3-(2,4-Dichloro­phen­yl)-1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazine

Yin, Z.-G.; Qian, H.-Y.; Yu-Zhen, C.; Yu-Li, F.

doi:10.1107/S160053680705787X

3-(2,4-Dichlorophenyl)-1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazine

Z.-G. Yin, H.-Y. Qian, C. Yu-Zhen and F. Yu-Li

In the title compound, C₂₄H₁₇Cl₂NO, the oxazine ring adopts a half-chair conformation. The dihedral angle between the phenyl ring and the naphthyl ring system is 78.56 (9)°. Intramolecular C—H

Cl hydrogen bonding is observed in the crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680705787X/xu2366sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680705787X/xu2366Isup2.hkl Contains datablock I

CCDC reference: 672995

checkCIF report

Key indicators

Single-crystal X-ray study
T = 291 K
Mean (C-C) = 0.003 Å
R factor = 0.047
wR factor = 0.104
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1A    ...          ?

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C11    = ...          S
PLAT793_ALERT_1_G Check the Absolute Configuration of C18    = ...          S

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The class of oxazine derivatives is useful heterocyclic compound which is widely used as antimalarial agent (Ren et al., 2001) and a versatile intermediate for the synthesis of carbapenems (Fuganti et al., 1994). Here we present the synthesis and crystal structure of the title compound.

In the molecule (Fig. 1), the oxazine ring is distorted and adopts a half chair conformation, O1 and N1 atoms deviate from the O1—C18—N1—C11—C1—C2 mean plane by 0.168 (1) and 0.282 (2)%A, respectively. The dihedral angle between the C12-phenyl ring and naphthyl system is 78.56 (9)°. Intra-molecular C—H···Cl hydrogen bond is observed in the crystal structure (Table 1), but no inter-molecular hydrogen bonding occurs in the crystal structure.

Related literature top

For general background, see: Fuganti et al. (1994); Ren et al. (2001).

Experimental top

1-(Amino(phenyl)methyl)naphthalen-2-ol (1 mmol, 0.249 g) was dissolved in anhydrous methanol, the solution was stirred for several min. and then 2,4-dichlorobenzyaldehyde (1 mmol 0.175 g) in methanol (8 ml) was added dropwise and the mixture was stirred at room temperature for 2 h. The product was isolated and recrystallized in a methanol solution, colourless single crystals were obtained after 2 d.

Computing details top

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

Figures top

Fig. 1. the ORTEP plot of (I). Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radii.

3-(2,4-Dichlorophenyl)-1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazine top

Crystal data top

C₂₄H₁₇Cl₂NO	Z = 2
M_r = 406.29	F(000) = 420
Triclinic, P1	D_x = 1.397 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.664 (3) Å	Cell parameters from 816 reflections
b = 8.224 (3) Å	θ = 2.3–20.1°
c = 18.106 (7) Å	µ = 0.35 mm⁻¹
α = 92.269 (6)°	T = 291 K
β = 99.420 (5)°	Block, colourless
γ = 98.624 (6)°	0.30 × 0.26 × 0.24 mm
V = 965.8 (7) Å³

Data collection top

Bruker SMART Apex CCD area-detector diffractometer	3386 reflections with I > 2σ(I)
Radiation source: sealed tube	R_int = 0.034
Graphite monochromator	θ_max = 26.0°, θ_min = 1.1°
ϕ and ω scans	h = −8→8
7267 measured reflections	k = −10→10
3783 independent reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.04P)² + 0.66P] where P = (F_o² + 2F_c²)/3
3783 reflections	(Δ/σ)_max < 0.001
256 parameters	Δρ_max = 0.16 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₄H₁₇Cl₂NO	γ = 98.624 (6)°
M_r = 406.29	V = 965.8 (7) Å³
Triclinic, P1	Z = 2
a = 6.664 (3) Å	Mo Kα radiation
b = 8.224 (3) Å	µ = 0.35 mm⁻¹
c = 18.106 (7) Å	T = 291 K
α = 92.269 (6)°	0.30 × 0.26 × 0.24 mm
β = 99.420 (5)°

Data collection top

Bruker SMART Apex CCD area-detector diffractometer	3386 reflections with I > 2σ(I)
7267 measured reflections	R_int = 0.034
3783 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.16 e Å⁻³
3783 reflections	Δρ_min = −0.21 e Å⁻³
256 parameters

