3-(1,3-Benzodioxol-5-yl)-1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazine

Abstract

In the title compound, C₂₅H₁₉NO₃, the oxazine ring displays a half-chair conformation. The fused benzene ring is nearly parallel to the naphthyl ring system, the dihedral angle between this benzene ring and the naphthyl system being 8.52 (11)°. The imino group is not involved in hydrogen bonding in the crystal structure.

Related literature

For general background, see: Katayama & Oshiyama (1997 ▶); Mahajan et al. (1991 ▶); Mishra et al. (1998 ▶).

Experimental

Crystal data

• C₂₅H₁₉NO₃

• M _r = 381.41

• Monoclinic,

• a = 9.180 (3) Å

• b = 5.7585 (18) Å

• c = 17.320 (5) Å

• β = 97.707 (4)°

• V = 907.3 (5) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 291 (2) K

• 0.30 × 0.26 × 0.24 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.97, T _max = 0.98

• 5964 measured reflections

• 2412 independent reflections

• 1824 reflections with I > 2σ(I)

• R _int = 0.041

Refinement

• R[F ² > 2σ(F ²)] = 0.063

• wR(F ²) = 0.134

• S = 1.18

• 2412 reflections

• 265 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.21 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The oxazine derivatives display various applications and widespresd potential biological and pharmacological activities such as antimicrobial (Mahajan et al., 1991), antitumor (Katayama & Oshiyama, 1997) and antihistaminic (Mishra et al., 1998). In view of these important properties, we reported the crystal strucutre of the tilte compound.

The oxazine ring in the molecular is not planar. The 1,3-benzodioxole ring makes the dihedral angles of 68.24 (11)° and 8.52 (11)° with the benzene ring and the naphthyl ring, respectively, while the plane O1/C1/C10/C11 is co-planar with the naphthalene ring with the dihedral angle 1.43 (11)°. The dihedral angle between the benzene ring and the naphthalene ring is 71.48 (16)°.

Experimental

1-(Amino(phenyl)methyl)naphthalen-2-ol (1 mmol, 0.249 g) was dissolved in anhydrous methanol, the mixture was stirred for several minitutes, 1,3-benzodioxole-5-carbaldehyde (1 mmol, 0.150 g) in methanol (6 ml) was added dropwise and the mixture was stirred at room temperature for 2 h. The product was isolated and recrystallized in dichloromethane. Colorless single crystals of (I) was obtained after 4 d.

Refinement

Imino H atom was located in a difference Fourier map and positional parameters were refined, U_iso(H) = 1.2U_eq(N). Other H atoms were placed in calculated positions, with C—H = 0.93 Å (aromatic) and 0.97 Å (methylene), and refined in riding mode with U_iso(H)=1.2U_eq(C). In absence of significant anomalous scattering, Friedel pairs were merged.

Figures

Fig. 1.

The ORTEP plot of (I). Displacement ellipsoids are drawn at the 30% probability level.

Crystal data

C25H19NO3	F000 = 400
Mr = 381.41	Dx = 1.396 Mg m−3
Monoclinic, P21	Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 912 reflections
a = 9.180 (3) Å	θ = 2.1–25.1º
b = 5.7585 (18) Å	µ = 0.09 mm−1
c = 17.320 (5) Å	T = 291 (2) K
β = 97.707 (4)º	Block, colorless
V = 907.3 (5) Å3	0.30 × 0.26 × 0.24 mm
Z = 2

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2412 independent reflections
Radiation source: sealed tube	1824 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.041
T = 291(2) K	θmax = 28.0º
φ and ω scans	θmin = 1.2º
Absorption correction: multi-scan(SADABS; Bruker, 2000)	h = −12→12
Tmin = 0.97, Tmax = 0.98	k = −7→7
5964 measured reflections	l = −15→22

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.134	w = 1/[σ2(Fo2) + (0.0517P)2 + 0.1645P] where P = (Fo2 + 2Fc2)/3
S = 1.18	(Δ/σ)max < 0.001
2412 reflections	Δρmax = 0.21 e Å−3
265 parameters	Δρmin = −0.20 e Å−3
1 restraint	Extinction correction: none
Primary atom site location: structure-invariant direct methods

