4-Tosyl-1-oxa-4-aza­spiro­[4.5]deca-6,9-dien-8-one

Yin, P.; Zhang, W.-W.; Yin, H.-B.; He, L.; Huang, W.-C.

doi:10.1107/S1600536809001524

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o649

doi:10.1107/S1600536809001524

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4-Tosyl-1-oxa-4-azaspiro[4.5]deca-6,9-dien-8-one

Ping Yin,^a Wen-Wen Zhang,^a Hai-Bin Yin,^b Ling He ^a and Wen-Cai Huang ^c ^*

^aDepartment of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu 610041, People's Republic of China, ^bGuangzhou Yuantong Pharmaceutical Technology Co Ltd, Guangzhou 510610, People's Republic of China, and ^cDepartment of Pharmaceutical and Bioengineering, School of Chemical Engineering, Sichuan University, Chengdu 610065, People's Republic of China
^*Correspondence e-mail: hwc@scu.edu.cn

(Received 6 January 2009; accepted 13 January 2009; online 28 February 2009)

In the molecule of the title compound, C₁₅H₁₅NO₄S, the two six-membered rings are almost parallel to each other [dihedral angle = 1.87 (9)°] and perpendicular to the mean plane through the five-membered ring [dihedral angles of 89.98 (10) and 89.04 (10)°]. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen-bonding interactions.

Related literature

For general background to the catalytic oxidation of phenol derivatives using transition metal complexes, see: Bernini et al. (2006 ); Cheung et al. (2005 ). For puckering parameters, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₅H₁₅NO₄S
M_r = 305.34
Monoclinic, P 2₁ /c
a = 11.882 (3) Å
b = 14.973 (6) Å
c = 8.369 (5) Å
β = 107.00 (3)°
V = 1423.9 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 294 K
0.30 × 0.25 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2996 measured reflections
2625 independent reflections
1526 reflections with I > 2σ(I)
R_int = 0.008
3 standard reflections every 300 reflections intensity decay: 1.6%

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.119
S = 1.02
2625 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O4ⁱ	0.93	2.48	3.211 (4)	134
C15—H15B⋯O2ⁱⁱ	0.96	2.57	3.520 (5)	171
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) x, y, z+1.

Data collection: DIFRAC (Gabe & White, 1993 ); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001524/rz2288sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809001524/rz2288Isup2.hkl

checkCIF report

Comment top

In the course of our studies aimed to prepare a substituted quinone from the corresponding aromatic ether by catalytic oxidation using transition metal complexes (Cheung et al., 2005; Bernini et al.,2006), the title compound was unexpectedly obtained in about 70% yield. In the molecule of the title compound (Fig. 1) the C1–C6 and C9–C14 six-membered rings are almost parallel to each other(dihedral angle 1.87 (9)°) and perpendicular to the mean plane through the O1/N1/C1/C7/C8 ring, forming dihedral angles of 89.98 (10) and 89.04 (10)°, respectively. The five-membered ring adopts an envelope conformation, with puckering parameters Q2 = 0.269 (3) Å and ϕ2 =104.4 (6)° ((Cremer & Pople, 1975). The crystal structure (Fig. 2) is enforced by intermolecular C—H···O hydrogen bonds (Table 1).

Related literature top

For general background to the catalytic oxidation of phenol derivatives using transition metal complexes, see: Bernini et al. (2006); Cheung et al. (2005). For puckering parameters, see: Cremer & Pople (1975).

Experimental top

A solution of 2-phenoxyethyl-p-toluenesulfon amide (1 mmol) and indobenzene diacetate (1.5 mmol) in dichloromethane was charged in a reaction flask and 4 A molecular sieves was added. Then, the mixture was stirred at 303 K under a nitrogen atmosphere for 4 h. After cooling to room temperature, the resulting mixture was filtered and the solvent was removed under vacuo. The residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (5:1 v/v) as the eluent. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation in a cyclohexane/ether solution (5:1 v/v) at room temperature.

Computing details top

Data collection: DIFRAC (Gabe & White, 1993); cell refinement: DIFRAC (Gabe & White, 1993); data reduction: NRCVAX (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Crystal packing of the title compound approximately viewed along the b axis.

