organic compounds
2-(Prop-2-enyloxy)benzamide
aInstitute of Inorganic Chemistry, University of Hamburg, Hamburg, Germany, bDepartment of Chemical Engineering, UAE University, AL Ain, Abu Dhabi, United Arab Emirates, cDepartment of Petroleum Engineering, UAE University, AL Ain, Abu Dhabi, United Arab Emirates, and dDepartment of Chemistry, UAE University, AL Ain, Abu Dhabi, United Arab Emirates
*Correspondence e-mail: thies@uaeu.ac.ae
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 Csp2—Csp3 and Csp3—O bonds is synperiplanar and antiperiplanar, respectively. In the crystal, N—H⋯O hydrogen bonds involving the amide groups generate C(4) and R23(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
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Refinement
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Data collection: CrysAlis PRO (Agilent, 2012); cell 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.
Supporting information
10.1107/S1600536812042250/gk2521sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042250/gk2521Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042250/gk2521Isup3.cml
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 νmax 3406, 3190, 1631, 1600, 1399, 1243, 996, 921, 757, 643, 627 cm-1; δH (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); δC (100.5 MHz, CDCl3) 69.9, 112.6, 119.4, 121.1, 121.4, 132.0, 132.6, 133.3, 156.9, 167.2.
on silica gel (CHCl3/MtBE/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/ MtBE/hexane (v/v/v 1:1:1).IR (KBr)All carbon-bound hydrogen atoms were placed in calculated positions with C—H
distances of 0.95 - 0.99 Å and refined as riding with Uiso(H)
=xUeq(C), where x = 1.5 for methyl and x = 1.2 for all other H-atoms.
The N-bound H atom positions were determined from difference electron
density map and refined freely. In the absence of significant anomalous
scattering effects Friedel pairs have been merged.
Data collection: CrysAlis PRO (Agilent, 2012); cell
CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); 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 (Sheldrick, 2008), PLATON (Spek, 2009).C10H11NO2 | Dx = 1.294 Mg m−3 |
Mr = 177.20 | Melting point: 377 K |
Orthorhombic, P212121 | Cu Kα radiation, λ = 1.5418 Å |
a = 5.08891 (17) Å | Cell parameters from 2824 reflections |
b = 11.2542 (4) Å | θ = 3.9–72.6° |
c = 15.8802 (6) Å | µ = 0.74 mm−1 |
V = 909.48 (5) Å3 | T = 100 K |
Z = 4 | Needle, colourless |
F(000) = 376 | 0.30 × 0.09 × 0.08 mm |
Agilent SuperNova Atlas diffractometer | 1079 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 1016 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.025 |
Detector resolution: 10.4127 pixels mm-1 | θmax = 72.7°, θmin = 4.8° |
ω scans | h = −6→3 |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2012) | k = −12→13 |
Tmin = 0.862, Tmax = 0.951 | l = −19→19 |
4718 measured reflections |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0609P)2 + 0.1267P] where P = (Fo2 + 2Fc2)/3 |
