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Acta Cryst. (2008). E64, o2307    [ doi:10.1107/S1600536808035812 ]

1-(4-Methyl-1-naphthyl)ethanone

Y.-H. Hu, X.-L. Zhao, W.-G. Yang, J.-F. Yao and X.-T. Lu

Abstract top

In the molecule of the title compound, C13H12O, the two aromatic rings are oriented at a dihedral angle of 2.90 (3)°. An intramolecular C-H...O hydrogen bond results in the formation of a non-planar six-membered ring, which adopts an envelope conformation. In the crystal structure, intermolecular C-H...O hydrogen bonds link the molecules.

Comment top

The title compound is a dye and plastic processing aid of intermediate, 1,4-naphthalenedicarboxylic acid. As part of our ongoing studies in this area, we report herein its crystal structure.

In the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C3-C8) and B (C1-C3/C8-C10) are, of course, planar and the dihedral angle between them is A/B = 2.90 (3)°. The intramolecular C-H···O hydrogen bond (Table 1) results in the formation of a nonplanar six-membered ring C (C2-C4/C12/O/H2A) adopting envelope conformation with O atom displaced by -0.533 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related structures, see: Dixon et al. (1981); Grummitt & Buck (1943); Merritt & Braun (1950). For bond-length data, see: Allen et al. (1987).

Experimental top

In a three-necked flask, naphthalene (256.0 g, 2.00 mol), paraformaldehyde (110.0 g, 1.22 mol), glacial acetic acid (260 ml), concentrated hydrochloric acid (362 ml) and phosphoric acid (165 ml, 85%) are heated with efficient stirring in a water bath at 353-358 K for 6 h. The product is washed two times with cold water (1 liter), a solution of potassium carbonate (20.0 g) in cold water (500 ml), and finally with cold water (500 ml). Ether (200 ml) is added to the oil layer and the solution is given a preliminary drying with anhydrous potassium carbonate (10.0 g) for 1 h. The lower aqueous layer is separated and the ether solution again dried with potassium carbonate (20.0 g) for 8-10 h. The ether solution is distilled first at atmospheric pressure to remove the ether, and then followed by distillation under reduced pressure to obtain 1-chloromethylnaphthalene. In a three-necked flask, magnesium (63.2 g), absolute ether (100 ml), a crystal of iodine, a solution of 1-chloromethylnaphthalene (150.0 g, 0.85 mol) in absolute ether (750 ml) and absolute ether (1080 ml) are mixed, and the ether solution of the chloride is added to the mixture in 5 h, and then stirred and heated at reflux for an additional 1 h to obtain 1-methylnaphthalene. The yield was 88-92% (Grummitt & Buck, 1943). Acetyl chloride (39.3 g, 0.48 mol, 38 ml) is added over 45 min to a stirred mixture of 1-methylnaphthalene (Aldrich) (67.0 g, 0.48 mol), dry dichloromethane (340 ml) and finely ground anhydrous aluminium chloride (76.0 g, 0.57 mol) at 273 K. After the addition is completed, the mixture is stirred at ambient temperature for 4 h, and then heated under reflux for 2.5 h (Dixon et al., 1981). The reaction solution is washed with hydrochloric acid many times. The aqueous phase followed by distillation under reduced pressure gave the title compound (yield; 71%) (Merritt & Braun, 1950). Crystals suitable for X-ray analysis are obtained by slow evaporation of an petroleum ether solution.