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

	x	y	z	U_iso*/U_eq
C1	−0.0160 (3)	0.4644 (2)	0.26512 (12)	0.0363 (4)
C2	−0.1740 (3)	0.5189 (2)	0.21512 (10)	0.0317 (4)
C3	−0.3762 (3)	0.4255 (3)	0.19891 (12)	0.0378 (5)
H3	−0.4789	0.4654	0.1669	0.045*
C4	−0.4207 (3)	0.2810 (3)	0.22920 (13)	0.0437 (5)
H4	−0.5538	0.2222	0.2192	0.052*
C5	−0.2576 (3)	0.2171 (3)	0.27800 (12)	0.0381 (5)
C6	−0.0633 (3)	0.3062 (2)	0.29281 (11)	0.0350 (4)
C7	0.1011 (4)	0.2367 (3)	0.33856 (12)	0.0440 (5)
H7	0.2338	0.2958	0.3506	0.053*
C8	0.0552 (3)	0.0841 (3)	0.36297 (12)	0.0395 (5)
H8	0.1598	0.0375	0.3906	0.047*
C9	−0.1457 (4)	−0.0061 (3)	0.34780 (14)	0.0481 (6)
H9	−0.1714	−0.1090	0.3669	0.058*
C10	−0.3037 (4)	0.0551 (3)	0.30547 (13)	0.0465 (6)
H10	−0.4359	−0.0053	0.2947	0.056*
C11	0.1908 (3)	0.5714 (3)	0.28337 (11)	0.0341 (4)
H11	0.2941	0.5128	0.2663	0.041*
C12	0.2558 (3)	0.6199 (3)	0.36802 (12)	0.0388 (5)
C13	0.1190 (3)	0.6381 (3)	0.41515 (11)	0.0408 (5)
H13	−0.0217	0.6114	0.3975	0.049*
C14	0.1890 (4)	0.6959 (3)	0.48886 (13)	0.0470 (5)
H14	0.0935	0.7079	0.5200	0.056*
C15	0.3972 (4)	0.7365 (3)	0.51786 (13)	0.0481 (6)
H15	0.4417	0.7756	0.5676	0.058*
C16	0.5396 (4)	0.7171 (3)	0.46977 (14)	0.0554 (7)
H16	0.6801	0.7459	0.4874	0.066*
C17	0.4700 (3)	0.6547 (3)	0.39579 (12)	0.0391 (5)
H17	0.5638	0.6360	0.3648	0.047*
C18	0.0708 (3)	0.7100 (2)	0.17348 (11)	0.0332 (4)
H18	0.1195	0.6285	0.1427	0.040*
C19	0.0854 (3)	0.8725 (2)	0.13725 (11)	0.0356 (4)
C20	0.2413 (3)	0.9202 (3)	0.09702 (12)	0.0409 (5)
C21	0.2598 (4)	1.0652 (3)	0.06420 (12)	0.0419 (5)
H21	0.3635	1.0925	0.0361	0.050*
C22	0.1272 (3)	1.1695 (2)	0.07259 (11)	0.0333 (4)
C23	−0.0264 (3)	1.1347 (3)	0.11365 (13)	0.0419 (5)
H23	−0.1131	1.2106	0.1207	0.050*
C24	−0.0500 (3)	0.9809 (3)	0.14506 (12)	0.0410 (5)
H24	−0.1576	0.9520	0.1713	0.049*
Cl1	0.41832 (9)	0.78745 (8)	0.08509 (4)	0.05364 (18)
Cl2	0.15778 (9)	1.36256 (7)	0.03317 (3)	0.04927 (17)
N1	0.1937 (3)	0.7299 (2)	0.24802 (10)	0.0359 (4)
H1A	0.138 (4)	0.797 (3)	0.2759 (14)	0.043*
O1	−0.1441 (2)	0.65590 (19)	0.17832 (8)	0.0403 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0295 (10)	0.0336 (10)	0.0448 (12)	0.0019 (8)	0.0074 (8)	−0.0025 (9)
C2	0.0261 (9)	0.0415 (11)	0.0264 (9)	−0.0008 (8)	0.0073 (7)	−0.0010 (8)
C3	0.0324 (10)	0.0398 (11)	0.0389 (11)	−0.0012 (9)	0.0066 (8)	−0.0008 (9)
C4	0.0298 (10)	0.0464 (12)	0.0520 (13)	−0.0084 (9)	0.0130 (9)	−0.0001 (10)
C5	0.0294 (10)	0.0428 (11)	0.0399 (11)	−0.0066 (8)	0.0131 (8)	−0.0070 (9)
C6	0.0372 (11)	0.0364 (10)	0.0286 (10)	−0.0029 (8)	0.0072 (8)	−0.0038 (8)
C7	0.0546 (14)	0.0467 (12)	0.0306 (10)	0.0130 (10)	0.0027 (9)	0.0034 (9)
C8	0.0362 (11)	0.0452 (12)	0.0384 (11)	0.0061 (9)	0.0113 (9)	0.0015 (9)
C9	0.0502 (14)	0.0424 (12)	0.0492 (13)	−0.0049 (10)	0.0120 (11)	0.0029 (10)
C10	0.0428 (13)	0.0446 (12)	0.0473 (13)	−0.0130 (10)	0.0128 (10)	−0.0017 (10)
C11	0.0282 (10)	0.0416 (11)	0.0278 (9)	−0.0028 (8)	−0.0031 (7)	0.0114 (8)
C12	0.0349 (11)	0.0468 (12)	0.0351 (11)	0.0109 (9)	0.0012 (8)	0.0087 (9)
C13	0.0397 (11)	0.0541 (13)	0.0303 (10)	0.0138 (10)	0.0047 (9)	0.0020 (9)
C14	0.0559 (14)	0.0395 (12)	0.0411 (12)	−0.0034 (10)	0.0054 (10)	0.0003 (9)
C15	0.0543 (14)	0.0510 (13)	0.0362 (11)	0.0067 (11)	0.0030 (10)	−0.0071 (10)
C16	0.0403 (13)	0.0630 (16)	0.0516 (14)	−0.0134 (11)	0.0005 (11)	−0.0193 (12)
C17	0.0329 (11)	0.0475 (12)	0.0421 (12)	0.0208 (9)	0.0076 (9)	0.0070 (9)
C18	0.0310 (10)	0.0354 (10)	0.0316 (10)	0.0033 (8)	0.0008 (8)	0.0064 (8)
C19	0.0369 (11)	0.0313 (10)	0.0360 (10)	0.0015 (8)	0.0027 (8)	0.0005 (8)
C20	0.0409 (12)	0.0381 (11)	0.0424 (12)	0.0029 (9)	0.0059 (9)	0.0060 (9)
C21	0.0537 (13)	0.0375 (11)	0.0325 (11)	0.0102 (10)	−0.0021 (9)	0.0046 (9)
C22	0.0375 (10)	0.0315 (10)	0.0260 (9)	0.0023 (8)	−0.0057 (8)	−0.0001 (7)
C23	0.0423 (12)	0.0381 (11)	0.0477 (13)	0.0094 (9)	0.0119 (10)	0.0037 (9)
C24	0.0427 (12)	0.0519 (13)	0.0314 (10)	0.0115 (10)	0.0109 (9)	0.0054 (9)
Cl1	0.0490 (3)	0.0618 (4)	0.0551 (4)	0.0125 (3)	0.0175 (3)	0.0144 (3)
Cl2	0.0547 (3)	0.0395 (3)	0.0520 (3)	0.0126 (2)	−0.0025 (3)	0.0124 (2)
N1	0.0295 (9)	0.0434 (10)	0.0324 (9)	−0.0014 (7)	0.0026 (7)	0.0111 (7)
O1	0.0280 (7)	0.0484 (9)	0.0420 (8)	0.0047 (6)	−0.0019 (6)	0.0125 (7)

