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Acta Cryst. (2008). E64, o1052    [ doi:10.1107/S160053680801009X ]

(S)-N-(1-Hydroxymethyl-2-methylpropyl)-2-methoxybenzamide

J. Li, W. Wang, J. Lan and J. You

Abstract top

The title compound, C13H19NO3, is an important synthetic intermediate. Weak O-H...O and N-H...O hydrogen bonds enhance the stability of the crystal structure.

Comment top

Oxazoline ligands have been proved to be a class of chiral ligands, being capable of forming a broad variety of metal complexes that are capable of catalyzing a great number of reactions with excellent enantioselectivity (Rechavi & Lemaire, 2002). It is believed that the oxazoline ring can be modified structurally by replacing the O atom with a substituted N atom, leading to new types of imidazoline ligands (Ma & You, 2007). However, all those ligands can prepared by this compound as an intermediate. Herein, we report the synthesis and structure of the title compound (I).

As shown in Fig. 1, there is a chiral center at C9 derived from L-valinol. The C—N bond lengths are 1.318 (4) Å and 1.463 (4) Å, and the C8—N1—C9 angle is 125.3 (3) °. A combination of O—H···O and N—H···O hydrogen bonds interactions provide packing forces in the crystal structure of the title compound.

Related literature top

For related literature, see: Ma & You (2007); Rechavi & Lemaire (2002).

Experimental top

NaH (8.7 g, 60%, 0.216 mol) was added portionwise to a stirred solution of L-valinol (22.1 g, 0.215 mol) in dry THF (120 ml). The mixture was stirred at ambient temperature for 1 h. To this solution was added 2-Methoxy-benzoic acid methyl ester (17.8 g, 0.107 mol) dissolved in THF (50 ml). The mixture was refluxed for 12 h under nitrogen, quenched with H2O (10 ml) and concentrated by evaporation of the solvent. The residue was dissolved in CH2Cl2 (100 ml), washed with H2O, brine, and dried over MgSO4. And then removal of the solvent in vacuo gave a white solid, which was recrystallized from ethyl acetate and petroleum ether to afford the title compound as white crystals (22.8 g, 90%).

Refinement top

H atoms were positioned geometrically and refined in the riding model approximation with O—H = 0.82 Å, N—H = 0.86 Å, and C—H = 0.93, 0.96, 0.97 or 0.98 Å. The Uiso(H) = 1.5 Ueq(C) for the CH3 while it was set to 1.2 Ueq(C,N,O) for all other H atoms. Due to abscence of significant anomalous dispersion effects, the reflection data were merged.