Refinement top

H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms with Uiso(H) = xUeq(C), where x = 1.5 for methyl H and x = 1.2 for aromatic H atoms.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom- numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bond is shown as dashed line.
[Figure 2] Fig. 2. A partial packing diagram. Hydrogen bonds are shown as dashed lines.
1-(4-Methyl-1-naphthyl)ethanone top
Crystal data top
C13H12OF(000) = 784
Mr = 184.23Dx = 1.208 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 15.449 (3) Åθ = 9–13°
b = 7.8290 (16) ŵ = 0.08 mm−1
c = 16.755 (3) ÅT = 294 K
V = 2026.5 (7) Å3Block, colorless
Z = 80.30 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		905 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.0000
graphiteθmax = 25.3°, θmin = 2.4°
ω/2θ scansh = 0→18
Absorption correction: ψ scan
(North et al., 1968)		k = 0→9
Tmin = 0.978, Tmax = 0.993l = 0→20
1932 measured reflections3 standard reflections every 120 min
1846 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.05P)2 + 0.8P]
where P = (Fo2 + 2Fc2)/3
1846 reflections(Δ/σ)max < 0.001
127 parametersΔρmax = 0.14 e Å−3
0 restraintsΔρmin = −0.16 e Å−3
Crystal data top
C13H12OV = 2026.5 (7) Å3
Mr = 184.23Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 15.449 (3) ŵ = 0.08 mm−1
b = 7.8290 (16) ÅT = 294 K
c = 16.755 (3) Å0.30 × 0.20 × 0.10 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		905 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)		Rint = 0.0000
Tmin = 0.978, Tmax = 0.993θmax = 25.3°
1932 measured reflections3 standard reflections every 120 min
1846 independent reflections intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.155Δρmax = 0.14 e Å−3
S = 1.01Δρmin = −0.16 e Å−3
1846 reflectionsAbsolute structure: ?
127 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
O0.72633 (18)−0.0605 (3)0.52877 (14)0.1022 (9)
C10.4927 (2)0.1819 (5)0.5918 (2)0.0830 (11)
H1A0.45900.18270.54570.100*
C20.5750 (2)0.1221 (4)0.58895 (18)0.0665 (9)
H2A0.59730.08290.54070.080*
C30.62766 (19)0.1181 (3)0.65824 (17)0.0498 (7)
C40.7163 (2)0.0658 (3)0.65707 (18)0.0573 (8)
C50.7619 (2)0.0651 (4)0.7276 (2)0.0679 (9)
H5A0.81980.03260.72720.082*
C60.7234 (2)0.1121 (4)0.79985 (19)0.0710 (10)
H6A0.75540.10340.84670.085*
C70.6410 (2)0.1698 (4)0.80342 (17)0.0611 (8)
C80.59134 (18)0.1753 (3)0.73121 (18)0.0531 (7)
C90.5063 (2)0.2390 (5)0.7314 (2)0.0731 (10)
H9A0.48250.27940.77870.088*
C100.4583 (2)0.2424 (4)0.6633 (3)0.0829 (11)
H10A0.40220.28540.66450.100*
C110.6043 (3)0.2281 (5)0.88156 (17)0.0941 (13)
H11A0.64740.21630.92250.141*
H11B0.55480.15970.89480.141*
H11C0.58730.34570.87750.141*
C120.7628 (3)0.0157 (4)0.5827 (2)0.0733 (10)
C130.8571 (2)0.0651 (4)0.5755 (2)0.0961 (13)
H13A0.87940.02590.52530.144*
H13B0.88930.01370.61830.144*
H13C0.86250.18710.57860.144*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O0.127 (2)0.098 (2)0.0814 (16)−0.0038 (18)0.0255 (17)−0.0239 (15)
C10.081 (3)0.079 (3)0.090 (3)−0.011 (2)−0.028 (2)0.017 (2)
C20.078 (2)0.061 (2)0.061 (2)−0.0079 (19)−0.0101 (18)0.0077 (16)
C30.0557 (18)0.0421 (16)0.0516 (16)−0.0036 (14)0.0025 (15)0.0035 (14)
C40.066 (2)0.0455 (17)0.0601 (18)−0.0005 (16)0.0093 (18)0.0039 (15)
