7-(Benz­yloxy)spiro­[2H-1,3-benzoxazine-2,1′-cyclo­hexa­n]-4(3H)-one

Jian, S.-Z.; Lei, M.

doi:10.1107/S160053680502845X

7-(Benzyloxy)spiro[2H-1,3-benzoxazine-2,1′-cyclohexan]-4(3H)-one

In the title compound, C₂₀H₂₁NO₃, the dihedral angle between the two benzene rings is 8.79 (7)° and the cyclohexane ring adopts a chair conformation. The molecules are linked by paired N—H

O hydrogen bonds into centrosymmetric R₂²(8) dimers.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680502845X/dn6250sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S160053680502845X/dn6250Isup2.hkl Contains datablock I

CCDC reference: 287550

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.002 Å
R factor = 0.039
wR factor = 0.086
Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.876     0.983
            Tmin(prime) and Tmax expected:      0.977     0.983
            RR(prime) =      0.896
            Please check that your absorption correction is appropriate.
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.90
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C1      ..       6.27 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 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
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The molecular structure of (I) is shown in Fig. 1. The dihedral angle between the benzene ring of the 2H-benzoxazine system and the phenyl ring is 8.79 (7)°. The bulky chair-like six-membered cyclohexane ring in the compound could be used in asymmetric induction, as we have reported previously (Jian et al., 2005).

In the crystal structure, atom N1 acts as a hydrogen donor to atom O1 of a symmetry-related molecule (Table 1), leading to the formation of centrosymmetric R₂²(8) dimers (Fig. 2).

Experimental top

To a mixture of 7-hydroxy-[2H-1,3-benzoxazine-2,1'-cyclohexan]-4(3H)-one (2.0 g, 8.6 mmol) and NaH (0.40 g, 11.7 mmol, 70%) in dimethylformamide (30 ml), benzyl chloride (0.9 ml, 8 mmol) was added dropwise. This mixture was stirred at room temperature for 30 min and then at 333 K overnight. Then, CH₂Cl₂ (30 ml) and water (10 ml) were added to the reaction mixture. The organic layer was washed successively with water (3 × 10 ml), dried over anhydrous Na₂SO₄ and evaporated in vacuo. Recrystallization of the resulting white solid from MeOH gave colourless crystals of (I) (m.p. 470–471 K). Spectroscopic analysis: ¹H NMR (500 MHz, CDCl₃, δ, p.p.m.): 1.39–2.11 (m, 10 H), 5.08 (s, 2 H), 6.52 (s, 1 H), 6.66 (brs, 1 H), 6.67 (dd, 1 H), 7.35–7.44 (m, 5 H), 7.83 (d, 1 H).

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecule of compound (I) in the crystal. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of the dimer formed by paired N—H···O hydrogen bonds in the crystal structure of (I). H atoms not involved in hydrogen bonds have been omitted for clarity. [Symmetry code: (i) −x, 1 − y, 1 − z.]

7-(Benzyloxy)spiro[2H-1,3-benzoxazine-2,1'-cyclohexan]-4(3H)-one top

Crystal data top

C₂₀H₂₁NO₃	F(000) = 688
M_r = 323.38	D_x = 1.283 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6953 reflections
a = 6.0904 (2) Å	θ = 2.6–27.5°
b = 8.9171 (3) Å	µ = 0.09 mm⁻¹
c = 30.8699 (8) Å	T = 295 K
β = 93.147 (1)°	Prism, colourless
V = 1673.98 (9) Å³	0.26 × 0.25 × 0.2 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	2271 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→7
T_min = 0.976, T_max = 0.983	k = −11→11
7297 measured reflections	l = −39→40
3819 independent reflections

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.037P)²] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.039	(Δ/σ)_max < 0.001
wR(F²) = 0.086	Δρ_max = 0.14 e Å⁻³
S = 1	Δρ_min = −0.13 e Å⁻³
3819 reflections	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
222 parameters	Extinction coefficient: 0.0164 (11)
0 restraints