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 30% probability displacement ellipsoids and the atomic numbering.
(S)-N-(1-Hydroxymethyl-2-methylpropyl)-2-methoxybenzamide top
Crystal data top
C13H19NO3F000 = 512
Mr = 237.29Dx = 1.202 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 25 reflections
a = 9.015 (4) Åθ = 4.5–6.7º
b = 10.386 (4) ŵ = 0.09 mm−1
c = 14.005 (4) ÅT = 291 (2) K
V = 1311.3 (9) Å3Block, colourless
Z = 40.50 × 0.44 × 0.40 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.010
Radiation source: fine-focus sealed tubeθmax = 25.5º
Monochromator: graphiteθmin = 2.4º
T = 291(2) Kh = −3→10
ω/2θ scansk = −3→12
Absorption correction: nonel = −5→16
1457 measured reflections3 standard reflections
1397 independent reflections every 120 reflections
848 reflections with I > 2σ(I) intensity decay: 0.4%
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.045  w = 1/[σ2(Fo2) + (0.0778P)2 + 0.0096P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.136(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.21 e Å−3
1397 reflectionsΔρmin = −0.14 e Å−3
164 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.069 (8)
Secondary atom site location: difference Fourier map
Crystal data top
C13H19NO3V = 1311.3 (9) Å3
Mr = 237.29Z = 4
Orthorhombic, P212121Mo Kα
a = 9.015 (4) ŵ = 0.09 mm−1
b = 10.386 (4) ÅT = 291 (2) K
c = 14.005 (4) Å0.50 × 0.44 × 0.40 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.010
Absorption correction: none3 standard reflections
1457 measured reflections every 120 reflections
1397 independent reflections intensity decay: 0.4%
848 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.045Δρmax = 0.21 e Å−3
wR(F2) = 0.136Δρmin = −0.14 e Å−3
S = 1.02Absolute structure: ?
1397 reflectionsFlack parameter: ?
164 parametersRogers parameter: ?
H-atom parameters constrained
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
xyzUiso*/Ueq
O10.1432 (3)0.3872 (3)0.16126 (19)0.0666 (8)
O20.5192 (3)0.3286 (3)−0.00264 (18)0.0703 (8)
O30.2632 (4)0.0046 (3)−0.0111 (2)0.0810 (10)
H30.19450.0562−0.01400.097*
N10.3536 (3)0.2340 (2)0.0926 (2)0.0487 (8)
H1N10.27110.24330.12270.058*
C10.1842 (4)0.4786 (3)0.0963 (3)0.0514 (9)
C20.1074 (5)0.5935 (4)0.0851 (3)0.0709 (12)
H20.02400.60990.12230.085*
C30.1535 (6)0.6826 (4)0.0201 (4)0.0878 (16)
H3A0.10090.75910.01330.105*
C40.2760 (6)0.6610 (4)−0.0355 (4)0.0929 (18)
H40.30780.7226−0.07910.112*
C50.3519 (5)0.5457 (4)−0.0255 (3)0.0745 (13)
H50.43370.5300−0.06420.089*
C60.3096 (4)0.4533 (3)0.0402 (3)0.0489 (9)
C70.0018 (6)0.3961 (7)0.2048 (3)0.109 (2)
H7A−0.00380.47390.24160.163*
H7B−0.01300.32330.24600.163*
H7C−0.07350.39700.15640.163*
C80.4020 (4)0.3328 (3)0.0425 (2)0.0459 (9)
C90.4288 (4)0.1097 (3)0.1012 (2)0.0456 (8)
H90.50500.10600.05140.055*
C100.3202 (5)0.0025 (3)0.0824 (3)0.0609 (10)
H10A0.3691−0.07940.09320.073*
H10B0.23870.00910.12730.073*
C110.5075 (5)0.0978 (4)0.1981 (3)0.0632 (11)
H110.55150.01150.20020.076*
C120.6339 (6)0.1925 (5)0.2074 (4)0.0939 (16)
H12A0.59570.27870.20450.141*
H12B0.70310.17940.15620.141*
H12C0.68320.17960.26740.141*
C130.4068 (6)0.1084 (6)0.2833 (3)0.107 (2)
H13A0.46300.09460.34060.160*
H13B0.32990.04470.27880.160*
H13C0.36310.19260.28490.160*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0560 (16)0.0735 (18)0.0704 (16)0.0177 (16)0.0102 (13)0.0020 (15)
O20.0553 (16)0.0652 (18)0.0903 (18)−0.0022 (15)0.0249 (16)0.0137 (16)
O30.072 (2)0.071 (2)0.099 (2)0.0007 (16)−0.0180 (18)−0.0113 (17)
N10.0369 (15)0.0481 (16)0.0610 (17)0.0057 (15)0.0078 (14)0.0039 (14)
C10.050 (2)0.046 (2)0.058 (2)−0.0001 (18)−0.0117 (19)−0.0054 (18)
