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Acta Cryst. (2007). E63, o3684    [ doi:10.1107/S1600536807037348 ]

3-Benzyl-6-methyl-3,4-dihydro-2H-1,3-benzoxazine

X.-L. Chen and M.-H. Wu

Abstract top

In the title molecule, C16H17NO, the dihedral angle between the phenyl and benzene rings is 28.4 (1)°. The six-membered 3,4-dihydro-2H-1,3-oxazine ring adopts a screw boat conformation. In the crystal structure, weak C-H...[pi](arene) interactions are present.

Comment top

Benzoxazine is a unique heterocyclic compound obtained from a cyclization reaction involving phenol, formaldehyde, and amine (Holly & Cope, 1944). It has generated interest as use in antipsychotic agents and antimalarial agents (Ren et al., 2001) and in the research of serotonin and dopamine receptors (Gentles et al., 1991; Petterson et al., 1990; Peglion et al., 1997). The title compound was prepared by reaction of 4-methylphenol, formaldehyde and benzyl amine and it's crystal structure has been determined herein.

In the molecule (Fig. 1), the dihedral angle between the phenyl and benzene rings is 28.4 (1)°. The atoms C11/C10/N1/C8 are nearly planar with the torsion angle for C11—C10—N1—C8 being 176.8 (2)°, and the dihedral angle between the C11—C10—N1—C8 mean plane and phenyl ring (C11—C16) is 65.6 (2)°.

In the crystal structure, molecules are linked by two types of weak C—H···(arene) interactions, involving atom H4 and the centroid of atoms C11–16, Cg1i, (symmetry code: (i) 3/2 − x,1/2 + y,3/2 − z), and H8B and the centroid of C2—C7, Cg2ii, (symmetry code: (ii) x,-1 + y, z) (Fig. 2).

Related literature top

For background information, see: Holly & Cope (1944); Ren et al. (2001); Gentles et al. (1991); Petterson et al. (1990); Peglion et al. (1997).

Experimental top

Formaldehyde (8 mL, 40%, 0.1 mol) was added slowly with stirring to a mixture of methanol (35 mL), benzylamine (10.7 g, 0.1 mol) and 4-methylphenol (10.8 g, 0.1 mol) over 2 h. The mixture was stirred for additional 60 h at room temperature. The resulting bright yellow solid was filtered and washed with methanol. The solid residue was recrystallized from methanol to give colorless crystals of the title compound in yield 88%, which were suitable for X-ray analysis.