Crystal data top

C₂₀H₂₁NO₃	V = 1673.98 (9) Å³
M_r = 323.38	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 6.0904 (2) Å	µ = 0.09 mm⁻¹
b = 8.9171 (3) Å	T = 295 K
c = 30.8699 (8) Å	0.26 × 0.25 × 0.2 mm
β = 93.147 (1)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	3819 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2271 reflections with I > 2σ(I)
T_min = 0.976, T_max = 0.983	R_int = 0.026
7297 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1	Δρ_max = 0.14 e Å⁻³
3819 reflections	Δρ_min = −0.13 e Å⁻³
222 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.75202 (15)	0.61146 (10)	0.48484 (3)	0.0599 (3)
O2	0.71423 (13)	0.29428 (10)	0.39181 (2)	0.0448 (2)
O3	0.06383 (16)	0.51657 (11)	0.32576 (3)	0.0656 (3)
N1	0.86055 (18)	0.38777 (12)	0.45878 (4)	0.0487 (3)
C1	0.7229 (2)	0.50427 (15)	0.45960 (4)	0.0468 (3)
C2	0.5411 (2)	0.50062 (14)	0.42608 (4)	0.0423 (3)
C3	0.3695 (2)	0.60314 (15)	0.42529 (4)	0.0520 (4)
H3	0.3615	0.6722	0.4477	0.062*
C4	0.2114 (2)	0.60407 (15)	0.39184 (4)	0.0544 (4)
H4	0.0954	0.6719	0.3919	0.065*
C5	0.2256 (2)	0.50319 (16)	0.35785 (4)	0.0492 (3)
C6	0.3932 (2)	0.39837 (15)	0.35776 (4)	0.0459 (3)
H6	0.4018	0.3302	0.3351	0.055*
C7	0.54871 (19)	0.39805 (14)	0.39264 (4)	0.0401 (3)
C8	0.80888 (18)	0.25229 (14)	0.43416 (4)	0.0401 (3)
C9	0.6472 (2)	0.15420 (14)	0.45691 (4)	0.0453 (3)
H9A	0.7081	0.1295	0.4857	0.054*
H9B	0.5118	0.2095	0.46	0.054*
C10	0.5965 (2)	0.01062 (16)	0.43206 (5)	0.0568 (4)
H10A	0.519	0.0346	0.4046	0.068*
H10B	0.501	−0.0519	0.4486	0.068*
C11	0.8048 (2)	−0.07562 (17)	0.42350 (5)	0.0663 (4)
H11A	0.8711	−0.1123	0.4508	0.08*
H11B	0.7679	−0.1616	0.4053	0.08*
C12	0.9687 (2)	0.02193 (17)	0.40143 (5)	0.0566 (4)
H12A	0.9112	0.0456	0.3723	0.068*
H12B	1.1047	−0.0334	0.399	0.068*
C13	1.01683 (19)	0.16685 (15)	0.42607 (4)	0.0493 (3)
H13A	1.0936	0.1439	0.4536	0.059*
H13B	1.1124	0.2293	0.4096	0.059*
C14	0.0463 (2)	0.40645 (17)	0.29279 (5)	0.0623 (4)
H14A	0.0182	0.3091	0.3054	0.075*
H14B	0.1828	0.4006	0.2781	0.075*
C15	−0.1395 (2)	0.44823 (16)	0.26089 (4)	0.0506 (3)
C16	−0.2991 (2)	0.54910 (19)	0.27076 (5)	0.0644 (4)
H16	−0.2926	0.5957	0.2978	0.077*
C17	−0.4702 (3)	0.5822 (2)	0.24079 (5)	0.0806 (5)
H17	−0.5769	0.6517	0.2475	0.097*
C18	−0.4814 (3)	0.5125 (2)	0.20146 (5)	0.0808 (5)
H18	−0.5968	0.534	0.1814	0.097*
C19	−0.3250 (3)	0.4116 (2)	0.19132 (5)	0.0784 (5)
H19	−0.3341	0.3637	0.1645	0.094*
C20	−0.1536 (3)	0.38067 (19)	0.22073 (5)	0.0676 (4)
H20	−0.0454	0.3131	0.2134	0.081*
H1	0.982 (2)	0.3870 (16)	0.4752 (4)	0.063 (4)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0725 (7)	0.0436 (6)	0.0611 (6)	−0.0002 (5)	−0.0188 (5)	−0.0127 (5)
O2	0.0479 (5)	0.0473 (5)	0.0387 (5)	0.0051 (4)	−0.0024 (4)	0.0000 (4)
O3	0.0735 (7)	0.0584 (7)	0.0614 (6)	0.0163 (5)	−0.0261 (5)	−0.0065 (5)
N1	0.0447 (6)	0.0427 (7)	0.0567 (7)	−0.0020 (5)	−0.0150 (5)	−0.0084 (5)
C1	0.0531 (8)	0.0390 (8)	0.0473 (8)	−0.0074 (6)	−0.0051 (6)	−0.0014 (6)
C2	0.0484 (7)	0.0354 (7)	0.0424 (7)	−0.0029 (6)	−0.0031 (6)	0.0006 (6)
C3	0.0643 (9)	0.0402 (8)	0.0506 (8)	0.0033 (7)	−0.0040 (7)	−0.0058 (6)
C4	0.0587 (8)	0.0427 (8)	0.0606 (8)	0.0118 (7)	−0.0084 (7)	−0.0027 (7)
C5	0.0546 (8)	0.0439 (8)	0.0475 (8)	0.0027 (6)	−0.0116 (6)	0.0053 (6)
C6	0.0552 (8)	0.0427 (8)	0.0391 (7)	0.0006 (6)	−0.0041 (6)	0.0001 (6)
C7	0.0419 (7)	0.0362 (7)	0.0421 (7)	−0.0004 (6)	0.0011 (5)	0.0036 (6)
C8	0.0376 (6)	0.0411 (7)	0.0406 (7)	−0.0010 (5)	−0.0059 (5)	−0.0018 (6)
C9	0.0425 (7)	0.0471 (8)	0.0461 (7)	0.0011 (6)	0.0012 (6)	0.0006 (6)
C10	0.0486 (8)	0.0464 (9)	0.0760 (10)	−0.0104 (7)	0.0091 (7)	−0.0035 (7)
C11	0.0609 (10)	0.0442 (9)	0.0935 (12)	0.0019 (7)	0.0018 (8)	−0.0110 (8)
C12	0.0418 (7)	0.0600 (10)	0.0676 (9)	0.0110 (7)	−0.0018 (6)	−0.0152 (7)
C13	0.0348 (6)	0.0548 (9)	0.0580 (8)	−0.0005 (6)	−0.0012 (6)	−0.0015 (7)
C14	0.0655 (9)	0.0605 (10)	0.0586 (9)	0.0068 (8)	−0.0171 (7)	−0.0023 (8)
C15	0.0493 (8)	0.0547 (9)	0.0469 (8)	−0.0031 (7)	−0.0043 (6)	0.0079 (7)
C16	0.0599 (9)	0.0775 (11)	0.0549 (9)	0.0055 (8)	−0.0057 (7)	−0.0024 (8)
C17	0.0623 (10)	0.0985 (14)	0.0793 (12)	0.0219 (9)	−0.0110 (9)	−0.0005 (11)
C18	0.0672 (10)	0.1095 (16)	0.0633 (10)	0.0014 (11)	−0.0198 (8)	0.0153 (10)
C19	0.0818 (12)	0.1036 (15)	0.0481 (9)	0.0015 (11)	−0.0101 (8)	−0.0002 (9)
C20	0.0673 (10)	0.0804 (12)	0.0546 (9)	0.0082 (8)	−0.0030 (8)	−0.0039 (8)