C50.063 (2)0.060 (2)0.081 (2)0.0066 (17)−0.005 (2)0.0095 (18)
C60.079 (3)0.074 (2)0.061 (2)0.000 (2)−0.0125 (18)0.0105 (17)
C70.073 (2)0.0565 (19)0.0535 (18)−0.0008 (18)0.0024 (18)0.0037 (15)
C80.0516 (18)0.0464 (16)0.0614 (18)−0.0009 (15)0.0018 (16)0.0054 (14)
C90.066 (2)0.074 (2)0.079 (2)0.005 (2)0.010 (2)0.0109 (19)
C100.053 (2)0.072 (2)0.124 (3)−0.0011 (19)0.000 (2)0.021 (2)
C110.122 (3)0.101 (3)0.059 (2)0.013 (3)0.011 (2)−0.004 (2)
C120.095 (3)0.0495 (19)0.076 (2)0.0060 (19)0.021 (2)0.0012 (18)
C130.079 (3)0.081 (3)0.128 (3)0.007 (2)0.046 (2)0.004 (2)
Geometric parameters (Å, °) top
O—C121.220 (4)C7—C81.434 (4)
C1—C21.357 (4)C7—C111.498 (4)
C1—C101.394 (5)C8—C91.405 (4)
C1—H1A0.9300C9—C101.360 (4)
C2—C31.418 (4)C9—H9A0.9300
C2—H2A0.9300C10—H10A0.9300
C3—C81.418 (4)C11—H11A0.9600
C3—C41.430 (4)C11—H11B0.9600
C4—C51.376 (4)C11—H11C0.9600
C4—C121.491 (4)C12—C131.513 (5)
C5—C61.398 (4)C13—H13A0.9600
C5—H5A0.9300C13—H13B0.9600
C6—C71.352 (4)C13—H13C0.9600
C6—H6A0.9300
C2—C1—C10120.3 (3)C3—C8—C7120.4 (3)
C2—C1—H1A119.9C10—C9—C8121.0 (3)
C10—C1—H1A119.9C10—C9—H9A119.5
C1—C2—C3121.1 (3)C8—C9—H9A119.5
C1—C2—H2A119.4C9—C10—C1120.5 (3)
C3—C2—H2A119.4C9—C10—H10A119.8
C8—C3—C2118.2 (3)C1—C10—H10A119.8
C8—C3—C4118.8 (3)C7—C11—H11A109.5
C2—C3—C4123.0 (3)C7—C11—H11B109.5
C5—C4—C3118.7 (3)H11A—C11—H11B109.5
C5—C4—C12118.1 (3)C7—C11—H11C109.5
C3—C4—C12123.2 (3)H11A—C11—H11C109.5
C4—C5—C6121.7 (3)H11B—C11—H11C109.5
C4—C5—H5A119.2O—C12—C4121.7 (3)
C6—C5—H5A119.2O—C12—C13120.8 (3)
C7—C6—C5121.8 (3)C4—C12—C13117.5 (3)
C7—C6—H6A119.1C12—C13—H13A109.5
C5—C6—H6A119.1C12—C13—H13B109.5
C6—C7—C8118.5 (3)H13A—C13—H13B109.5
C6—C7—C11119.8 (3)C12—C13—H13C109.5
C8—C7—C11121.7 (3)H13A—C13—H13C109.5
C9—C8—C3118.9 (3)H13B—C13—H13C109.5
C9—C8—C7120.6 (3)
C10—C1—C2—C30.5 (5)C2—C3—C8—C7178.4 (3)
C1—C2—C3—C81.3 (4)C4—C3—C8—C7−4.1 (4)
C1—C2—C3—C4−176.1 (3)C6—C7—C8—C9−178.1 (3)
C8—C3—C4—C53.1 (4)C11—C7—C8—C91.1 (5)
C2—C3—C4—C5−179.6 (3)C6—C7—C8—C31.2 (4)
C8—C3—C4—C12−175.4 (3)C11—C7—C8—C3−179.5 (3)
C2—C3—C4—C122.0 (4)C3—C8—C9—C101.6 (5)
C3—C4—C5—C60.8 (5)C7—C8—C9—C10−179.1 (3)
C12—C4—C5—C6179.3 (3)C8—C9—C10—C10.2 (5)
C4—C5—C6—C7−3.9 (5)C2—C1—C10—C9−1.3 (5)
C5—C6—C7—C82.7 (5)C5—C4—C12—O146.1 (3)
C5—C6—C7—C11−176.5 (3)C3—C4—C12—O−35.4 (5)
C2—C3—C8—C9−2.3 (4)C5—C4—C12—C13−34.8 (4)
C4—C3—C8—C9175.2 (3)C3—C4—C12—C13143.7 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O0.932.302.920 (4)124
C13—H13C···Oi0.962.553.296 (4)135
Symmetry codes: (i) −x+3/2, y+1/2, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C2—H2A···O0.932.302.920 (4)124
C13—H13C···Oi0.962.553.296 (4)135
Symmetry codes: (i) −x+3/2, y+1/2, z.
references
References top

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.

Dixon, E. A., Fischer, A. & Robinson, F. P. (1981). Can. J. Chem. 59, 2629–2641.

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands.

Grummitt, O. & Buck, A. C. (1943). J. Am. Chem. Soc. 65, 295–296.

Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany.

Merritt, C. & Braun, C. E. (1950). Org. Synth. 30, 1–2.

North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.

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

Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.