e Å⁻³
1550 reflections	Δρ_min = −0.23 e Å⁻³
113 parameters

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

	x	y	z	U_iso*/U_eq
O1	0.8163 (2)	0.3454 (2)	0.1877 (2)	0.0356 (6)
N1	0.7947 (3)	0.3179 (2)	0.4330 (3)	0.0323 (7)
H1A	0.8203	0.2728	0.5166	0.039*
C1	1.0048 (4)	0.0859 (3)	0.3289 (4)	0.0401 (8)
C2	0.9317 (3)	0.1756 (3)	0.3242 (3)	0.0317 (7)
C3	0.8422 (3)	0.2867 (3)	0.3095 (3)	0.0290 (7)
C4	0.7008 (4)	0.4254 (3)	0.4350 (4)	0.0365 (8)
H4A	0.7389	0.4971	0.3855	0.044*
H4B	0.7015	0.4487	0.5427	0.044*
C5	0.5485 (3)	0.4009 (3)	0.3545 (3)	0.0323 (7)
C6	0.4870 (4)	0.4688 (3)	0.2258 (4)	0.0413 (8)
H6A	0.5418	0.5309	0.1873	0.050*
C7	0.3471 (4)	0.4469 (4)	0.1532 (4)	0.0483 (9)
H7A	0.3058	0.4943	0.0653	0.058*
C8	0.2665 (4)	0.3569 (4)	0.2069 (4)	0.0466 (9)
H8A	0.1702	0.3415	0.1559	0.056*
C9	0.3268 (4)	0.2895 (3)	0.3353 (4)	0.0464 (9)
H9A	0.2715	0.2277	0.3736	0.056*
C10	0.4673 (4)	0.3113 (3)	0.4089 (4)	0.0411 (8)
H10A	0.5081	0.2643	0.4974	0.049*
H1	1.061 (4)	0.014 (4)	0.328 (4)	0.050 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0461 (13)	0.0335 (12)	0.0286 (12)	−0.0005 (10)	0.0112 (9)	0.0028 (9)
N1	0.0378 (14)	0.0352 (14)	0.0246 (13)	0.0058 (11)	0.0076 (10)	0.0010 (10)
C1	0.0344 (17)	0.0376 (19)	0.049 (2)	0.0016 (16)	0.0091 (14)	−0.0036 (15)
C2	0.0313 (16)	0.0355 (17)	0.0297 (16)	−0.0050 (13)	0.0091 (12)	−0.0018 (12)
C3	0.0285 (15)	0.0301 (15)	0.0275 (15)	−0.0076 (12)	0.0038 (11)	−0.0021 (12)
C4	0.0432 (18)	0.0323 (16)	0.0342 (17)	0.0031 (14)	0.0086 (13)	−0.0064 (13)
C5	0.0406 (17)	0.0284 (15)	0.0292 (15)	0.0061 (13)	0.0104 (12)	−0.0050 (12)
C6	0.050 (2)	0.0380 (18)	0.0368 (18)	0.0070 (15)	0.0116 (15)	0.0024 (14)
C7	0.051 (2)	0.054 (2)	0.0379 (19)	0.0174 (18)	0.0061 (16)	0.0028 (16)
C8	0.0387 (18)	0.053 (2)	0.046 (2)	0.0078 (16)	0.0040 (15)	−0.0089 (16)
C9	0.043 (2)	0.0391 (19)	0.057 (2)	−0.0032 (15)	0.0112 (16)	−0.0014 (16)
C10	0.0459 (19)	0.0358 (17)	0.0412 (18)	0.0040 (14)	0.0080 (15)	0.0049 (14)

Geometric parameters (Å, º) top

O1—C3	1.235 (4)	C5—C6	1.384 (5)
N1—C3	1.314 (4)	C6—C7	1.376 (5)
N1—C4	1.458 (4)	C6—H6A	0.9500
N1—H1A	0.8800	C7—C8	1.374 (6)
C1—C2	1.180 (5)	C7—H7A	0.9500
C1—H1	0.93 (4)	C8—C9	1.376 (5)
C2—C3	1.453 (4)	C8—H8A	0.9500
C4—C5	1.502 (5)	C9—C10	1.383 (5)
C4—H4A	0.9900	C9—H9A	0.9500
C4—H4B	0.9900	C10—H10A	0.9500
C5—C10	1.378 (5)

C3—N1—C4	121.7 (3)	C6—C5—C4	120.6 (3)
C3—N1—H1A	119.2	C7—C6—C5	120.4 (3)
C4—N1—H1A	119.2	C7—C6—H6A	119.8
C2—C1—H1	178 (2)	C5—C6—H6A	119.8
C1—C2—C3	176.9 (3)	C8—C7—C6	120.6 (3)
O1—C3—N1	124.5 (3)	C8—C7—H7A	119.7
O1—C3—C2	120.3 (3)	C6—C7—H7A	119.7
N1—C3—C2	115.2 (3)	C7—C8—C9	119.3 (3)
N1—C4—C5	112.8 (2)	C7—C8—H8A	120.4
N1—C4—H4A	109.0	C9—C8—H8A	120.4
C5—C4—H4A	109.0	C8—C9—C10	120.4 (3)
N1—C4—H4B	109.0	C8—C9—H9A	119.8
C5—C4—H4B	109.0	C10—C9—H9A	119.8
H4A—C4—H4B	107.8	C5—C10—C9	120.4 (3)
C10—C5—C6	119.0 (3)	C5—C10—H10A	119.8
C10—C5—C4	120.4 (3)	C9—C10—H10A	119.8

C4—N1—C3—O1	2.1 (5)	C5—C6—C7—C8	−0.3 (5)
C4—N1—C3—C2	−178.4 (3)	C6—C7—C8—C9	0.6 (5)
C3—N1—C4—C5	76.0 (4)	C7—C8—C9—C10	−0.5 (5)
N1—C4—C5—C10	63.6 (4)	C6—C5—C10—C9	0.3 (5)
N1—C4—C5—C6	−117.3 (3)	C4—C5—C10—C9	179.4 (3)
C10—C5—C6—C7	−0.2 (5)	C8—C9—C10—C5	0.0 (5)
C4—C5—C6—C7	−179.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	1.99	2.839 (3)	163
C1—H1···O1ⁱⁱ	0.93 (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.

Experimental details

Crystal data
Chemical formula	C₁₀H₉NO
M_r	159.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	9.495 (2), 10.703 (2), 8.9120 (19)
β (°)	101.637 (3)
V (Å³)	887.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.57 × 0.30 × 0.30

Data collection
Diffractometer	Bruker APEX area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.848, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5825, 1550, 1510
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.070, 0.221, 1.26
No. of reflections	1550
No. of parameters	113
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.23

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1ⁱ	0.88	1.99	2.839 (3)	162.6
C1—H1···O1ⁱⁱ	0.93 (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.

Acknowledgements

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.

References

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