Geometric parameters (Å, º) top

O1—C1	1.2397 (14)	C10—H10A	0.97
O2—C7	1.3697 (14)	C10—H10B	0.97
O2—C8	1.4485 (12)	C11—C12	1.514 (2)
O3—C5	1.3637 (14)	C11—H11A	0.97
O3—C14	1.4141 (16)	C11—H11B	0.97
N1—C1	1.3359 (16)	C12—C13	1.5198 (18)
N1—C8	1.4525 (15)	C12—H12A	0.97
N1—H1	0.875 (14)	C12—H12B	0.97
C1—C2	1.4741 (16)	C13—H13A	0.97
C2—C7	1.3819 (17)	C13—H13B	0.97
C2—C3	1.3875 (17)	C14—C15	1.5056 (18)
C3—C4	1.3729 (17)	C14—H14A	0.97
C3—H3	0.93	C14—H14B	0.97
C4—C5	1.3883 (18)	C15—C16	1.371 (2)
C4—H4	0.93	C15—C20	1.3769 (19)
C5—C6	1.3838 (18)	C16—C17	1.387 (2)
C6—C7	1.3945 (16)	C16—H16	0.93
C6—H6	0.93	C17—C18	1.362 (2)
C8—C13	1.5105 (17)	C17—H17	0.93
C8—C9	1.5180 (17)	C18—C19	1.359 (2)
C9—C10	1.5155 (17)	C18—H18	0.93
C9—H9A	0.97	C19—C20	1.373 (2)
C9—H9B	0.97	C19—H19	0.93
C10—C11	1.5193 (19)	C20—H20	0.93

