(±)-3-(2,6-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/S1600536807055432

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(±)-3-(2,6-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 is distorted and adopts an envelope conformation. The dihedral angle between the dichlorophenyl ring and the naphthyl system is 85.30 (13)°. An intramolecular N—H

Cl hydrogen bond is observed.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055432/dn2255sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055432/dn2255Isup2.hkl Contains datablock I

CCDC reference: 672880

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.004 Å
R factor = 0.050
wR factor = 0.151
Data-to-parameter ratio = 15.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.94 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C3     -   C4      ..       5.31 su
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         C4
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C11
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C2
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C6
PLAT420_ALERT_2_C D-H Without Acceptor       N1     -   H1     ...          ?
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  CL2     ..       2.88 Ang.

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of C7     = ...          R
PLAT793_ALERT_1_G Check the Absolute Configuration of C8     = ...          S
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 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(I).

The oxazine ring is distorted and adopts a half chair conformation(Fig.1), the dihedral angle between the O1/C15/C16 plane and the N1/C1/C7/C8 plane is 46.08°.

The ring puckering parameters (Cremer & Pople, 1975) for the oxazine are, Q = 0.450 (2) Å, θ = 125.0 (3) ° and ϕ = 298.2 (3) ° indicating an enveloppe conformation. The dichlorophenyl ring makes dihedral angles of 61.27 (18)° and 61.35 (15)° with the benzene ring and the naphthyl system, respectively. The C7—O1 and C7—N1 bond lengths are 1.454 (3) Å and 1.429 (3)\%A. The structure is stabilized by intramolecular N1—H1···Cl2 hydrogen bond(table 1).

Related literature top

For related literature, see: Cremer & Pople (1975); 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 mixture was stirred for several minitutes, 2,6-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 methanol, colourless single crystals of (I) was obtained after 3 d.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. Molecular view of (I) with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as small spheres of arbitrary radii.

(+/-)-3-(2,6-Dichlorophenyl)-1-phenyl-2,3-dihydro-1H-naphtho[1,2-e][1,3]oxazine top

Crystal data top

C₂₄H₁₇Cl₂NO	F(000) = 1680
M_r = 406.29	D_x = 1.380 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 1420 reflections
a = 10.8041 (9) Å	θ = 2.2–24.3°
b = 10.0189 (9) Å	µ = 0.35 mm⁻¹
c = 36.119 (3) Å	T = 298 K
V = 3909.7 (6) Å³	Block, colourless
Z = 8	0.27 × 0.23 × 0.22 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4060 independent reflections
Radiation source: sealed tube	2484 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and ω scans	θ_max = 26.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −13→13
T_min = 0.912, T_max = 0.928	k = −12→12
43758 measured reflections	l = −45→45

Refinement top

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)] = 0.050	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.151	w = 1/[σ²(F_o²) + (0.0627P)² + 1.1294P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
4060 reflections	Δρ_max = 0.22 e Å⁻³
257 parameters	Δρ_min = −0.40 e Å⁻³
1 restraint	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (4)