Refinement top

All H atoms were placed in calculated positions (C—H = 0.93–0.97 Å) and included in the riding model approximation, with Uiso (H) = 1.2Uiso (C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top
[Figure 1] Fig. 1. View of the molecule with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. The packing viewed down the b axis. Intermolecular C—H···π interactions are shown as dashed lines.
3-Benzyl-6-methyl-3,4-dihydro-2H-1,3-benzoxazine top
Crystal data top
C16H17NOF000 = 512
Mr = 239.31Dx = 1.219 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1790 reflections
a = 13.4112 (11) Åθ = 3.2–22.2º
b = 5.1816 (4) ŵ = 0.08 mm−1
c = 19.4220 (17) ÅT = 290 (2) K
β = 105.007 (1)ºBlock, colorless
V = 1303.63 (19) Å30.20 × 0.20 × 0.10 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer		2418 independent reflections
Radiation source: fine-focus sealed tube1721 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 290(2) Kθmax = 25.5º
φ and ω scansθmin = 1.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		h = −16→16
Tmin = 0.985, Tmax = 0.993k = −5→6
8116 measured reflectionsl = −21→23
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)] = 0.056H-atom parameters constrained
wR(F2) = 0.150  w = 1/[σ2(Fo2) + (0.0644P)2 + 0.2864P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
2418 reflectionsΔρmax = 0.15 e Å−3
164 parametersΔρmin = −0.14 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
C16H17NOV = 1303.63 (19) Å3
Mr = 239.31Z = 4
Monoclinic, P21/nMo Kα
a = 13.4112 (11) ŵ = 0.08 mm−1
b = 5.1816 (4) ÅT = 290 (2) K
c = 19.4220 (17) Å0.20 × 0.20 × 0.10 mm
β = 105.007 (1)º
Data collection top
Bruker SMART CCD
diffractometer		2418 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)		1721 reflections with I > 2σ(I)
Tmin = 0.985, Tmax = 0.993Rint = 0.034
8116 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.056164 parameters
wR(F2) = 0.150H-atom parameters constrained
S = 1.05Δρmax = 0.15 e Å−3
2418 reflectionsΔρmin = −0.14 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
C10.6350 (2)0.7043 (6)1.07179 (14)0.0944 (9)
H1A0.64720.88701.07410.142*
H1B0.67590.62441.11440.142*
H1C0.56330.67141.06760.142*
C20.66457 (17)0.5940 (5)1.00776 (13)0.0629 (6)
C30.61450 (16)0.6715 (5)0.93952 (14)0.0685 (7)
H30.56130.79140.93320.082*
C40.64120 (15)0.5760 (5)0.88051 (12)0.0618 (6)
H40.60660.63230.83510.074*
C50.71923 (14)0.3970 (4)0.88896 (10)0.0489 (5)
C60.77210 (14)0.3136 (4)0.95650 (10)0.0467 (5)
C70.74327 (16)0.4150 (4)1.01466 (11)0.0565 (6)
H70.77820.36051.06010.068*
C80.85903 (16)0.1211 (4)0.96335 (11)0.0544 (5)
H8A0.91400.16201.00530.065*
H8B0.8339−0.05060.96960.065*
C90.81595 (15)0.1013 (4)0.83811 (11)0.0536 (6)
H9A0.7788−0.05720.84120.064*
H9B0.84330.08850.79660.064*
C100.96489 (15)0.3522 (4)0.89932 (10)0.0519 (5)
H10A1.01920.35870.94340.062*
H10B0.92300.50620.89700.062*
C111.01278 (14)0.3519 (4)0.83739 (10)0.0480 (5)
C120.98730 (19)0.5350 (4)0.78431 (13)0.0702 (7)
H120.93850.66030.78640.084*
C131.0325 (2)0.5370 (5)0.72802 (14)0.0847 (8)
H131.01440.66340.69300.102*
C141.10317 (19)0.3551 (5)0.72380 (13)0.0738 (7)
H141.13430.35720.68620.089*
C151.12840 (18)0.1695 (6)0.77481 (14)0.0792 (8)
H151.17600.04250.77150.095*
C161.08396 (17)0.1677 (5)0.83165 (12)0.0692 (7)
H161.10240.04040.86640.083*
N10.90020 (12)0.1235 (3)0.90035 (8)0.0484 (4)
O10.74424 (10)0.3150 (3)0.82815 (7)0.0597 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0824 (18)0.121 (2)0.094 (2)−0.0074 (17)0.0484 (16)−0.0340 (18)
C20.0527 (13)0.0740 (15)0.0689 (15)−0.0104 (11)0.0278 (12)−0.0150 (12)
C30.0454 (12)0.0731 (16)0.0891 (19)0.0073 (11)0.0212 (12)−0.0068 (14)
C40.0438 (11)0.0787 (16)0.0608 (14)0.0053 (11)0.0100 (10)0.0053 (12)
C50.0418 (10)0.0559 (12)0.0495 (12)−0.0029 (9)0.0127 (9)−0.0003 (10)
C60.0455 (11)0.0509 (12)0.0454 (12)−0.0044 (9)0.0148 (9)0.0027 (9)