1079 reflections | (Δ/σ)max < 0.001 |
126 parameters | Δρmax = 0.17 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
C10H11NO2 | V = 909.48 (5) Å3 |
Mr = 177.20 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 5.08891 (17) Å | µ = 0.74 mm−1 |
b = 11.2542 (4) Å | T = 100 K |
c = 15.8802 (6) Å | 0.30 × 0.09 × 0.08 mm |
Agilent SuperNova Atlas diffractometer | 1079 independent reflections |
Absorption correction: gaussian (CrysAlis PRO; Agilent, 2012) | 1016 reflections with I > 2σ(I) |
Tmin = 0.862, Tmax = 0.951 | Rint = 0.025 |
4718 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.087 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.17 e Å−3 |
1079 reflections | Δρmin = −0.18 e Å−3 |
126 parameters |
Experimental. Numerical absorption correction based on gaussian integration over a multifaceted crystal model |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.2397 (4) | 0.43317 (15) | 0.31664 (10) | 0.0181 (4) | |
C10 | 0.9389 (4) | 0.59453 (19) | 0.49447 (12) | 0.0289 (4) | |
C2 | 0.4129 (3) | 0.52840 (15) | 0.30222 (11) | 0.0188 (4) | |
C3 | 0.3949 (4) | 0.59415 (17) | 0.22777 (12) | 0.0238 (4) | |
C4 | 0.2055 (4) | 0.56545 (18) | 0.16826 (11) | 0.0262 (4) | |
C5 | 0.0314 (4) | 0.47271 (17) | 0.18190 (11) | 0.0244 (4) | |
C6 | 0.0478 (4) | 0.40808 (16) | 0.25658 (11) | 0.0208 (4) | |
C7 | 0.2401 (3) | 0.35748 (15) | 0.39466 (11) | 0.0181 (4) | |
C8 | 0.7520 (4) | 0.65550 (15) | 0.35506 (12) | 0.0231 (4) | |
C9 | 0.9255 (4) | 0.66806 (17) | 0.43007 (12) | 0.0268 (4) | |
H10A | 0.8310 | 0.5257 | 0.4958 | 0.035* | |
H10B | 1.0565 | 0.6104 | 0.5396 | 0.035* | |
H1A | 0.484 (5) | 0.288 (2) | 0.4772 (13) | 0.028 (6)* | |
H1B | 0.623 (5) | 0.358 (2) | 0.4113 (16) | 0.040 (7)* | |
H3 | 0.5120 | 0.6584 | 0.2179 | 0.029* | |
H4 | 0.1950 | 0.6099 | 0.1175 | 0.031* | |
H5 | −0.0975 | 0.4534 | 0.1408 | 0.029* | |
H6 | −0.0741 | 0.3458 | 0.2667 | 0.025* | |
H8A | 0.6389 | 0.7267 | 0.3496 | 0.028* | |
H8B | 0.8604 | 0.6488 | 0.3035 | 0.028* | |
H9 | 1.0373 | 0.7356 | 0.4316 | 0.032* | |
N1 | 0.4686 (3) | 0.33298 (15) | 0.43084 (10) | 0.0218 (3) | |
O1 | 0.0291 (2) | 0.31561 (12) | 0.42082 (8) | 0.0224 (3) | |
O2 | 0.5922 (2) | 0.55184 (11) | 0.36411 (7) | 0.0217 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0162 (8) | 0.0185 (8) | 0.0197 (8) | 0.0023 (7) | 0.0017 (7) | −0.0006 (6) |
C2 | 0.0149 (8) | 0.0194 (8) | 0.0221 (8) | 0.0015 (7) | 0.0019 (7) | 0.0001 (7) |
C3 | 0.0226 (9) | 0.0230 (8) | 0.0259 (9) | 0.0029 (8) | 0.0040 (7) | 0.0037 (7) |
C4 | 0.0309 (10) | 0.0275 (10) | 0.0202 (8) | 0.0076 (9) | 0.0018 (8) | 0.0044 (7) |
C5 | 0.0245 (9) | 0.0280 (9) | 0.0207 (8) | 0.0049 (8) | −0.0038 (7) | −0.0032 (7) |
C6 | 0.0180 (8) | 0.0205 (8) | 0.0239 (8) | 0.0014 (7) | −0.0004 (8) | −0.0028 (7) |
C7 | 0.0159 (8) | 0.0173 (8) | 0.0210 (8) | 0.0005 (7) | 0.0006 (7) | −0.0019 (6) |
C8 | 0.0213 (9) | 0.0177 (8) | 0.0304 (9) | −0.0038 (8) | 0.0011 (8) | 0.0008 (7) |
C9 | 0.0211 (9) | 0.0240 (9) | 0.0353 (10) | −0.0040 (8) | 0.0013 (8) | −0.0066 (8) |
