(1′S,4′S)-5-(2,5-Dimethyl­phen­yl)-4′-meth­oxy-6-oxa-3-aza­spiro­[bicyclo­[3.1.0]hexane-2,1′-cyclo­hexa­n]-4-one

He, X.-R.; Xu, B.-R.; Cheng, J.-L.; Zhao, J.-H.

doi:10.1107/S1600536813005138

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 3| March 2013| Page o453

doi:10.1107/S1600536813005138

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(1′S,4′S)-5-(2,5-Dimethylphenyl)-4′-methoxy-6-oxa-3-azaspiro[bicyclo[3.1.0]hexane-2,1′-cyclohexan]-4-one

Xing-Rui He,^a Bing-Rong Xu,^a Jing-Li Cheng ^b and Jin-Hao Zhao ^b ^*

^aCollege of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310032, People's Republic of China, and ^bInstitute of Pesticide and Environmental Toxicology, Zhejiang University, Hangzhou 310029, People's Republic of China
^*Correspondence e-mail: jinhaozhao@zju.edu.cn

(Received 30 January 2013; accepted 22 February 2013; online 28 February 2013)

In the title compound, C₁₈H₂₃NO₃, the cyclohexane ring has a chair conformation. The oxirane plane (OCC) makes a dihedral angle of 76.15 (13)° with that of the pyrrolidine ring to which it is fused. The mean plane of the cyclohexane ring and the benzene ring are almost normal to the pyrrolidine ring, with dihedral angles of 88.47 (8) and 77.85 (8)°, respectively. In the crystal, molecules are linked via pairs of N—H⋯O hydrogen bonds, forming inversion dimers. These dimers are linked via pairs of C—H⋯O hydrogen bonds, forming chains along the a-axis direction.

Related literature

For the pesticide spirotetramat, the central unit of the title compound, see: Fischer & Weiss (2008 ); Maus (2008 ). For structures of spirotetramat derivatives, see: Fischer et al. (2010 ). For the metabolic transformation of spirotetramat, see: Bruck et al. (2009 )

Experimental

Crystal data

C₁₈H₂₃NO₃
M_r = 301.37
Monoclinic, P 2₁ /n
a = 9.1932 (4) Å
b = 9.8139 (4) Å
c = 17.6979 (7) Å
β = 91.198 (1)°
V = 1596.38 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.53 × 0.38 × 0.36 mm

Data collection

Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.946, T_max = 0.970
15333 measured reflections
3629 independent reflections
2407 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.122
S = 1.00
3629 reflections
203 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.86	2.25	3.0760 (17)	160
C9—H9A⋯O2ⁱⁱ	0.97	2.56	3.413 (2)	147
Symmetry codes: (i) -x+2, -y+2, -z+1; (ii) -x+1, -y+2, -z+1.

Data collection: PROCESS-AUTO (Rigaku, 2006 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku,2007 ); 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, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813005138/su2559sup1.cif

Supporting information file. DOI: 10.1107/S1600536813005138/su2559Isup2.cdx

Structure factors: contains datablock I. DOI: 10.1107/S1600536813005138/su2559Isup4.hkl

Supporting information file. DOI: 10.1107/S1600536813005138/su2559Isup4.cml

checkCIF report

Comment top

Spirotetramat is a new systemic insecticide which belongs chemically to the class of spirocyclic tetramic acid derivatives and be developed by Bayer CropScience AG (Fischer et al., 2008; Maus, 2008). Recently, it has been found that when spirotetramat was introduced into plants or animals, it was hydrolysed to its enol form and as a weak acid this metabolite can move acropetally and basipetally with small log P (Bruck et al., 2009). That is, the excellent bioactivities of spirotetramat maybe caused by this metabolite, which stimulated our interest in the synthesis of some novel analogues of this metabolite. We have designed a new simple route to synthesized the title compound and report herein on its crystal structure.