Crystal data top

C₂₄H₁₇Cl₂NO	V = 3909.7 (6) Å³
M_r = 406.29	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 10.8041 (9) Å	µ = 0.35 mm⁻¹
b = 10.0189 (9) Å	T = 298 K
c = 36.119 (3) Å	0.27 × 0.23 × 0.22 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4060 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	2484 reflections with I > 2σ(I)
T_min = 0.912, T_max = 0.928	R_int = 0.047
43758 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	1 restraint
wR(F²) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.22 e Å⁻³
4060 reflections	Δρ_min = −0.40 e Å⁻³
257 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
Cl1	0.35756 (10)	−0.01015 (9)	0.47316 (3)	0.1301 (4)
Cl2	−0.05546 (8)	0.25328 (10)	0.42897 (3)	0.1288 (4)
O1	0.09492 (15)	0.05472 (17)	0.39088 (5)	0.0714 (5)
N1	0.24544 (18)	0.23064 (18)	0.40158 (5)	0.0577 (5)
H1	0.1936 (18)	0.2944 (18)	0.4028 (7)	0.069*
C1	0.1477 (2)	0.1169 (2)	0.45289 (6)	0.0616 (6)
C2	0.2172 (3)	0.0667 (3)	0.48184 (8)	0.0848 (9)
C3	0.1796 (6)	0.0765 (5)	0.51820 (10)	0.1315 (17)
H3	0.2287	0.0428	0.5371	0.158*
C4	0.0693 (7)	0.1363 (6)	0.52598 (13)	0.160 (3)
H4	0.0429	0.1420	0.5504	0.192*
C5	−0.0030 (5)	0.1882 (4)	0.49849 (14)	0.1293 (17)
H5	−0.0779	0.2292	0.5041	0.155*
C6	0.0363 (3)	0.1790 (3)	0.46230 (8)	0.0840 (8)
C7	0.1943 (2)	0.1069 (2)	0.41385 (6)	0.0577 (5)
H7	0.2612	0.0409	0.4137	0.069*
C8	0.2899 (2)	0.2203 (2)	0.36306 (6)	0.0545 (5)
H8	0.3082	0.3110	0.3545	0.065*
C9	0.4104 (2)	0.1421 (2)	0.36226 (6)	0.0564 (6)
C10	0.5121 (3)	0.1931 (3)	0.38075 (8)	0.0844 (8)
H10	0.5061	0.2749	0.3928	0.101*
C11	0.6226 (3)	0.1236 (5)	0.38154 (10)	0.1080 (11)
H11	0.6904	0.1590	0.3940	0.130*
C12	0.6325 (3)	0.0028 (4)	0.36396 (11)	0.1008 (11)
H12	0.7066	−0.0443	0.3649	0.121*
C13	0.5331 (2)	−0.0489 (3)	0.34496 (8)	0.0822 (8)
H13	0.5399	−0.1302	0.3327	0.099*
C14	0.4232 (2)	0.0211 (2)	0.34435 (6)	0.0625 (6)
H14	0.3560	−0.0140	0.3315	0.075*
C15	0.18997 (19)	0.1652 (2)	0.33852 (6)	0.0547 (5)
C16	0.0986 (2)	0.0886 (2)	0.35411 (7)	0.0610 (6)
C17	−0.0003 (2)	0.0385 (3)	0.33265 (9)	0.0773 (7)
H17	−0.0624	−0.0114	0.3438	0.093*
C18	−0.0047 (3)	0.0632 (3)	0.29574 (9)	0.0852 (8)
H18	−0.0697	0.0289	0.2818	0.102*
C19	0.0876 (2)	0.1399 (3)	0.27812 (8)	0.0737 (7)
C20	0.0857 (3)	0.1656 (3)	0.23973 (9)	0.0939 (10)
H20	0.0224	0.1297	0.2254	0.113*
C21	0.1733 (4)	0.2410 (4)	0.22337 (9)	0.1035 (11)
H21	0.1708	0.2556	0.1980	0.124*
C22	0.2678 (3)	0.2969 (3)	0.24464 (7)	0.0895 (9)
H22	0.3269	0.3509	0.2334	0.107*
C23	0.2741 (3)	0.2731 (3)	0.28176 (7)	0.0729 (7)
H23	0.3383	0.3104	0.2955	0.088*
C24	0.1852 (2)	0.1931 (2)	0.29982 (6)	0.0609 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.1270 (8)	0.0978 (6)	0.1654 (9)	0.0119 (5)	−0.0736 (7)	−0.0025 (6)
Cl2	0.0843 (6)	0.1073 (7)	0.1950 (11)	0.0303 (5)	0.0179 (6)	0.0009 (7)
O1	0.0700 (11)	0.0685 (10)	0.0757 (11)	−0.0240 (8)	0.0004 (8)	−0.0048 (8)
N1	0.0622 (11)	0.0528 (11)	0.0580 (11)	−0.0092 (9)	0.0081 (9)	−0.0083 (9)
C1	0.0713 (15)	0.0489 (12)	0.0646 (14)	−0.0111 (11)	0.0114 (12)	−0.0030 (10)
C2	0.119 (2)	0.0648 (16)	0.0710 (18)	−0.0322 (16)	−0.0129 (16)	0.0017 (13)
C3	0.210 (5)	0.119 (3)	0.065 (2)	−0.084 (3)	−0.012 (3)	0.002 (2)
C4	0.269 (8)	0.130 (4)	0.082 (3)	−0.111 (5)	0.069 (4)	−0.040 (3)
C5	0.159 (4)	0.091 (3)	0.138 (3)	−0.045 (2)	0.091 (3)	−0.044 (3)
C6	0.090 (2)	0.0641 (15)	0.098 (2)	−0.0122 (14)	0.0370 (17)	−0.0110 (14)
C7	0.0571 (12)	0.0524 (12)	0.0635 (14)	−0.0051 (10)	0.0047 (11)	−0.0061 (10)
C8	0.0579 (13)	0.0556 (13)	0.0499 (12)	−0.0091 (10)	0.0031 (10)	−0.0052 (10)
C9	0.0503 (12)	0.0688 (14)	0.0501 (12)	−0.0107 (11)	0.0028 (10)	0.0029 (10)
C10	0.0659 (17)	0.105 (2)	0.0820 (18)	−0.0120 (16)	−0.0122 (14)	−0.0117 (16)
C11	0.0606 (19)	0.146 (3)	0.118 (3)	−0.018 (2)	−0.0249 (17)	0.009 (2)
C12	0.0507 (16)	0.124 (3)	0.128 (3)	0.0081 (18)	0.0072 (17)	0.032 (2)
C13	0.0639 (17)	0.0863 (19)	0.097 (2)	0.0076 (14)	0.0183 (15)	0.0106 (16)
C14	0.0507 (13)	0.0715 (15)	0.0654 (14)	−0.0034 (11)	0.0071 (10)	−0.0002 (12)
C15	0.0493 (12)	0.0532 (12)	0.0617 (14)	0.0032 (10)	−0.0030 (10)	−0.0102 (10)
C16	0.0564 (13)	0.0573 (13)	0.0693 (16)	−0.0006 (11)	−0.0041 (11)	−0.0107 (11)
C17	0.0573 (14)	0.0706 (16)	0.104 (2)	−0.0080 (12)	−0.0128 (14)	−0.0130 (15)
C18	0.0732 (18)	0.0804 (18)	0.102 (2)	0.0057 (15)	−0.0364 (16)	−0.0224 (16)
C19	0.0710 (16)	0.0706 (16)	0.0795 (18)	0.0176 (14)	−0.0211 (14)	−0.0187 (13)
C20	0.103 (2)	0.102 (2)	0.076 (2)	0.030 (2)	−0.0342 (18)	−0.0223 (17)
C21	0.128 (3)	0.122 (3)	0.0605 (18)	0.041 (2)	−0.016 (2)	−0.0045 (18)
C22	0.104 (2)	0.102 (2)	0.0623 (17)	0.0224 (18)	0.0041 (16)	0.0032 (15)
C23	0.0777 (17)	0.0803 (17)	0.0608 (15)	0.0121 (14)	0.0002 (13)	−0.0053 (13)
C24	0.0617 (14)	0.0614 (13)	0.0594 (14)	0.0156 (12)	−0.0084 (11)	−0.0092 (11)