C7—O2—C8	114.50 (9)	H10A—C10—H10B	108
C5—O3—C14	119.02 (11)	C12—C11—C10	111.42 (12)
C1—N1—C8	122.60 (10)	C12—C11—H11A	109.3
C1—N1—H1	120.4 (9)	C10—C11—H11A	109.3
C8—N1—H1	116.7 (9)	C12—C11—H11B	109.3
O1—C1—N1	122.92 (11)	C10—C11—H11B	109.3
O1—C1—C2	122.29 (12)	H11A—C11—H11B	108
N1—C1—C2	114.67 (11)	C11—C12—C13	112.14 (12)
C7—C2—C3	118.63 (11)	C11—C12—H12A	109.2
C7—C2—C1	118.96 (12)	C13—C12—H12A	109.2
C3—C2—C1	122.27 (11)	C11—C12—H12B	109.2
C4—C3—C2	120.91 (12)	C13—C12—H12B	109.2
C4—C3—H3	119.5	H12A—C12—H12B	107.9
C2—C3—H3	119.5	C8—C13—C12	111.80 (10)
C3—C4—C5	119.61 (13)	C8—C13—H13A	109.3
C3—C4—H4	120.2	C12—C13—H13A	109.3
C5—C4—H4	120.2	C8—C13—H13B	109.3
O3—C5—C6	124.14 (12)	C12—C13—H13B	109.3
O3—C5—C4	114.81 (12)	H13A—C13—H13B	107.9
C6—C5—C4	121.06 (11)	O3—C14—C15	108.86 (12)
C5—C6—C7	118.00 (12)	O3—C14—H14A	109.9
C5—C6—H6	121	C15—C14—H14A	109.9
C7—C6—H6	121	O3—C14—H14B	109.9
O2—C7—C2	121.07 (10)	C15—C14—H14B	109.9
O2—C7—C6	117.16 (11)	H14A—C14—H14B	108.3
C2—C7—C6	121.74 (12)	C16—C15—C20	118.51 (13)
O2—C8—N1	108.74 (10)	C16—C15—C14	122.25 (13)
O2—C8—C13	106.08 (9)	C20—C15—C14	119.22 (14)
N1—C8—C13	110.27 (10)	C15—C16—C17	120.47 (15)
O2—C8—C9	109.28 (9)	C15—C16—H16	119.8
N1—C8—C9	111.38 (10)	C17—C16—H16	119.8
C13—C8—C9	110.92 (11)	C18—C17—C16	119.81 (16)
C10—C9—C8	111.84 (11)	C18—C17—H17	120.1
C10—C9—H9A	109.2	C16—C17—H17	120.1
C8—C9—H9A	109.2	C19—C18—C17	120.36 (15)
C10—C9—H9B	109.2	C19—C18—H18	119.8
C8—C9—H9B	109.2	C17—C18—H18	119.8
H9A—C9—H9B	107.9	C18—C19—C20	119.85 (16)
C9—C10—C11	111.51 (11)	C18—C19—H19	120.1
C9—C10—H10A	109.3	C20—C19—H19	120.1
C11—C10—H10A	109.3	C19—C20—C15	120.98 (16)
C9—C10—H10B	109.3	C19—C20—H20	119.5
C11—C10—H10B	109.3	C15—C20—H20	119.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.874 (12)	1.982 (12)	2.8541 (15)	176.9 (11)

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₁NO₃
M_r	323.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	6.0904 (2), 8.9171 (3), 30.8699 (8)
β (°)	93.147 (1)
V (Å³)	1673.98 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.26 × 0.25 × 0.2

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.976, 0.983
No. of measured, independent and observed [I > 2σ(I)] reflections	7297, 3819, 2271
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.086, 1
No. of reflections	3819
No. of parameters	222
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.13

Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, CrystalStructure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999) and PLATON (Spek, 2003).