Geometric parameters (Å, º) top

C1—C2	1.411 (3)	C13—H13	0.9300
C1—C6	1.422 (3)	C14—C15	1.386 (3)
C1—C11	1.499 (3)	C14—H14	0.9300
C2—O1	1.337 (2)	C15—C16	1.411 (4)
C2—C3	1.426 (3)	C15—H15	0.9300
C3—C4	1.342 (3)	C16—C17	1.394 (3)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.460 (3)	C17—H17	0.9300
C4—H4	0.9300	C18—N1	1.449 (3)
C5—C6	1.368 (3)	C18—O1	1.453 (2)
C5—C10	1.448 (3)	C18—C19	1.509 (3)
C6—C7	1.463 (3)	C18—H18	0.9800
C7—C8	1.355 (3)	C19—C24	1.379 (3)
C7—H7	0.9300	C19—C20	1.383 (3)
C8—C9	1.409 (3)	C20—C21	1.351 (3)
C8—H8	0.9300	C20—Cl1	1.756 (2)
C9—C10	1.369 (4)	C21—C22	1.342 (3)
C9—H9	0.9300	C21—H21	0.9300
C10—H10	0.9300	C22—C23	1.364 (3)
C11—N1	1.474 (3)	C22—Cl2	1.764 (2)
C11—C12	1.542 (3)	C23—C24	1.405 (3)
C11—H11	0.9800	C23—H23	0.9300
C12—C13	1.366 (3)	C24—H24	0.9300
C12—C17	1.416 (3)	N1—H1A	0.89 (2)
C13—C14	1.380 (3)

