3-Benzyl-6-bromo-3,4-dihydro-2H-benzo[e][1,3]oxazine

In the title compound, C₁₄H₁₅BrNO, the dihedral angle between the two benzene rings is 77.1 (3)°. In the crystal structure, the mol­ecules are linked through C—H...π(arene) inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.120
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.98
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Benzoxazine, which has been widely used as a potential agonist trigger, antipsychotic agent (Barker et al., 2006), antimalarial agent (Ren et al., 2001), and a serotonin and dopamine receptor (Gentles et al., 1991; Petterson et al., 1990; Peglion et al., 1997), is a useful heterocyclic compound. The title compound (I) was prepared by reaction of 4-bromophenol, formaldehyde and benzyl amine. The crystal structure of (I) is described here.

In the molecule (Fig. 1), the dihedral angle between the two benzene rings is 77.1 (3)°. N1 and C8 deviate markedly from the O1—C4—C5—C7—N1—C8 plane, with deviations of -0.320 (4) and 0.282 (7) Å, respectively.

In the crystal structure, molecules are linked by two C—H···π(arene) interactions, which connect H12 to the centroid of C1–C6, Cg2, in an adjacent molecule (symmetry code: –X, –Y, 1-Z), and H8A to the centroid of C2–C7, Cg3, in a second adjacent molecule (symmetry code: 1+X, Y, Z).

Related literature

For related literature, see: Barker et al. (2006); Gentles et al. (1991); Peglion et al. (1997); Petterson et al. (1990); Ren et al. (2001).

S2. Experimental

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-bromophenol (10.8 g, 0.1 mol) over 2 h. The mixture was stirred for an 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 (I) suitable for X-ray analysis, with a yield of 85%. ¹HNMR(CDCl₃, 400 MHz), 7.36 (m, 8H, aromatic), 4.87 (s, 2H, N—CH₂—O), 3.94 (s, 2H, N—CH₂-heterocyclic), 3.90 (s, 2H, N—CH₂-benzyl).

S3. Refinement

All H atoms were placed in calculated positions (C—H = 0.93 Å) and included in the riding model approximation, with U_iso(H) = 1.2U_iso(C).

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 2001); 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

	Fig. 1. View of the molecule of (I) with the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. The crystal packing of (I), viewed down the c axis.

3-Benzyl-6-bromo-3,4-dihydro-2H-benzo[e][1,3]oxazine

Crystal data

C15H14BrNO	Z = 2
Mr = 304.18	F(000) = 308
Triclinic, P1	Dx = 1.523 Mg m^−3
a = 6.2944 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.7466 (10) Å	Cell parameters from 1924 reflections
c = 10.9927 (10) Å	θ = 3.3–24.8°
α = 65.554 (1)°	µ = 3.09 mm^−1
β = 78.674 (1)°	T = 291 K
γ = 86.678 (2)°	Block, colourless
V = 663.51 (11) Å^3	0.20 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2567 independent reflections
Radiation source: fine-focus sealed tube	2029 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.022
φ and ω scans	θmax = 26.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 2001)	h = −7→7
Tmin = 0.577, Tmax = 0.748	k = −13→11
4516 measured reflections	l = −13→13