C10 | 0.0270 (10) | 0.0315 (9) | 0.0283 (9) | 0.0002 (9) | −0.0022 (9) | −0.0070 (8) |
N1 | 0.0153 (7) | 0.0260 (8) | 0.0240 (7) | −0.0007 (6) | 0.0000 (6) | 0.0071 (6) |
O1 | 0.0153 (6) | 0.0243 (6) | 0.0276 (6) | −0.0017 (5) | 0.0006 (5) | 0.0053 (5) |
O2 | 0.0195 (6) | 0.0210 (6) | 0.0246 (6) | −0.0045 (5) | −0.0015 (5) | 0.0033 (5) |
C1—C2 | 1.406 (2) | C7—N1 | 1.326 (2) |
C1—C6 | 1.394 (2) | C7—O1 | 1.244 (2) |
C1—C7 | 1.504 (2) | C8—H8A | 0.9900 |
C2—C3 | 1.398 (2) | C8—H8B | 0.9900 |
C2—O2 | 1.367 (2) | C8—C9 | 1.489 (3) |
C3—H3 | 0.9500 | C8—O2 | 1.429 (2) |
C3—C4 | 1.388 (3) | C9—H9 | 0.9500 |
C4—H4 | 0.9500 | C9—C10 | 1.317 (3) |
C4—C5 | 1.386 (3) | C10—H10A | 0.9500 |
C5—H5 | 0.9500 | C10—H10B | 0.9500 |
C5—C6 | 1.394 (2) | N1—H1A | 0.90 (2) |
C6—H6 | 0.9500 | N1—H1B | 0.89 (3) |
C1—C6—H6 | 119.4 | C7—N1—H1A | 123.2 (16) |
C10—C9—C8 | 126.30 (18) | C7—N1—H1B | 124.0 (16) |
C10—C9—H9 | 116.9 | C8—C9—H9 | 116.9 |
C2—C1—C7 | 124.39 (15) | C9—C10—H10A | 120.0 |
C2—C3—H3 | 120.1 | C9—C10—H10B | 120.0 |
C2—O2—C8 | 117.72 (13) | C9—C8—H8A | 109.8 |
C3—C2—C1 | 120.00 (16) | C9—C8—H8B | 109.8 |
C3—C4—H4 | 119.6 | H10A—C10—H10B | 120.0 |
C4—C3—C2 | 119.89 (18) | H1A—N1—H1B | 113 (2) |
C4—C3—H3 | 120.1 | H8A—C8—H8B | 108.2 |
C4—C5—H5 | 120.4 | N1—C7—C1 | 118.44 (16) |
C4—C5—C6 | 119.20 (17) | O1—C7—C1 | 119.23 (15) |
C5—C4—C3 | 120.84 (17) | O1—C7—N1 | 122.25 (16) |
C5—C4—H4 | 119.6 | O2—C2—C1 | 116.64 (14) |
C5—C6—C1 | 121.22 (17) | O2—C2—C3 | 123.36 (16) |
C5—C6—H6 | 119.4 | O2—C8—H8A | 109.8 |
C6—C1—C2 | 118.81 (15) | O2—C8—H8B | 109.8 |
C6—C1—C7 | 116.76 (16) | O2—C8—C9 | 109.54 (15) |
C6—C5—H5 | 120.4 |
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···Cgii | 0.99 | 2.68 | 3.461 (2) | 137 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C10H11NO2 |
Mr | 177.20 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 5.08891 (17), 11.2542 (4), 15.8802 (6) |
V (Å3) | 909.48 (5) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 0.74 |
Crystal size (mm) | 0.30 × 0.09 × 0.08 |
Data collection | |
Diffractometer | Agilent SuperNova Atlas diffractometer |
Absorption correction | Gaussian (CrysAlis PRO; Agilent, 2012) |
Tmin, Tmax | 0.862, 0.951 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4718, 1079, 1016 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.619 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.087, 1.03 |
No. of reflections | 1079 |
No. of parameters | 126 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.17, −0.18 |
Computer programs: CrysAlis PRO (Agilent, 2012), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) within OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2009); Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).
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···Cgii | 0.99 | 2.68 | 3.461 (2) | 137 |
Symmetry codes: (i) x+1/2, −y+1/2, −z+1; (ii) x+1, y, z. |
References
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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.