Geometric parameters (Å, º) top

Cl1—C2	1.729 (4)	C11—C12	1.371 (5)
Cl2—C6	1.728 (3)	C11—H11	0.9300
O1—C16	1.371 (3)	C12—C13	1.376 (4)
O1—C7	1.454 (3)	C12—H12	0.9300
N1—C7	1.428 (3)	C13—C14	1.379 (3)
N1—C8	1.476 (3)	C13—H13	0.9300
N1—H1	0.851 (10)	C14—H14	0.9300
C1—C2	1.382 (4)	C15—C16	1.372 (3)
C1—C6	1.397 (4)	C15—C24	1.426 (3)
C1—C7	1.500 (3)	C16—C17	1.412 (3)
C2—C3	1.378 (5)	C17—C18	1.357 (4)
C3—C4	1.363 (7)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.410 (4)
C4—C5	1.366 (7)	C18—H18	0.9300
C4—H4	0.9300	C19—C20	1.411 (4)
C5—C6	1.377 (5)	C19—C24	1.418 (3)
C5—H5	0.9300	C20—C21	1.347 (5)
C7—H7	0.9800	C20—H20	0.9300
C8—C15	1.502 (3)	C21—C22	1.396 (5)
C8—C9	1.520 (3)	C21—H21	0.9300
C8—H8	0.9800	C22—C23	1.363 (4)
C9—C14	1.381 (3)	C22—H22	0.9300
C9—C10	1.384 (3)	C23—C24	1.411 (4)
C10—C11	1.382 (5)	C23—H23	0.9300
C10—H10	0.9300