4-Tosyl-1-oxa-4-azaspiro[4.5]deca-6,9-dien-8-one top

Crystal data top

C₁₅H₁₅NO₄S	F(000) = 640
M_r = 305.34	D_x = 1.424 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.882 (3) Å	Cell parameters from 22 reflections
b = 14.973 (6) Å	θ = 4.5–7.7°
c = 8.369 (5) Å	µ = 0.24 mm⁻¹
β = 107.00 (3)°	T = 294 K
V = 1423.9 (11) Å³	Block, colourless
Z = 4	0.30 × 0.25 × 0.20 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
Radiation source: fine-focus sealed tube	θ_max = 25.5°, θ_min = 1.8°
Graphite monochromator	h = −14→3
ω/2–θ scans	k = −18→0
2996 measured reflections	l = −9→10
2625 independent reflections	3 standard reflections every 300 reflections
1526 reflections with I > 2σ(I)	intensity decay: 1.6%

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0523P)² + 0.2087P] where P = (F_o² + 2F_c²)/3
2625 reflections	(Δ/σ)_max < 0.001
192 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.27 e Å⁻³

Crystal data top

C₁₅H₁₅NO₄S	V = 1423.9 (11) Å³
M_r = 305.34	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.882 (3) Å	µ = 0.24 mm⁻¹
b = 14.973 (6) Å	T = 294 K
c = 8.369 (5) Å	0.30 × 0.25 × 0.20 mm
β = 107.00 (3)°