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
C1	0.4757 (4)	1.2105 (7)	0.2026 (2)	0.0336 (8)
C2	0.5763 (4)	1.3803 (7)	0.1817 (2)	0.0357 (9)
H2	0.5449	1.4902	0.1438	0.043*
C3	0.7154 (4)	1.3826 (8)	0.2163 (2)	0.0394 (9)
H3	0.7794	1.4958	0.2026	0.047*
C4	0.7663 (4)	1.2181 (7)	0.2729 (2)	0.0333 (8)
C5	0.9118 (4)	1.2228 (7)	0.3104 (2)	0.0366 (9)
H5	0.9719	1.3457	0.2999	0.044*
C6	0.9709 (5)	1.0510 (8)	0.3631 (2)	0.0407 (10)
H6	1.0664	1.0603	0.3888	0.049*
C7	0.8740 (4)	0.8566 (8)	0.3752 (2)	0.0402 (9)
H7	0.9091	0.7295	0.4052	0.048*
C8	0.7357 (4)	0.8655 (8)	0.3425 (2)	0.0386 (9)
H8	0.6735	0.7503	0.3568	0.046*
C9	0.6719 (4)	1.0330 (7)	0.2877 (2)	0.0321 (8)
C10	0.5191 (4)	1.0343 (8)	0.2527 (2)	0.0376 (9)
C11	0.4128 (4)	0.8432 (8)	0.2724 (2)	0.0400 (9)
H11	0.4613	0.6936	0.2670	0.048*
C12	0.3653 (4)	0.8494 (7)	0.3526 (2)	0.0362 (8)
C13	0.4046 (4)	1.0273 (7)	0.4006 (2)	0.0328 (8)
H13	0.4569	1.1531	0.3849	0.039*
C14	0.3628 (4)	1.0156 (8)	0.4770 (2)	0.0421 (10)
H14	0.3893	1.1363	0.5118	0.051*
C15	0.2837 (5)	0.8292 (9)	0.5011 (3)	0.0461 (10)
H15	0.2581	0.8223	0.5512	0.055*
C16	0.2441 (4)	0.6531 (8)	0.4472 (2)	0.0395 (9)
H16	0.1881	0.5293	0.4613	0.047*
C17	0.2874 (4)	0.6570 (9)	0.3703 (3)	0.0441 (10)
H17	0.2642	0.5369	0.3349	0.053*
C18	0.2306 (4)	1.0885 (7)	0.2003 (2)	0.0378 (9)
H18	0.2162	1.1499	0.2515	0.045*
C19	0.0807 (5)	1.1079 (8)	0.1429 (2)	0.0411 (9)
C20	0.0568 (4)	1.2985 (8)	0.0972 (2)	0.0368 (9)
H20	0.1311	1.4084	0.0973	0.044*
C21	−0.0776 (4)	1.3335 (8)	0.0497 (2)	0.0360 (8)
H21	−0.0999	1.4701	0.0219	0.043*
C22	−0.1737 (4)	1.1502 (7)	0.0475 (2)	0.0326 (8)
C23	−0.1516 (5)	0.9640 (8)	0.0947 (2)	0.0427 (10)
C24	−0.0182 (4)	0.9259 (8)	0.1459 (2)	0.0360 (9)
H24	0.0002	0.7955	0.1773	0.043*
C25	−0.3700 (5)	0.9157 (8)	0.0285 (2)	0.0459 (11)
H25A	−0.4622	0.9372	0.0491	0.055*
H25B	−0.3875	0.8163	−0.0170	0.055*
N1	0.2826 (4)	0.8559 (7)	0.2088 (2)	0.0388 (8)
H1	0.246 (5)	0.740 (9)	0.182 (3)	0.047*
O1	0.3362 (3)	1.2333 (5)	0.16696 (15)	0.0380 (7)
O2	−0.3139 (3)	1.1315 (6)	0.00830 (16)	0.0414 (7)
O3	−0.2657 (3)	0.8142 (5)	0.08500 (15)	0.0392 (7)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.039 (2)	0.030 (2)	0.0311 (18)	0.0063 (17)	0.0014 (15)	−0.0124 (15)