The molecular structure of the title molecule is shown in Fig. 1. The cyclohexane ring adopts a chair conformation; atoms C5, C6, C8 and C9 lie in a plane with atoms C4 and C7 deviating by 0.676 (4) and -0.664 (0) Å, respectively. The oxirane plane (O2/C2/C3) makes a dihedral angle of 76.15 (13)° with the pyrrolidine ring (N1/C1-C4) to which it is fused. The mean plane of the cyclohexane ring (C4-C9) and the benzene ring (C11-C16) are almost normal to the pyrrolidine ring with dihedral angles of 88.47 (8) and 77.85 (8)°, respectively.

In the crystal, molecules are linked via a pair of N-H···O hydrogen bonds forming inversion dimers (Table 1). These dimers are linked via a pair of C-H···O hydrogen bonds forming chains along the a axis direction (Table 1).

Related literature top

For the pesticide spirotetramat, the central unit of the title compound, see: Fischer & Weiss (2008); Maus (2008). For structures of spirotetramat derivatives, see: Fischer et al. (2010). For the metabolic transformation of spirotetramat, see: Bruck et al. (2009)

Experimental top

The synthesis of the title compound is described in Fig. 2. A solution of sulfuryl chloride (0.80 g, 6mmoL) in anhydrous chloroform (10 ml) was added drop wise to a solution of compound 2 (0.90 g, 3mmoL) in anhydrous chloroform (20 ml) at 0 degree and stirred for 10 min. The reaction mixture was allowed to warm to room temperature and stirred at room temperature for 1 h. The reaction mixture was then washed with water (15 ml), saturated sodium bicarbonate (15 ml) and saturated sodium chloride solution and dried over anhydrous Na₂SO₄. The solvent was evaporated, and the residual solid was crystallized from ethanol to afford 0.95 g compound 3 as a white solid: yield 94.8%. To a solution of compound 3 (100 mg, 0.30 mmoL) in 2-propanol (10 ml) was added NaBH₄ (13.6 mg, 0.36 mmoL) at 0 degree. Then the reaction mixture was allowed to room temperature and stirred for 2 h. After removal of the solvent in vacuo, 1 N HCl (10 ml) was added to the residue and the whole mixture was extracted with CH₂Cl₂ (8 ml τimes 3). The organic layer was washed successively with 3% Na₂CO₃ (8 ml) and water (8 ml) and dried over Na₂SO₄. Evaporation of the solvent gave a residue, which was purified by flash chromatography on silica gel using a mixture of petroleum ether (boiling point range 60–90 degree) and ethyl acetate (1:1 by volume) as the eluent to afford 32 mg compound 4 as a white solid [yield 35.6%; ESI-MS: 336 (M+H)+ (100%)]. Spectroscopic data for the title compound is available in the archived CIF.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 2006); cell refinement: PROCESS-AUTO (Rigaku, 2006); data reduction: CrystalStructure (Rigaku,2007); 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, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 40% probability level.
	Fig. 2. Reaction scheme.

(1'S,4'S)-5-(2,5-Dimethylphenyl)-4'-methoxy-6-oxa-3-azaspiro[bicyclo[3.1.0]hexane-2,1'-cyclohexan]-4-one top

Crystal data top

C₁₈H₂₃NO₃	F(000) = 648
M_r = 301.37	D_x = 1.254 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9900 reflections
a = 9.1932 (4) Å	θ = 3.0–27.4°
b = 9.8139 (4) Å	µ = 0.09 mm⁻¹
c = 17.6979 (7) Å	T = 296 K
β = 91.198 (1)°	Block, colourless
V = 1596.38 (11) Å³	0.53 × 0.38 × 0.36 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	3629 independent reflections
Radiation source: rotating anode	2407 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
Detector resolution: 10.00 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −11→11
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
T_min = 0.946, T_max = 0.970	l = −22→22
15333 measured reflections