C70.0551 (12)0.0681 (14)0.0490 (12)−0.0105 (11)0.0183 (10)0.0000 (10)
C80.0574 (12)0.0553 (13)0.0507 (12)0.0028 (10)0.0142 (10)0.0075 (10)
C90.0532 (12)0.0547 (13)0.0549 (13)−0.0072 (10)0.0174 (10)−0.0106 (10)
C100.0486 (11)0.0532 (13)0.0533 (12)−0.0022 (9)0.0122 (9)−0.0082 (10)
C110.0430 (11)0.0462 (11)0.0533 (12)−0.0061 (9)0.0098 (9)−0.0050 (10)
C120.0850 (17)0.0537 (14)0.0780 (16)0.0071 (12)0.0323 (14)0.0064 (12)
C130.114 (2)0.0709 (18)0.0777 (18)−0.0083 (16)0.0406 (17)0.0111 (14)
C140.0683 (15)0.093 (2)0.0680 (16)−0.0250 (14)0.0311 (13)−0.0078 (15)
C150.0533 (14)0.106 (2)0.0810 (18)0.0149 (14)0.0229 (13)−0.0101 (16)
C160.0594 (14)0.0826 (17)0.0672 (15)0.0217 (12)0.0192 (12)0.0082 (13)
N10.0499 (9)0.0460 (10)0.0502 (10)0.0005 (7)0.0146 (8)−0.0014 (8)
O10.0562 (8)0.0794 (11)0.0420 (8)0.0072 (8)0.0102 (7)−0.0010 (7)
Geometric parameters (Å, °) top
C1—C21.512 (3)C9—O11.447 (2)
C1—H1A0.9600C9—H9A0.9700
C1—H1B0.9600C9—H9B0.9700
C1—H1C0.9600C10—N11.472 (2)
C2—C31.381 (3)C10—C111.503 (2)
C2—C71.385 (3)C10—H10A0.9700
C3—C41.378 (3)C10—H10B0.9700
C3—H30.9300C11—C161.375 (3)
C4—C51.376 (3)C11—C121.377 (3)
C4—H40.9300C12—C131.381 (3)
C5—O11.376 (2)C12—H120.9300
C5—C61.389 (3)C13—C141.354 (4)
C6—C71.388 (3)C13—H130.9300
C6—C81.514 (3)C14—C151.359 (3)
C7—H70.9300C14—H140.9300
C8—N11.467 (2)C15—C161.384 (3)
C8—H8A0.9700C15—H150.9300
C8—H8B0.9700C16—H160.9300
C9—N11.430 (2)
C2—C1—H1A109.5O1—C9—H9A108.8
C2—C1—H1B109.5N1—C9—H9B108.8
H1A—C1—H1B109.5O1—C9—H9B108.8
C2—C1—H1C109.5H9A—C9—H9B107.7
H1A—C1—H1C109.5N1—C10—C11112.67 (15)
H1B—C1—H1C109.5N1—C10—H10A109.1
C3—C2—C7117.16 (19)C11—C10—H10A109.1
C3—C2—C1120.9 (2)N1—C10—H10B109.1
C7—C2—C1121.9 (2)C11—C10—H10B109.1
C4—C3—C2121.8 (2)H10A—C10—H10B107.8
C4—C3—H3119.1C16—C11—C12117.43 (19)
C2—C3—H3119.1C16—C11—C10121.01 (19)
C5—C4—C3119.8 (2)C12—C11—C10121.56 (18)
C5—C4—H4120.1C11—C12—C13121.5 (2)
C3—C4—H4120.1C11—C12—H12119.2
O1—C5—C4116.91 (18)C13—C12—H12119.2
O1—C5—C6122.45 (17)C14—C13—C12120.0 (2)
C4—C5—C6120.59 (18)C14—C13—H13120.0
C7—C6—C5117.98 (18)C12—C13—H13120.0
C7—C6—C8123.24 (18)C13—C14—C15119.6 (2)
C5—C6—C8118.77 (17)C13—C14—H14120.2
C2—C7—C6122.7 (2)C15—C14—H14120.2
C2—C7—H7118.6C14—C15—C16120.6 (2)
C6—C7—H7118.6C14—C15—H15119.7
N1—C8—C6111.64 (16)C16—C15—H15119.7
N1—C8—H8A109.3C11—C16—C15120.8 (2)
C6—C8—H8A109.3C11—C16—H16119.6
N1—C8—H8B109.3C15—C16—H16119.6
C6—C8—H8B109.3C9—N1—C8108.58 (15)
H8A—C8—H8B108.0C9—N1—C10113.14 (16)
N1—C9—O1113.82 (15)C8—N1—C10111.64 (15)
N1—C9—H9A108.8C5—O1—C9115.02 (15)
C7—C2—C3—C40.0 (3)C16—C11—C12—C13−1.1 (3)
C1—C2—C3—C4179.1 (2)C10—C11—C12—C13179.0 (2)
C2—C3—C4—C50.5 (3)C11—C12—C13—C140.5 (4)
C3—C4—C5—O1−178.12 (18)C12—C13—C14—C150.7 (4)
C3—C4—C5—C6−0.7 (3)C13—C14—C15—C16−1.2 (4)
O1—C5—C6—C7177.70 (17)C12—C11—C16—C150.5 (3)
C4—C5—C6—C70.4 (3)C10—C11—C16—C15−179.5 (2)
O1—C5—C6—C8−1.3 (3)C14—C15—C16—C110.6 (4)
C4—C5—C6—C8−178.59 (18)O1—C9—N1—C863.2 (2)
C3—C2—C7—C6−0.2 (3)O1—C9—N1—C10−61.4 (2)
C1—C2—C7—C6−179.4 (2)C6—C8—N1—C9−50.5 (2)
C5—C6—C7—C20.1 (3)C6—C8—N1—C1074.9 (2)
C8—C6—C7—C2179.00 (19)C11—C10—N1—C9−60.3 (2)
C7—C6—C8—N1−157.35 (18)C11—C10—N1—C8176.84 (15)
C5—C6—C8—N121.6 (3)C4—C5—O1—C9−171.58 (17)
N1—C10—C11—C16−65.1 (2)C6—C5—O1—C911.0 (3)
N1—C10—C11—C12114.8 (2)N1—C9—O1—C5−43.0 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cg1i0.932.933.820 (3)159
C8—H8B···Cg2ii0.972.983.907 (2)159
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x, y−1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cg1i0.932.933.820 (3)159
C8—H8B···Cg2ii0.972.983.907 (2)159
Symmetry codes: (i) −x+3/2, y+1/2, −z+3/2; (ii) x, y−1, z.
Acknowledgements top

We gratefully acknowledge financial support of this work as the Plan of Group of Young Scientists Innovation Foundation of Hubei Province under grant No. 2004 T006.

references
References top

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