C20.064 (3)0.060 (3)0.089 (3)0.015 (2)−0.016 (2)−0.019 (2)
C30.070 (3)0.048 (2)0.146 (4)0.002 (2)−0.043 (3)0.008 (3)
C40.067 (3)0.059 (3)0.152 (5)−0.011 (3)−0.030 (3)0.047 (3)
C50.053 (2)0.066 (2)0.104 (3)−0.010 (2)−0.011 (2)0.031 (3)
C60.044 (2)0.0442 (18)0.059 (2)−0.0051 (17)−0.0149 (17)0.0013 (17)
C70.077 (3)0.156 (6)0.094 (3)0.036 (4)0.030 (3)0.020 (4)
C80.037 (2)0.046 (2)0.054 (2)−0.0041 (17)−0.0023 (16)0.0044 (18)
C90.0387 (18)0.0447 (19)0.0534 (19)0.0069 (17)0.0040 (15)−0.0004 (17)
C100.053 (2)0.050 (2)0.080 (3)0.0044 (19)0.000 (2)0.004 (2)
C110.062 (3)0.061 (3)0.067 (2)0.016 (2)−0.009 (2)0.011 (2)
C120.096 (3)0.093 (3)0.093 (3)0.000 (3)−0.037 (3)−0.011 (3)
C130.120 (4)0.146 (5)0.054 (2)0.031 (5)0.004 (3)0.016 (3)
Geometric parameters (Å, °) top
O1—C11.365 (4)C6—C81.504 (5)
O1—C71.416 (5)C7—H7A0.9600
O2—C81.232 (4)C7—H7B0.9600
O3—C101.406 (5)C7—H7C0.9600
O3—H30.8200C9—C101.506 (5)
N1—C81.318 (4)C9—C111.537 (5)
N1—C91.463 (4)C9—H90.9800
N1—H1N10.8600C10—H10A0.9700
C1—C21.389 (5)C10—H10B0.9700
C1—C61.402 (5)C11—C131.503 (6)
C2—C31.363 (6)C11—C121.511 (6)
C2—H20.9300C11—H110.9800
C3—C41.369 (7)C12—H12A0.9600
C3—H3A0.9300C12—H12B0.9600
C4—C51.386 (6)C12—H12C0.9600
C4—H40.9300C13—H13A0.9600
C5—C61.383 (5)C13—H13B0.9600
C5—H50.9300C13—H13C0.9600
C1—O1—C7119.1 (4)N1—C8—C6118.4 (3)
C10—O3—H3109.5N1—C9—C10109.7 (3)
C8—N1—C9125.3 (3)N1—C9—C11111.0 (3)
C8—N1—H1N1117.4C10—C9—C11113.3 (3)
C9—N1—H1N1117.4N1—C9—H9107.5
O1—C1—C2122.5 (4)C10—C9—H9107.5
O1—C1—C6117.5 (3)C11—C9—H9107.5
C2—C1—C6120.0 (4)O3—C10—C9112.9 (3)
C3—C2—C1120.4 (4)O3—C10—H10A109.0
C3—C2—H2119.8C9—C10—H10A109.0
C1—C2—H2119.8O3—C10—H10B109.0
C2—C3—C4121.0 (4)C9—C10—H10B109.0
C2—C3—H3A119.5H10A—C10—H10B107.8
C4—C3—H3A119.5C13—C11—C12109.8 (4)
C3—C4—C5118.8 (4)C13—C11—C9114.6 (3)
C3—C4—H4120.6C12—C11—C9111.8 (3)
C5—C4—H4120.6C13—C11—H11106.7
C6—C5—C4122.0 (5)C12—C11—H11106.7
C6—C5—H5119.0C9—C11—H11106.7
C4—C5—H5119.0C11—C12—H12A109.5
C5—C6—C1117.7 (4)C11—C12—H12B109.5
C5—C6—C8116.0 (3)H12A—C12—H12B109.5
C1—C6—C8126.2 (3)C11—C12—H12C109.5
O1—C7—H7A109.5H12A—C12—H12C109.5
O1—C7—H7B109.5H12B—C12—H12C109.5
H7A—C7—H7B109.5C11—C13—H13A109.5
O1—C7—H7C109.5C11—C13—H13B109.5
H7A—C7—H7C109.5H13A—C13—H13B109.5
H7B—C7—H7C109.5C11—C13—H13C109.5
O2—C8—N1122.0 (3)H13A—C13—H13C109.5
O2—C8—C6119.6 (3)H13B—C13—H13C109.5
C7—O1—C1—C213.4 (5)C9—N1—C8—C6179.2 (3)
C7—O1—C1—C6−167.0 (4)C5—C6—C8—O29.9 (5)
O1—C1—C2—C3179.3 (3)C1—C6—C8—O2−171.7 (3)
C6—C1—C2—C3−0.3 (6)C5—C6—C8—N1−169.6 (3)
C1—C2—C3—C4−0.0 (6)C1—C6—C8—N18.8 (5)
C2—C3—C4—C50.9 (7)C8—N1—C9—C10−130.9 (4)
C3—C4—C5—C6−1.5 (7)C8—N1—C9—C11103.2 (4)
C4—C5—C6—C11.2 (6)N1—C9—C10—O363.2 (4)
C4—C5—C6—C8179.7 (4)C11—C9—C10—O3−172.2 (3)
O1—C1—C6—C5−179.8 (3)N1—C9—C11—C1359.7 (4)
C2—C1—C6—C5−0.2 (5)C10—C9—C11—C13−64.2 (5)
O1—C1—C6—C81.8 (5)N1—C9—C11—C12−66.1 (4)
C2—C1—C6—C8−178.6 (3)C10—C9—C11—C12170.0 (3)
C9—N1—C8—O2−0.3 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.822.002.806 (4)170
N1—H1N1···O10.861.962.656 (4)137
Symmetry codes: (i) x−1/2, −y+1/2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O2i0.822.002.806 (4)170
N1—H1N1···O10.861.962.656 (4)137
Symmetry codes: (i) x−1/2, −y+1/2, −z.
references
References top

Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA.

Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst. 22, 384–387.

Gabe, E. J. & White, P. S. (1993). DIFRAC. American Crystallographic Association, Pittsburgh Meeting. Abstract PA104.

Ma, K. & You, J. (2007). Chem. Eur. J. 13, 1863–1871.

Rechavi, D. & Lemaire, M. (2002). Chem. Rev. 102, 3467–3494.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.