C2—C1—C6	116.83 (18)	C14—C13—H13	119.9
C2—C1—C11	118.91 (18)	C13—C14—C15	122.0 (2)
C6—C1—C11	124.21 (19)	C13—C14—H14	119.0
O1—C2—C1	123.06 (17)	C15—C14—H14	119.0
O1—C2—C3	115.88 (18)	C14—C15—C16	118.2 (2)
C1—C2—C3	121.02 (19)	C14—C15—H15	120.9
C4—C3—C2	121.0 (2)	C16—C15—H15	120.9
C4—C3—H3	119.5	C17—C16—C15	120.1 (2)
C2—C3—H3	119.5	C17—C16—H16	120.0
C3—C4—C5	119.18 (19)	C15—C16—H16	120.0
C3—C4—H4	120.4	C16—C17—C12	119.6 (2)
C5—C4—H4	120.4	C16—C17—H17	120.2
C6—C5—C10	121.7 (2)	C12—C17—H17	120.2
C6—C5—C4	119.6 (2)	N1—C18—O1	109.70 (16)
C10—C5—C4	118.57 (18)	N1—C18—C19	110.19 (16)
C5—C6—C1	122.0 (2)	O1—C18—C19	107.78 (16)
C5—C6—C7	119.0 (2)	N1—C18—H18	109.7
C1—C6—C7	118.94 (19)	O1—C18—H18	109.7
C8—C7—C6	118.3 (2)	C19—C18—H18	109.7
C8—C7—H7	120.8	C24—C19—C20	117.6 (2)
C6—C7—H7	120.8	C24—C19—C18	121.76 (19)
C7—C8—C9	122.1 (2)	C20—C19—C18	120.58 (19)
C7—C8—H8	118.9	C21—C20—C19	122.2 (2)
C9—C8—H8	118.9	C21—C20—Cl1	118.04 (18)
C10—C9—C8	121.2 (2)	C19—C20—Cl1	119.74 (17)
C10—C9—H9	119.4	C22—C21—C20	119.4 (2)
C8—C9—H9	119.4	C22—C21—H21	120.3
C9—C10—C5	117.6 (2)	C20—C21—H21	120.3
C9—C10—H10	121.2	C21—C22—C23	122.2 (2)
C5—C10—H10	121.2	C21—C22—Cl2	119.43 (17)
N1—C11—C1	112.31 (16)	C23—C22—Cl2	118.29 (16)
N1—C11—C12	104.43 (17)	C22—C23—C24	118.1 (2)
C1—C11—C12	112.58 (17)	C22—C23—H23	121.0
N1—C11—H11	109.1	C24—C23—H23	121.0
C1—C11—H11	109.1	C19—C24—C23	120.4 (2)
C12—C11—H11	109.1	C19—C24—H24	119.8
C13—C12—C17	119.7 (2)	C23—C24—H24	119.8
C13—C12—C11	123.50 (19)	C18—N1—C11	111.41 (16)
C17—C12—C11	116.68 (19)	C18—N1—H1A	107.6 (16)
C12—C13—C14	120.2 (2)	C11—N1—H1A	108.0 (16)
C12—C13—H13	119.9	C2—O1—C18	113.20 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18···Cl1	0.98	2.60	3.030 (3)	107

Experimental details

Crystal data
Chemical formula	C₂₄H₁₇Cl₂NO
M_r	406.29
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	6.664 (3), 8.224 (3), 18.106 (7)
α, β, γ (°)	92.269 (6), 99.420 (5), 98.624 (6)
V (Å³)	965.8 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Bruker SMART Apex CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7267, 3783, 3386
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.104, 1.02
No. of reflections	3783
No. of parameters	256
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.21

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000), SHELXTL (Bruker, 2000.