C2	0.0389 (19)	0.037 (2)	0.0284 (16)	−0.0056 (18)	−0.0063 (14)	−0.0042 (17)
C3	0.0299 (17)	0.043 (2)	0.047 (2)	0.0083 (18)	0.0127 (16)	0.0024 (19)
C4	0.0272 (17)	0.034 (2)	0.0397 (19)	0.0003 (16)	0.0071 (15)	−0.0007 (16)
C5	0.045 (2)	0.038 (2)	0.0265 (17)	−0.0072 (18)	0.0017 (16)	−0.0114 (16)
C6	0.040 (2)	0.041 (2)	0.038 (2)	0.0099 (19)	−0.0060 (17)	−0.0057 (18)
C7	0.0345 (19)	0.041 (2)	0.044 (2)	0.0158 (19)	0.0009 (16)	0.0089 (19)
C8	0.0339 (18)	0.043 (2)	0.041 (2)	0.0136 (18)	0.0123 (16)	0.0105 (19)
C9	0.0268 (17)	0.033 (2)	0.0381 (18)	0.0110 (16)	0.0101 (14)	−0.0079 (17)
C10	0.0371 (19)	0.043 (2)	0.0286 (17)	−0.0135 (19)	−0.0113 (15)	−0.0011 (17)
C11	0.0356 (18)	0.040 (2)	0.044 (2)	−0.001 (2)	0.0023 (16)	−0.0123 (19)
C12	0.0419 (19)	0.0265 (19)	0.0380 (19)	0.0106 (17)	−0.0025 (16)	−0.0006 (17)
C13	0.0241 (16)	0.034 (2)	0.0412 (19)	0.0112 (15)	0.0079 (14)	−0.0127 (16)
C14	0.046 (2)	0.045 (2)	0.0308 (18)	0.007 (2)	−0.0139 (16)	0.0014 (19)
C15	0.044 (2)	0.048 (3)	0.044 (2)	0.011 (2)	−0.0022 (18)	0.001 (2)
C16	0.0318 (18)	0.042 (2)	0.044 (2)	0.0108 (18)	0.0020 (16)	0.012 (2)
C17	0.037 (2)	0.044 (2)	0.052 (2)	0.0013 (19)	0.0081 (17)	0.007 (2)
C18	0.045 (2)	0.035 (2)	0.0345 (18)	0.0014 (19)	0.0093 (16)	0.0072 (17)
C19	0.046 (2)	0.035 (2)	0.040 (2)	0.0108 (19)	−0.0046 (17)	−0.0032 (18)
C20	0.0304 (17)	0.045 (2)	0.0375 (19)	−0.0078 (18)	0.0136 (15)	0.0042 (19)
C21	0.0363 (18)	0.037 (2)	0.0359 (18)	−0.0073 (18)	0.0113 (15)	0.0153 (17)
C22	0.0390 (19)	0.0253 (18)	0.0303 (16)	0.0039 (17)	−0.0076 (14)	−0.0012 (16)
C23	0.047 (2)	0.036 (2)	0.042 (2)	−0.0057 (19)	−0.0068 (18)	0.0018 (18)
C24	0.0367 (19)	0.039 (2)	0.0338 (18)	0.0135 (17)	0.0096 (15)	−0.0067 (17)
C25	0.039 (2)	0.049 (3)	0.045 (2)	−0.007 (2)	−0.0106 (18)	−0.001 (2)
N1	0.0329 (16)	0.0346 (19)	0.0460 (18)	−0.0174 (15)	−0.0059 (13)	0.0043 (16)
O1	0.0395 (14)	0.0368 (15)	0.0384 (14)	0.0117 (13)	0.0078 (11)	0.0163 (13)
O2	0.0378 (14)	0.0425 (17)	0.0416 (14)	−0.0021 (14)	−0.0035 (12)	0.0058 (14)
O3	0.0398 (14)	0.0368 (16)	0.0396 (13)	0.0003 (13)	−0.0003 (11)	0.0185 (13)