C16—O1—C7	116.25 (17)	C12—C11—H11	119.9
C7—N1—C8	110.97 (16)	C10—C11—H11	119.9
C7—N1—H1	112.4 (17)	C11—C12—C13	120.2 (3)
C8—N1—H1	108.3 (17)	C11—C12—H12	119.9
C2—C1—C6	116.5 (2)	C13—C12—H12	119.9
C2—C1—C7	120.3 (2)	C12—C13—C14	119.2 (3)
C6—C1—C7	123.2 (2)	C12—C13—H13	120.4
C3—C2—C1	122.3 (4)	C14—C13—H13	120.4
C3—C2—Cl1	117.6 (3)	C13—C14—C9	121.7 (2)
C1—C2—Cl1	120.1 (2)	C13—C14—H14	119.2
C4—C3—C2	119.1 (5)	C9—C14—H14	119.2
C4—C3—H3	120.5	C16—C15—C24	119.1 (2)
C2—C3—H3	120.5	C16—C15—C8	118.7 (2)
C3—C4—C5	121.2 (4)	C24—C15—C8	122.2 (2)
C3—C4—H4	119.4	O1—C16—C15	123.9 (2)
C5—C4—H4	119.4	O1—C16—C17	114.9 (2)
C4—C5—C6	119.2 (5)	C15—C16—C17	121.2 (2)
C4—C5—H5	120.4	C18—C17—C16	120.1 (3)
C6—C5—H5	120.4	C18—C17—H17	120.0
C5—C6—C1	121.8 (4)	C16—C17—H17	120.0
C5—C6—Cl2	117.1 (3)	C17—C18—C19	121.2 (2)
C1—C6—Cl2	121.1 (2)	C17—C18—H18	119.4
N1—C7—O1	114.88 (18)	C19—C18—H18	119.4
N1—C7—C1	111.32 (17)	C18—C19—C20	122.2 (3)
O1—C7—C1	108.22 (17)	C18—C19—C24	118.8 (2)
N1—C7—H7	107.4	C20—C19—C24	119.1 (3)
O1—C7—H7	107.4	C21—C20—C19	121.5 (3)
C1—C7—H7	107.4	C21—C20—H20	119.2
N1—C8—C15	110.36 (17)	C19—C20—H20	119.2
N1—C8—C9	109.43 (17)	C20—C21—C22	119.9 (3)
C15—C8—C9	114.52 (17)	C20—C21—H21	120.1
N1—C8—H8	107.4	C22—C21—H21	120.1
C15—C8—H8	107.4	C23—C22—C21	120.5 (3)
C9—C8—H8	107.4	C23—C22—H22	119.7
C14—C9—C10	118.1 (2)	C21—C22—H22	119.8
C14—C9—C8	123.17 (19)	C22—C23—C24	121.3 (3)
C10—C9—C8	118.7 (2)	C22—C23—H23	119.3
C11—C10—C9	120.7 (3)	C24—C23—H23	119.3
C11—C10—H10	119.7	C23—C24—C19	117.7 (2)
C9—C10—H10	119.7	C23—C24—C15	122.6 (2)
C12—C11—C10	120.1 (3)	C19—C24—C15	119.7 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.85 (1)	2.88 (2)	3.406 (2)	122 (2)

Experimental details

Crystal data
Chemical formula	C₂₄H₁₇Cl₂NO
M_r	406.29
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	10.8041 (9), 10.0189 (9), 36.119 (3)
V (Å³)	3909.7 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.27 × 0.23 × 0.22

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.912, 0.928
No. of measured, independent and observed [I > 2σ(I)] reflections	43758, 4060, 2484
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.151, 1.05
No. of reflections	4060
No. of parameters	257
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.40

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.851 (10)	2.88 (2)	3.406 (2)	121.6 (19)

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