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Acta Cryst. (2007). E63, o3713    [ doi:10.1107/S1600536807037828 ]

N-Benzylacetamide

W. Smiszek-Lindert and J. Kusz

Abstract top

Molecules of N-benzylacetamide, C9H11NO, are interconnected by a framework of weak intermolecular N-H...O hydrogen bonds. The molecules form infinite hydrogen-bonded chains, parallel to the a direction.

Comment top

We report here the synthesis, isolation of single crystals and structure determination of N-benzylacetamide, (I).

The title compound is subject of our study of a generation mechanism of IR spectra of hydrogen-bonded molecular crystals (Flakus & Michta, 2004, 2005; Flakus et al., 2007; Flakus, Tyl & Jones, 2003; Flakus & Pyzik, 2006). The spectral studies were preceded by determination of the crystal X-ray structure. Measurement of the IR spectra and theoretical analysis of the results concerned e.g. the linear dichroic effects, the H/D isotopic and temperature effects, observed in the solid-state IR spectra of the hydrogen and of the deuterium bond at the frequency ranges of the νN—H and νN—D bands, respectively. Some spectacular effects are especially visible for those systems, where the proton-acceptor atom is oxygen (Flakus & Michta, 2003).

The structure of (I) with the atomic numbering scheme is presented in Fig. 1. Molecules of (I) are interconnected by a framework of intermolecular N—H···O hydrogen bonds, viz. N1—H1N···O1, respectively, as shown in Fig. 2 and detailed in Table 1. The Fig. 2 also shows that in the crystal structure of (I) the molecules interact via N—H···O hydrogen bonds, forming infinite chains perpendicular to the b axis. The values of the H—A and D···A distances and the D—H···A angle (Table 1) characterize this bond as a weak hydrogen bond (Desiraju & Steiner, 1999), and agree with relevant data for N-benzylacetamide forming intermolecular N—H···O hydrogen bonds [D···A = 2.90 (12)Å and D—H···A = 168.7 (9)°]. The weakening of the intermolecular hydrogen bond in (I) is supported by IR spectroscopic data. The band of the isolated N—H stretching vibration, νN—H, was located in the 3400–3100 cm−1 frequency range.

Related literature top

For related literature, see: Desiraju & Steiner (1999); Flakus & Michta (2003, 2004, 2005); Flakus & Pyzik (2006); Flakus et al. (2003, 2007); Kotera et al. (1968).

Experimental top

Benzylamine (30 g, 0.28 mol) was added to a solution of acetic acid (170 g, 2.83 mol) at 130–150°C with stirring. The reaction mixture was then brought to reflux for 6 h, allowed to cool and excess of acetic acid solution was evaporated under reduced pressure to give a white precipitate. The precipitate was dissolved in petroleum ether and the solution was left for crystallization at room temperature. After a few days, the deposited white crystals were collected and recrystallized from petroleum ether, giving single, needle-shaped crystals of quality suitable for X-ray measurement. The yield 34 g, 80%; m.p. 57°C; literature m.p. 58 − 59°C (Kotera et al., 1968).

The IR spectra of N-benzylacetamide crystals were measured by a transmission method in the frequency ranges of the proton and deuteron stretching vibration bands, νN—H and νN—D. Spectral experiment were performed at room temperature and at the temperature of liquid nitrogen (77 K), using polarized radiation. The solid-state spectra were measured with the 2 cm−1 resolution for the normal incidence of the radiation beam, using the FT—IR Nicolet Magna 560 spectrometer.