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.008
2996 measured reflections	3 standard reflections every 300 reflections
2625 independent reflections	intensity decay: 1.6%
1526 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 1.02	Δρ_max = 0.30 e Å⁻³
2625 reflections	Δρ_min = −0.27 e Å⁻³
192 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
S1	0.28106 (6)	0.58803 (5)	0.06825 (9)	0.0407 (2)
O1	0.09259 (19)	0.57997 (15)	−0.3866 (3)	0.0638 (7)
O2	−0.1639 (2)	0.7616 (2)	−0.1273 (4)	0.1088 (11)
O3	0.20120 (17)	0.62375 (14)	0.1501 (3)	0.0500 (5)
O4	0.35194 (17)	0.51210 (13)	0.1369 (3)	0.0531 (6)
N1	0.20196 (18)	0.55681 (15)	−0.1165 (3)	0.0408 (6)
C1	0.0935 (2)	0.60359 (18)	−0.2213 (4)	0.0420 (7)
C2	0.0995 (3)	0.70272 (19)	−0.2139 (4)	0.0448 (7)
H2	0.1650	0.7308	−0.2304	0.054*
C3	0.0165 (3)	0.7524 (2)	−0.1852 (4)	0.0532 (8)
H3	0.0239	0.8142	−0.1869	0.064*
C4	−0.0868 (3)	0.7143 (3)	−0.1509 (5)	0.0648 (10)
C5	−0.0943 (3)	0.6167 (2)	−0.1518 (4)	0.0612 (9)
H5	−0.1587	0.5897	−0.1301	0.073*
C6	−0.0124 (3)	0.5663 (2)	−0.1826 (4)	0.0523 (8)
H6	−0.0207	0.5046	−0.1802	0.063*
C7	0.1620 (3)	0.5036 (2)	−0.3849 (4)	0.0662 (10)
H7A	0.1950	0.5048	−0.4780	0.079*
H7B	0.1151	0.4498	−0.3926	0.079*
C8	0.2563 (3)	0.5062 (2)	−0.2247 (4)	0.0613 (9)
H8A	0.2779	0.4465	−0.1815	0.074*
H8B	0.3257	0.5364	−0.2365	0.074*
C9	0.3779 (2)	0.67304 (18)	0.0454 (3)	0.0383 (7)
C10	0.3497 (3)	0.7621 (2)	0.0559 (4)	0.0493 (8)
H10	0.2795	0.7780	0.0765	0.059*
C11	0.4264 (3)	0.8267 (2)	0.0357 (4)	0.0536 (9)
H11	0.4072	0.8865	0.0431	0.064*
C12	0.5312 (3)	0.8055 (2)	0.0047 (4)	0.0472 (8)
C13	0.5568 (3)	0.7168 (2)	−0.0071 (4)	0.0535 (8)
H13	0.6266	0.7012	−0.0288	0.064*
C14	0.4821 (2)	0.6503 (2)	0.0123 (4)	0.0487 (8)
H14	0.5012	0.5907	0.0034	0.058*
C15	0.6133 (3)	0.8785 (2)	−0.0157 (4)	0.0669 (10)
H15A	0.5717	0.9187	−0.1021	0.100*
H15B	0.6783	0.8526	−0.0456	0.100*
H15C	0.6421	0.9105	0.0875	0.100*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0436 (4)	0.0356 (4)	0.0419 (4)	−0.0024 (4)	0.0108 (3)	0.0011 (4)
O1	0.0715 (15)	0.0670 (15)	0.0453 (13)	0.0231 (13)	0.0053 (11)	−0.0080 (12)
O2	0.0677 (17)	0.102 (2)	0.170 (3)	0.0206 (17)	0.0560 (19)	−0.020 (2)
O3	0.0541 (12)	0.0512 (12)	0.0523 (13)	−0.0066 (10)	0.0274 (11)	−0.0068 (10)
O4	0.0538 (13)	0.0428 (12)	0.0567 (13)	0.0034 (10)	0.0068 (10)	0.0121 (10)
N1	0.0385 (13)	0.0350 (13)	0.0467 (14)	0.0030 (10)	0.0090 (11)	−0.0056 (11)
C1	0.0415 (16)	0.0367 (17)	0.0463 (17)	0.0037 (13)	0.0106 (13)	−0.0020 (13)
C2	0.0433 (17)	0.0389 (17)	0.055 (2)	−0.0021 (14)	0.0191 (15)	0.0070 (15)
C3	0.0524 (19)	0.0370 (17)	0.069 (2)	0.0035 (15)	0.0153 (17)	−0.0028 (16)
C4	0.046 (2)	0.073 (3)	0.077 (3)	0.0122 (19)	0.0189 (18)	−0.006 (2)
C5	0.0384 (18)	0.068 (2)	0.076 (2)	−0.0077 (17)	0.0154 (17)	0.014 (2)
C6	0.0427 (17)	0.0369 (17)	0.070 (2)	−0.0053 (15)	0.0056 (16)	0.0093 (16)
C7	0.056 (2)	0.074 (3)	0.062 (2)	0.0135 (19)	0.0072 (18)	−0.0205 (19)
C8	0.0557 (19)	0.063 (2)	0.062 (2)	0.0097 (18)	0.0110 (17)	−0.0179 (18)
C9	0.0354 (16)	0.0394 (16)	0.0388 (16)	−0.0060 (13)	0.0088 (13)	0.0004 (13)
C10	0.0471 (18)	0.0431 (18)	0.065 (2)	−0.0050 (14)	0.0273 (16)	−0.0088 (16)
C11	0.064 (2)	0.0366 (17)	0.067 (2)	−0.0055 (16)	0.0306 (18)	−0.0081 (16)
C12	0.0453 (18)	0.050 (2)	0.0463 (19)	−0.0113 (15)	0.0135 (15)	−0.0031 (15)
C13	0.0389 (17)	0.060 (2)	0.064 (2)	−0.0015 (16)	0.0178 (16)	−0.0038 (18)
C14	0.0379 (16)	0.0429 (18)	0.063 (2)	0.0027 (14)	0.0107 (15)	−0.0012 (15)
C15	0.062 (2)	0.070 (2)	0.073 (2)	−0.0234 (19)	0.0262 (19)	−0.007 (2)