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.121	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0651P)^2 + 0.1104P] where P = (Fo^2 + 2Fc^2)/3
2567 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.35 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.14407 (6)	0.63851 (4)	0.09288 (4)	0.0672 (2)
C1	0.3047 (5)	0.5198 (3)	0.2233 (3)	0.0460 (8)
C2	0.5220 (5)	0.4985 (4)	0.1810 (4)	0.0511 (8)
H2	0.5885	0.5429	0.0902	0.061*
C3	0.6370 (5)	0.4108 (4)	0.2755 (4)	0.0536 (9)
H3	0.7807	0.3937	0.2477	0.064*
C4	0.5405 (5)	0.3479 (3)	0.4114 (3)	0.0452 (8)
C5	0.3205 (5)	0.3674 (3)	0.4537 (3)	0.0407 (7)
C6	0.2055 (5)	0.4537 (3)	0.3573 (3)	0.0428 (7)
H6	0.0593	0.4670	0.3836	0.051*
C7	0.2163 (5)	0.2921 (4)	0.6014 (3)	0.0478 (8)
H7A	0.2058	0.3538	0.6463	0.057*
H7B	0.0706	0.2625	0.6072	0.057*
C8	0.5623 (6)	0.2128 (4)	0.6429 (4)	0.0607 (10)
H8A	0.6417	0.1349	0.6944	0.073*
H8B	0.5749	0.2838	0.6742	0.073*
C9	0.3010 (5)	0.0537 (4)	0.6479 (4)	0.0502 (8)
H9A	0.4166	−0.0100	0.6733	0.060*
H9B	0.3053	0.0818	0.5514	0.060*
C10	0.0872 (5)	−0.0181 (3)	0.7260 (3)	0.0463 (8)
C11	−0.0042 (7)	−0.1055 (4)	0.6850 (5)	0.0651 (10)
H11	0.0647	−0.1173	0.6077	0.078*
C12	−0.1982 (8)	−0.1754 (4)	0.7594 (6)	0.0817 (14)
H12	−0.2574	−0.2346	0.7320	0.098*
C13	−0.3018 (7)	−0.1584 (5)	0.8710 (5)	0.0799 (14)
H13	−0.4321	−0.2054	0.9194	0.096*
C14	−0.2166 (7)	−0.0724 (5)	0.9135 (4)	0.0724 (12)
H14	−0.2881	−0.0609	0.9905	0.087*
C15	−0.0217 (6)	−0.0023 (4)	0.8403 (4)	0.0574 (9)
H15	0.0362	0.0564	0.8689	0.069*
O1	0.6632 (3)	0.2629 (3)	0.4997 (3)	0.0621 (7)
N1	0.3396 (4)	0.1730 (3)	0.6717 (3)	0.0459 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Br1	0.0550 (3)	0.0711 (3)	0.0505 (3)	0.00478 (19)	−0.00503 (17)	−0.00313 (19)
C1	0.0474 (17)	0.0404 (17)	0.0429 (18)	−0.0006 (14)	−0.0033 (14)	−0.0122 (14)
C2	0.0452 (17)	0.050 (2)	0.0427 (19)	−0.0100 (15)	0.0083 (14)	−0.0098 (16)
C3	0.0326 (16)	0.059 (2)	0.057 (2)	−0.0032 (15)	0.0062 (14)	−0.0176 (18)
C4	0.0331 (15)	0.0449 (18)	0.0473 (19)	−0.0071 (13)	−0.0014 (13)	−0.0106 (15)
C5	0.0356 (15)	0.0382 (17)	0.0442 (17)	−0.0033 (13)	0.0001 (13)	−0.0158 (14)
C6	0.0380 (15)	0.0371 (17)	0.0455 (19)	−0.0017 (13)	0.0026 (13)	−0.0135 (14)
C7	0.0414 (16)	0.0505 (19)	0.0434 (19)	0.0055 (14)	0.0017 (14)	−0.0162 (15)
C8	0.0441 (18)	0.073 (3)	0.052 (2)	−0.0128 (18)	−0.0074 (16)	−0.0115 (19)
C9	0.0424 (17)	0.054 (2)	0.0463 (19)	0.0057 (15)	−0.0020 (14)	−0.0164 (16)
C10	0.0479 (18)	0.0422 (18)	0.0440 (19)	0.0046 (14)	−0.0116 (14)	−0.0123 (15)
C11	0.082 (3)	0.046 (2)	0.069 (3)	0.003 (2)	−0.012 (2)	−0.026 (2)
C12	0.092 (3)	0.047 (2)	0.106 (4)	−0.016 (2)	−0.028 (3)	−0.025 (3)
C13	0.066 (3)	0.064 (3)	0.081 (3)	−0.023 (2)	−0.023 (2)	0.006 (2)
C14	0.059 (2)	0.097 (3)	0.042 (2)	−0.015 (2)	−0.0064 (18)	−0.008 (2)
C15	0.0487 (19)	0.078 (3)	0.0404 (19)	−0.0148 (18)	−0.0062 (15)	−0.0183 (19)
O1	0.0344 (11)	0.0765 (18)	0.0554 (15)	0.0014 (11)	−0.0043 (10)	−0.0092 (13)
N1	0.0378 (13)	0.0516 (16)	0.0418 (15)	−0.0008 (12)	−0.0058 (11)	−0.0132 (13)

Geometric parameters (Å, º)