Refinement top

Some of the hydrogen atoms were located in a difference Fourier map and refined freely; other H atoms were placed in calculated positions 0,98 Å (methyl C) and refined as riding with Uiso (H) = 1,5Ueq (C) for the methyl H atoms.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. The conformation of N-benzylacetamide molecule with the atom numbering scheme. Atomic displacement ellipsoids represent 50% probability level.
[Figure 2] Fig. 2. The crystal packing of the title compound, viewed approximately down the b axis. The intermolecular N—H···O interactions are represented by dashed lines.
N-benzylacetamide top
Crystal data top
C9H11NOZ = 4
Mr = 149.19F000 = 320
Monoclinic, P21/cDx = 1.196 Mg m−3
a = 4.8383 (10) ÅMo Kα radiation
λ = 0.71073 Å
b = 14.906 (3) ŵ = 0.08 mm−1
c = 11.663 (2) ÅT = 298 (2) K
β = 100.04 (3)ºNeedle, white
V = 828.3 (3) Å30.60 × 0.12 × 0.01 mm
Data collection top
Oxford Diffraction KM-4 CCD Sapphire3
diffractometer		1377 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.017
Monochromator: graphiteθmax = 32.8º
T = 298(2) Kθmin = 3.3º
θ scansh = −3→7
Absorption correction: nonek = −22→22
7651 measured reflectionsl = −17→16
2718 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039H atoms treated by a mixture of
independent and constrained refinement
wR(F2) = 0.096  w = 1/[σ2(Fo2) + (0.0459P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2718 reflectionsΔρmax = 0.18 e Å−3
133 parametersΔρmin = −0.18 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C9H11NOV = 828.3 (3) Å3
Mr = 149.19Z = 4
Monoclinic, P21/cMo Kα
a = 4.8383 (10) ŵ = 0.08 mm−1
b = 14.906 (3) ÅT = 298 (2) K
c = 11.663 (2) Å0.60 × 0.12 × 0.01 mm
β = 100.04 (3)º
Data collection top
Oxford Diffraction KM-4 CCD Sapphire3
diffractometer		2718 independent reflections
Absorption correction: none1377 reflections with I > 2σ(I)
7651 measured reflectionsRint = 0.017
Refinement top
R[F2 > 2σ(F2)] = 0.039133 parameters
wR(F2) = 0.096H atoms treated by a mixture of
independent and constrained refinement
S = 1.00Δρmax = 0.18 e Å−3
2718 reflectionsΔρmin = −0.18 e Å−3
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 > 2sigma(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
N10.17528 (16)0.41069 (5)0.71931 (7)0.0389 (2)
O1−0.22568 (12)0.44356 (5)0.78353 (6)0.0548 (2)
C10.22770 (18)0.31836 (6)0.55164 (8)0.0382 (2)
C20.3398 (2)0.23405 (7)0.54011 (9)0.0454 (3)
C30.4952 (2)0.21655 (8)0.45370 (9)0.0520 (3)
C40.5422 (2)0.28301 (9)0.37859 (9)0.0553 (3)
C50.4327 (3)0.36742 (9)0.38894 (9)0.0569 (3)
C60.2780 (2)0.38484 (8)0.47474 (9)0.0490 (3)
C70.0568 (2)0.33683 (8)0.64518 (10)0.0471 (3)
C80.02600 (17)0.45714 (6)0.78448 (8)0.0372 (2)
C90.1794 (2)0.52948 (8)0.85890 (9)0.0546 (3)
H1N0.362 (2)0.4186 (7)0.7291 (9)0.052 (3)*
H20.302 (2)0.1875 (7)0.5928 (10)0.061 (3)*
H30.572 (2)0.1552 (8)0.4457 (10)0.068 (3)*
H40.648 (3)0.2737 (8)0.3205 (11)0.070 (4)*
H50.465 (3)0.4141 (9)0.3392 (11)0.083 (4)*
H60.213 (2)0.4431 (8)0.4854 (10)0.060 (3)*
H9A0.11170.58710.82960.082*
H9B0.37660.52510.85730.082*
H9C0.14830.52270.93750.082*
H17−0.141 (3)0.3521 (7)0.6096 (9)0.063 (3)*
H270.045 (2)0.2809 (8)0.6986 (10)0.067 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0224 (4)0.0499 (5)0.0451 (5)−0.0047 (3)0.0080 (3)−0.0065 (4)