Geometric parameters (Å, º) top

S1—O3	1.427 (2)	C7—C8	1.478 (4)
S1—O4	1.431 (2)	C7—H7A	0.9700
S1—N1	1.626 (2)	C7—H7B	0.9700
S1—C9	1.763 (3)	C8—H8A	0.9700
O1—C7	1.409 (4)	C8—H8B	0.9700
O1—C1	1.424 (4)	C9—C10	1.384 (4)
O2—C4	1.218 (4)	C9—C14	1.388 (4)
N1—C8	1.469 (4)	C10—C11	1.372 (4)
N1—C1	1.503 (3)	C10—H10	0.9300
C1—C2	1.487 (4)	C11—C12	1.381 (4)
C1—C6	1.496 (4)	C11—H11	0.9300
C2—C3	1.313 (4)	C12—C13	1.373 (4)
C2—H2	0.9300	C12—C15	1.508 (4)
C3—C4	1.455 (4)	C13—C14	1.374 (4)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.463 (5)	C14—H14	0.9300
C5—C6	1.314 (4)	C15—H15A	0.9600
C5—H5	0.9300	C15—H15B	0.9600
C6—H6	0.9300	C15—H15C	0.9600

O3—S1—O4	120.05 (13)	O1—C7—H7B	110.5
O3—S1—N1	106.48 (12)	C8—C7—H7B	110.5
O4—S1—N1	105.19 (12)	H7A—C7—H7B	108.7
O3—S1—C9	109.16 (13)	N1—C8—C7	102.7 (2)
O4—S1—C9	106.92 (13)	N1—C8—H8A	111.2
N1—S1—C9	108.57 (13)	C7—C8—H8A	111.2
C7—O1—C1	110.7 (2)	N1—C8—H8B	111.2
C8—N1—C1	109.7 (2)	C7—C8—H8B	111.2
C8—N1—S1	119.94 (18)	H8A—C8—H8B	109.1
C1—N1—S1	125.44 (18)	C10—C9—C14	119.7 (3)
O1—C1—C2	106.0 (2)	C10—C9—S1	120.7 (2)
O1—C1—C6	110.4 (2)	C14—C9—S1	119.5 (2)
C2—C1—C6	113.4 (2)	C11—C10—C9	119.3 (3)
O1—C1—N1	102.3 (2)	C11—C10—H10	120.4
C2—C1—N1	114.7 (2)	C9—C10—H10	120.4
C6—C1—N1	109.3 (2)	C10—C11—C12	121.9 (3)
C3—C2—C1	123.0 (3)	C10—C11—H11	119.0
C3—C2—H2	118.5	C12—C11—H11	119.0
C1—C2—H2	118.5	C13—C12—C11	117.8 (3)
C2—C3—C4	122.4 (3)	C13—C12—C15	121.9 (3)
C2—C3—H3	118.8	C11—C12—C15	120.2 (3)
C4—C3—H3	118.8	C12—C13—C14	121.9 (3)
O2—C4—C3	121.4 (4)	C12—C13—H13	119.1
O2—C4—C5	122.2 (3)	C14—C13—H13	119.1
C3—C4—C5	116.3 (3)	C13—C14—C9	119.4 (3)
C6—C5—C4	121.8 (3)	C13—C14—H14	120.3
C6—C5—H5	119.1	C9—C14—H14	120.3
C4—C5—H5	119.1	C12—C15—H15A	109.5
C5—C6—C1	123.0 (3)	C12—C15—H15B	109.5
C5—C6—H6	118.5	H15A—C15—H15B	109.5
C1—C6—H6	118.5	C12—C15—H15C	109.5
O1—C7—C8	105.9 (3)	H15A—C15—H15C	109.5
O1—C7—H7A	110.5	H15B—C15—H15C	109.5
C8—C7—H7A	110.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.93	2.48	3.211 (4)	134
C15—H15B···O2ⁱⁱ	0.96	2.57	3.520 (5)	171

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅NO₄S
M_r	305.34
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	11.882 (3), 14.973 (6), 8.369 (5)
β (°)	107.00 (3)
V (Å³)	1423.9 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.24
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	2996, 2625, 1526
R_int	0.008
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.119, 1.02
No. of reflections	2625
No. of parameters	192
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.27

Computer programs: DIFRAC (Gabe & White, 1993), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.93	2.48	3.211 (4)	134
C15—H15B···O2ⁱⁱ	0.96	2.57	3.520 (5)	171

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x, y, z+1.

Acknowledgements

This work was financially supported by the Industry–Academia–Research Combination Project of the Ministry of Education of China and Guangdong Province (No.2007B090400016)

References

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