Br1—C1	1.901 (3)	C8—H8A	0.9700
C1—C6	1.374 (4)	C8—H8B	0.9700
C1—C2	1.394 (5)	C9—N1	1.453 (4)
C2—C3	1.377 (5)	C9—C10	1.504 (5)
C2—H2	0.9300	C9—H9A	0.9700
C3—C4	1.383 (5)	C9—H9B	0.9700
C3—H3	0.9300	C10—C15	1.379 (5)
C4—O1	1.361 (4)	C10—C11	1.389 (5)
C4—C5	1.404 (4)	C11—C12	1.389 (7)
C5—C6	1.384 (4)	C11—H11	0.9300
C5—C7	1.509 (5)	C12—C13	1.350 (7)
C6—H6	0.9300	C12—H12	0.9300
C7—N1	1.463 (4)	C13—C14	1.369 (7)
C7—H7A	0.9700	C13—H13	0.9300
C7—H7B	0.9700	C14—C15	1.392 (5)
C8—N1	1.425 (4)	C14—H14	0.9300
C8—O1	1.455 (4)	C15—H15	0.9300
C6—C1—C2	120.6 (3)	H8A—C8—H8B	107.6
C6—C1—Br1	120.1 (2)	N1—C9—C10	113.1 (3)
C2—C1—Br1	119.3 (3)	N1—C9—H9A	109.0
C3—C2—C1	119.1 (3)	C10—C9—H9A	109.0
C3—C2—H2	120.4	N1—C9—H9B	109.0
C1—C2—H2	120.4	C10—C9—H9B	109.0
C2—C3—C4	120.6 (3)	H9A—C9—H9B	107.8
C2—C3—H3	119.7	C15—C10—C11	118.1 (3)
C4—C3—H3	119.7	C15—C10—C9	122.0 (3)
O1—C4—C3	117.7 (3)	C11—C10—C9	120.0 (3)
O1—C4—C5	122.0 (3)	C12—C11—C10	120.1 (4)
C3—C4—C5	120.3 (3)	C12—C11—H11	119.9
C6—C5—C4	118.6 (3)	C10—C11—H11	119.9
C6—C5—C7	122.2 (3)	C13—C12—C11	120.8 (4)
C4—C5—C7	119.2 (3)	C13—C12—H12	119.6
C1—C6—C5	120.8 (3)	C11—C12—H12	119.6
C1—C6—H6	119.6	C12—C13—C14	120.5 (4)
C5—C6—H6	119.6	C12—C13—H13	119.8
N1—C7—C5	111.9 (2)	C14—C13—H13	119.8
N1—C7—H7A	109.2	C13—C14—C15	119.3 (4)
C5—C7—H7A	109.2	C13—C14—H14	120.3
N1—C7—H7B	109.2	C15—C14—H14	120.3
C5—C7—H7B	109.2	C10—C15—C14	121.2 (4)
H7A—C7—H7B	107.9	C10—C15—H15	119.4
N1—C8—O1	114.4 (3)	C14—C15—H15	119.4
N1—C8—H8A	108.7	C4—O1—C8	115.3 (2)
O1—C8—H8A	108.7	C8—N1—C9	114.3 (3)
N1—C8—H8B	108.7	C8—N1—C7	109.1 (3)
O1—C8—H8B	108.7	C9—N1—C7	113.9 (3)
C6—C1—C2—C3	−0.4 (5)	C15—C10—C11—C12	−0.8 (6)
Br1—C1—C2—C3	−179.0 (3)	C9—C10—C11—C12	178.0 (4)
C1—C2—C3—C4	−2.0 (6)	C10—C11—C12—C13	0.8 (7)
C2—C3—C4—O1	−179.7 (3)	C11—C12—C13—C14	−0.4 (7)
C2—C3—C4—C5	3.2 (6)	C12—C13—C14—C15	0.1 (7)
O1—C4—C5—C6	−178.9 (3)	C11—C10—C15—C14	0.5 (6)
C3—C4—C5—C6	−1.9 (5)	C9—C10—C15—C14	−178.2 (4)
O1—C4—C5—C7	0.0 (5)	C13—C14—C15—C10	−0.2 (6)
C3—C4—C5—C7	177.0 (3)	C3—C4—O1—C8	172.8 (3)
C2—C1—C6—C5	1.7 (5)	C5—C4—O1—C8	−10.1 (5)
Br1—C1—C6—C5	−179.7 (2)	N1—C8—O1—C4	42.2 (5)
C4—C5—C6—C1	−0.6 (5)	O1—C8—N1—C9	66.8 (4)
C7—C5—C6—C1	−179.4 (3)	O1—C8—N1—C7	−62.0 (4)
C6—C5—C7—N1	158.9 (3)	C10—C9—N1—C8	157.9 (3)
C4—C5—C7—N1	−19.9 (4)	C10—C9—N1—C7	−75.8 (3)
N1—C9—C10—C15	−21.0 (4)	C5—C7—N1—C8	48.8 (4)
N1—C9—C10—C11	160.3 (3)	C5—C7—N1—C9	−80.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8A···Cg3^i	0.97	2.75	3.706 (6)	178
C12—H12···Cg2^ii	0.93	2.71	3.632 (8)	173

Symmetry codes: (i) x+1, y, z; (ii) −x, −y, −z+1.