O10.0251 (4)0.0719 (5)0.0702 (5)−0.0032 (3)0.0162 (3)−0.0056 (4)
C10.0290 (4)0.0436 (6)0.0405 (5)−0.0056 (4)0.0021 (4)−0.0050 (4)
C20.0484 (6)0.0404 (6)0.0456 (6)−0.0050 (4)0.0035 (5)−0.0017 (5)
C30.0539 (6)0.0490 (7)0.0506 (6)0.0076 (5)0.0022 (5)−0.0127 (6)
C40.0531 (7)0.0732 (8)0.0406 (6)0.0062 (6)0.0107 (5)−0.0091 (6)
C50.0627 (7)0.0624 (8)0.0475 (6)0.0040 (6)0.0152 (5)0.0105 (6)
C60.0486 (6)0.0437 (6)0.0554 (6)0.0086 (5)0.0114 (5)0.0035 (5)
C70.0355 (5)0.0545 (7)0.0529 (6)−0.0121 (5)0.0123 (5)−0.0099 (5)
C80.0265 (4)0.0462 (6)0.0404 (5)0.0004 (4)0.0101 (4)0.0049 (4)
C90.0422 (6)0.0658 (7)0.0599 (7)−0.0076 (5)0.0203 (5)−0.0174 (6)
Geometric parameters (Å, °) top
N1—C81.3305 (12)C4—C51.3786 (18)
N1—C71.4544 (13)C4—H40.928 (12)
N1—H1N0.897 (11)C5—C61.3747 (16)
O1—C81.2325 (10)C5—H50.937 (14)
C1—C21.3845 (14)C6—H60.940 (11)
C1—C61.3863 (14)C7—H171.000 (12)
C1—C71.5046 (14)C7—H271.048 (12)
C2—C31.3831 (16)C8—C91.4976 (14)
C2—H20.966 (11)C9—H9A0.9600
C3—C41.3674 (16)C9—H9B0.9600
C3—H30.998 (12)C9—H9C0.9600
C8—N1—C7122.45 (8)C5—C6—C1121.00 (11)
C8—N1—H1N119.5 (7)C5—C6—H6120.6 (7)
C7—N1—H1N117.3 (7)C1—C6—H6118.3 (7)
C2—C1—C6118.04 (10)N1—C7—C1111.11 (8)
C2—C1—C7120.70 (9)N1—C7—H17108.9 (6)
C6—C1—C7121.26 (9)C1—C7—H17110.3 (6)
C3—C2—C1120.92 (10)N1—C7—H27107.8 (6)
C3—C2—H2121.0 (7)C1—C7—H27112.2 (6)
C1—C2—H2118.0 (7)H17—C7—H27106.3 (9)
C4—C3—C2120.15 (11)O1—C8—N1122.90 (9)
C4—C3—H3119.9 (7)O1—C8—C9120.84 (8)
C2—C3—H3120.0 (7)N1—C8—C9116.25 (8)
C3—C4—C5119.73 (11)C8—C9—H9A109.5
C3—C4—H4122.2 (8)C8—C9—H9B109.5
C5—C4—H4118.0 (8)H9A—C9—H9B109.5
C6—C5—C4120.15 (12)C8—C9—H9C109.5
C6—C5—H5118.8 (8)H9A—C9—H9C109.5
C4—C5—H5121.1 (8)H9B—C9—H9C109.5
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.90 (1)2.02 (1)2.906 (1)168.7 (9)
Symmetry codes: (i) x+1, y, z.
Selected geometric parameters (Å, °) top
N1—C81.3305 (12)C2—C31.3831 (16)
N1—C71.4544 (13)C3—C41.3674 (16)
O1—C81.2325 (10)C4—C51.3786 (18)
C1—C21.3845 (14)C5—C61.3747 (16)
C1—C61.3863 (14)C6—H60.940 (11)
C1—C71.5046 (14)C8—C91.4976 (14)
C8—N1—C7122.45 (8)C6—C5—C4120.15 (12)
C2—C1—C6118.04 (10)C5—C6—C1121.00 (11)
C2—C1—C7120.70 (9)N1—C7—C1111.11 (8)
C6—C1—C7121.26 (9)O1—C8—N1122.90 (9)
C3—C2—C1120.92 (10)O1—C8—C9120.84 (8)
C4—C3—C2120.15 (11)N1—C8—C9116.25 (8)
C3—C4—C5119.73 (11)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O1i0.90 (1)2.02 (1)2.906 (1)168.7 (9)
Symmetry codes: (i) x+1, y, z.
references
References top

Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology. New York: Oxford University Press.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Flakus, H. & Michta, A. (2003). Vib. Spectrosc. 33, 177–187.

Flakus, H. & Michta, A. (2004). J. Mol. Struct. 707, 17–b>O. Final page?

Flakus, H. & Michta, A. (2005). J. Mol. Struct. 741, 19–29.

Flakus, H. & Pyzik, A. (2006). Chem. Phys. 323, 479–b>000. Final page?

Flakus, H., Śmiszek-Lindert, W. & Stadnicka, K. (2007). Chem. Phys. 335, 221–232.

Flakus, H., Tyl, A. & Jones, P. G. (2003). Vib. Spectrosc. 33, 163–b>000. Final page?

Kotera, K., et al. (1968). Tetrahedron, 24, 5677–5690. [Please provide full list of authors, or the first 15 names if the total number is over 15]

Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171.29.2. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany

Westrip, S. P. (2007). PublCIF. In preparation.