Geometric parameters (Å, °)

C1—O1	1.351 (4)	C14—H14	0.9300
C1—C10	1.359 (6)	C15—C16	1.393 (7)
C1—C2	1.425 (6)	C15—H15	0.9300
C2—C3	1.336 (5)	C16—C17	1.440 (6)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.398 (6)	C17—H17	0.9300
C3—H3	0.9300	C18—N1	1.424 (6)
C4—C5	1.405 (5)	C18—O1	1.456 (5)
C4—C9	1.419 (5)	C18—C19	1.589 (6)
C5—C6	1.405 (6)	C18—H18	0.9800
C5—H5	0.9300	C19—C20	1.354 (6)
C6—C7	1.462 (6)	C19—C24	1.392 (6)
C6—H6	0.9300	C20—C21	1.403 (5)
C7—C8	1.320 (5)	C20—H20	0.9300
C7—H7	0.9300	C21—C22	1.373 (5)
C8—C9	1.423 (5)	C21—H21	0.9300
C8—H8	0.9300	C22—C23	1.347 (6)
C9—C10	1.452 (5)	C22—O2	1.376 (4)
C10—C11	1.539 (6)	C23—O3	1.350 (5)
C11—C12	1.511 (5)	C23—C24	1.429 (5)
C11—N1	1.514 (5)	C24—H24	0.9300
C11—H11	0.9800	C25—O3	1.401 (5)
C12—C13	1.339 (5)	C25—O2	1.408 (6)
C12—C17	1.375 (6)	C25—H25A	0.9700
C13—C14	1.428 (5)	C25—H25B	0.9700
C13—H13	0.9300	N1—H1	0.86 (5)
C14—C15	1.391 (7)
O1—C1—C10	122.9 (4)	C14—C15—C16	117.4 (4)
O1—C1—C2	115.1 (3)	C14—C15—H15	121.3
C10—C1—C2	122.0 (3)	C16—C15—H15	121.3
C3—C2—C1	120.4 (4)	C15—C16—C17	121.9 (4)
C3—C2—H2	119.8	C15—C16—H16	119.0
C1—C2—H2	119.8	C17—C16—H16	119.0
C2—C3—C4	121.2 (4)	C12—C17—C16	115.8 (4)
C2—C3—H3	119.4	C12—C17—H17	122.1
C4—C3—H3	119.4	C16—C17—H17	122.1
C3—C4—C5	121.3 (4)	N1—C18—O1	110.3 (3)
C3—C4—C9	118.7 (3)	N1—C18—C19	112.4 (3)
C5—C4—C9	119.8 (4)	O1—C18—C19	106.2 (3)
C4—C5—C6	123.2 (4)	N1—C18—H18	109.3
C4—C5—H5	118.4	O1—C18—H18	109.3
C6—C5—H5	118.4	C19—C18—H18	109.3
C5—C6—C7	116.3 (3)	C20—C19—C24	125.2 (4)
C5—C6—H6	121.9	C20—C19—C18	118.8 (4)
C7—C6—H6	121.9	C24—C19—C18	116.0 (4)
C8—C7—C6	118.5 (4)	C19—C20—C21	121.3 (4)
C8—C7—H7	120.7	C19—C20—H20	119.3
C6—C7—H7	120.7	C21—C20—H20	119.3
C7—C8—C9	126.8 (4)	C22—C21—C20	114.6 (4)
C7—C8—H8	116.6	C22—C21—H21	122.7
C9—C8—H8	116.6	C20—C21—H21	122.7
C4—C9—C8	115.0 (3)	C23—C22—C21	123.5 (3)
C4—C9—C10	120.0 (3)	C23—C22—O2	107.0 (3)
C8—C9—C10	124.8 (4)	C21—C22—O2	128.9 (3)
C1—C10—C9	117.0 (4)	C22—C23—O3	112.5 (3)
C1—C10—C11	122.3 (3)	C22—C23—C24	123.0 (4)
C9—C10—C11	120.6 (3)	O3—C23—C24	124.4 (4)
C12—C11—N1	111.8 (3)	C19—C24—C23	111.7 (4)
C12—C11—C10	117.1 (3)	C19—C24—H24	124.1
N1—C11—C10	105.4 (3)	C23—C24—H24	124.1
C12—C11—H11	107.3	O3—C25—O2	107.7 (3)
N1—C11—H11	107.3	O3—C25—H25A	110.2
C10—C11—H11	107.3	O2—C25—H25A	110.2
C13—C12—C17	125.6 (4)	O3—C25—H25B	110.2
C13—C12—C11	120.2 (4)	O2—C25—H25B	110.2
C17—C12—C11	114.2 (4)	H25A—C25—H25B	108.5
C12—C13—C14	117.2 (4)	C18—N1—C11	110.0 (3)
C12—C13—H13	121.4	C18—N1—H1	125 (3)
C14—C13—H13	121.4	C11—N1—H1	125 (3)
C15—C14—C13	122.0 (4)	C1—O1—C18	113.8 (3)
C15—C14—H14	119.0	C22—O2—C25	107.2 (3)
C13—C14—H14	119.0	C23—O3—C25	105.4 (3)