2-(Prop-2-enyloxy)benzamide

Bernhard Bugenhagen; Yosef Al Jasem; Farah Barkhad; Bassam al Hindawi; Thies Thiemann

doi:10.1107/S1600536812042250

. 2012 Oct 20;68(Pt 11):o3169–o3170. doi: 10.1107/S1600536812042250

2-(Prop-2-enyloxy)benzamide

Bernhard Bugenhagen ^a, Yosef Al Jasem ^b, Farah Barkhad ^c, Bassam al Hindawi ^d, Thies Thiemann ^d,^*

PMCID: PMC3515263 PMID: 23284483

Abstract

In the title molecule, C₁₀H₁₁NO₂, the benzene ring forms dihedral angles of 33.15 (2) and 6.20 (2)° with the mean planes of the amide and propenoxy groups, respectively. The amide –NH₂ group is oriented toward the propenoxy substituent and forms a weak intramolecular N—H⋯O hydrogen bond to the propenoxy O atom. The conformation of the propenoxy group at the Csp ²—Csp ³ and Csp ³—O bonds is synperiplanar and antiperiplanar, respectively. In the crystal, N—H⋯O hydrogen bonds involving the amide groups generate C(4) and R ² ₃(7) motifs that organize the molecules into tapes along the a-axis direction. There are C—H⋯π interactions between the propenoxy –CH₂ group and the aromatic system of neighboring molecules within the tape. The mean planes of the aromatic ring and the propenoxy group belonging to molecules located on opposite sites of the tape form an angle of 83.16 (2)°.

Related literature

For crystal structures of similar compounds, see: Al Jasem et al. (2012 ▶); Pagola & Stephens (2009 ▶); Johnstone et al. (2010 ▶); Pertlik (1990) ▶; Sasada et al. (1964 ▶). For uses of 2-alkoxybenzamides, see: van de Waterbeemd & Testa (1983 ▶); Kusunoki & Harada (1984 ▶). For the preparation of a related 2-alkoxybenzamide, see: Al Jasem et al. (2012 ▶).

Experimental

Crystal data

C₁₀H₁₁NO₂
M _r = 177.20
Orthorhombic,
a = 5.08891 (17) Å
b = 11.2542 (4) Å
c = 15.8802 (6) Å
V = 909.48 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.74 mm⁻¹
T = 100 K
0.30 × 0.09 × 0.08 mm

Data collection

Agilent SuperNova Atlas diffractometer
Absorption correction: Gaussian (CrysAlis PRO; Agilent, 2012 ▶) T _min = 0.862, T _max = 0.951
4718 measured reflections
1079 independent reflections
1016 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.087
S = 1.03
1079 reflections
126 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within OLEX2 (Dolomanov et al., 2009 ▶); molecular graphics: PLATON (Spek, 2009 ▶); Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97, PLATON.

Supplementary Material

Click here for additional data file.^{(19.3KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812042250/gk2521sup1.cif

e-68-o3169-sup1.cif^{(19.3KB, cif)}

Click here for additional data file.^{(53.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812042250/gk2521Isup2.hkl

e-68-o3169-Isup2.hkl^{(53.5KB, hkl)}

Click here for additional data file.^{(3.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812042250/gk2521Isup3.cml

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

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

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1ⁱ	0.90 (2)	2.01 (2)	2.905 (2)	178 (17)
N1—H1B⋯O1ⁱⁱ	0.89 (3)	2.12 (3)	2.863 (2)	140 (2)
N1—H1B⋯O2	0.89 (3)	2.31 (2)	2.754 (2)	110.8 (18)
C8—H8B⋯Cg ⁱⁱ	0.99	2.68	3.461 (2)	137

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

Comment

In 2-propenoxybenzamide (2-allyloxybenzamide) (Figure 1), the O1—C7—C1—C6 torsion angle characterizing the twist of the benzene ring relative to the amide group is -30.3 (2)° and the corresponding C8—O2—C2—C3 torsion angle for the propoxy group is 5.9 (2)°. There is an intramolecular N1—H1B···O2 bond within each molecule (Table 1). When compared to the structurally comparable 2-propoxybenzamide (Al Jasem et al., 2012), the torsion angle O1—C7—C1—C6 is much larger in the title compound. The amide groups generate C(4) and R²₃(7) hydrogen-bond motifs that organize the molecules into tapes along the a axis. The title compound exhibits a C10—H10A···O2 and a C8—H8··· π (Table 1) close contact, absent in 2-propoxybenzamide (Figure 2). The C4—H4···O1 intermolecular interaction in 2-propenoxybenzamide links the neighboring tapes of molecules along the a axis with each other (Figure 3). However, in 2-propoxybenzamide, where also a C–H···O intermolecular interaction is found, the interaction proceeds from the carbon ortho to the propoxy group, while in the present case, it proceeds from the carbon meta to the propenoxy group. As a result of more close intermolecular contacts in 2-propenoxybenzamide as compared to 2-propoxybenzamide, the difference in the packing between the two compounds is large. The main difference is that while in the 2-propoxybenzamide molecules are arranged into pairs by close contacts, where the pairs in one layer are not associated through close contacts, in the title compound all neighboring molecules form close contacts to each other. Nevertheless, both compounds exhibit particular molecular tapes, each compound with two different directions of tape propagation. In the title compound, the average plane (0 1 - 1) of a tape propagation has an angle of 68.78 (2)° with the corresponding plane (0 1 1) of the neighboring tape propagation. Due to the large dihedral angle between the benzene ring and the amide group in 2-propenoxybenzamide, the average plane (-1 2 2) of the benzene ring and the propenoxy group of a molecule in one stack makes an angle of 83.16 (2)° with the corresponding plane (1 2 2) of a molecule in the opposing motif within one tape.

Experimental

To powdered KOH (1.12 g, 20.0 mmol) in DMSO (18 ml) was added salicylamide (2.74 g, 20.0 mmol), and the resulting mixture was stirred for 10 min. at rt. Thereafter, n-propenyl bromide (4.2 g, mmol, 34.7 mmol) was added dropwise. The solution was stirred for 12 h at rt. Then, it was poured into water (200 ml) and extracted with chloroform (3 x 75 ml). The organic phase was dried over anhydrous MgSO₄, concentrated in vacuo, and the residue was subjected to column chromatography on silica gel (CHCl₃/M^tBE/hexane v/v/v 1:1:1) to give 2-propenoxybenzamide (2.76 g, 78%) as colorless crystals (m.p. 377 K). The crystal was grown from CHCl₃/ M^tBE/hexane (v/v/v 1:1:1).IR (KBr) ν_max 3406, 3190, 1631, 1600, 1399, 1243, 996, 921, 757, 643, 627 cm^-1; δ_H (400 MHz, CDCl₃) 4.67 (2H, d, ³J = 5.6 Hz), 5.36 (1H, dd, ³J = 10.4 Hz, ²J = 1.2 Hz), 5.44 (1H, dd, ³J = 17.2 Hz, ²J = 1.2 Hz), 6.03 – 6.13 (1H, dt, ³J = 17.2 Hz, ³J = 10.4 Hz, ³J = 5.6 Hz), 6.25 (1H, bs, NH), 6.96 (1H, d, ³J = 8.0 Hz), 7.07 (1H, dd, ³J = 8.0 Hz, ³J = 8.0 Hz), 7.80 (1H, bs, NH), 8.20 (1H, dd, ³J = 8.0 Hz, ⁴J = 1.6 Hz); δ_C (100.5 MHz, CDCl₃) 69.9, 112.6, 119.4, 121.1, 121.4, 132.0, 132.6, 133.3, 156.9, 167.2.