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)] = 0.045	H-atom parameters constrained
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0501P)² + 0.4587P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
3629 reflections	Δρ_max = 0.26 e Å⁻³
203 parameters	Δρ_min = −0.23 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.049 (3)

Crystal data top

C₁₈H₂₃NO₃	V = 1596.38 (11) Å³
M_r = 301.37	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.1932 (4) Å	µ = 0.09 mm⁻¹
b = 9.8139 (4) Å	T = 296 K
c = 17.6979 (7) Å	0.53 × 0.38 × 0.36 mm
β = 91.198 (1)°

Data collection top

Rigaku R-AXIS RAPID/ZJUG diffractometer	3629 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	2407 reflections with I > 2σ(I)
T_min = 0.946, T_max = 0.970	R_int = 0.040
15333 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.00	Δρ_max = 0.26 e Å⁻³
3629 reflections	Δρ_min = −0.23 e Å⁻³
203 parameters

Special details top

Experimental. Spectroscopic data for the title compound: ¹H NMR (500 MHz, CDCl₃): 7.28 (s, 1H, Ph—H), 7.21 (s, 1H, Ph—H), 7.11 (s, 1H, Ph—H), 5.57 (s, 1H, –NH–), 3.80 (d, J = 2.65 Hz, 1H, –CH—O—C–), 3.40–3.39 (m, 1H, –CH—O–), 3.37 (s, 3H, –OCH3), 2.35 (s, 3H, Ph—Me), 2.33 (s, 3H, Ph—Me), 2.04–2.00 (m, 1H, Cyclohexane-H1), 1.94–1.82 (m, 4H, Cyclohexane-H4), 1.75–1.62 (m, 3H, Cyclohexane-H3); ¹³C NMR (125 MHz, CDCl₃): 171.4, 135.4, 133.7, 130.1, 129.8, 128.8, 128.5, 75.3, 64.9, 62.8, 57.0, 55.7, 31.7, 28.2, 27.1, 26.4, 20.8, 19.3.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

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
O1	0.60742 (14)	0.85489 (13)	0.31242 (7)	0.0625 (4)
O2	0.42952 (12)	0.79911 (13)	0.47491 (7)	0.0565 (4)
O3	1.09024 (13)	0.91600 (12)	0.60804 (7)	0.0563 (4)
N1	0.71200 (14)	0.84251 (13)	0.43139 (7)	0.0448 (4)
C1	0.60987 (17)	0.81496 (16)	0.37776 (9)	0.0436 (5)
C2	0.49630 (16)	0.72456 (16)	0.41369 (9)	0.0423 (5)
C3	0.54729 (17)	0.70679 (17)	0.49249 (9)	0.0468 (5)
C4	0.69248 (17)	0.77653 (16)	0.50507 (8)	0.0418 (5)
C5	0.81229 (19)	0.67175 (16)	0.52153 (10)	0.0494 (5)
C6	0.96044 (18)	0.73875 (18)	0.53488 (10)	0.0520 (6)
C7	0.95550 (18)	0.84352 (17)	0.59826 (9)	0.0482 (5)
C8	0.83812 (18)	0.94787 (17)	0.58211 (9)	0.0491 (5)
C9	0.68976 (18)	0.88081 (18)	0.56940 (9)	0.0499 (5)
C10	1.2063 (2)	0.8335 (2)	0.63718 (12)	0.0688 (7)
C11	0.39938 (16)	0.63409 (15)	0.36728 (9)	0.0406 (5)
C12	0.45709 (17)	0.52733 (16)	0.32516 (9)	0.0444 (5)
C13	0.3604 (2)	0.44859 (18)	0.28230 (9)	0.0524 (6)
C14	0.21297 (19)	0.47469 (18)	0.27957 (9)	0.0515 (5)
C15	0.15504 (17)	0.58089 (18)	0.32083 (9)	0.0479 (5)
C16	0.25058 (17)	0.65911 (16)	0.36478 (9)	0.0455 (5)
C17	0.61810 (19)	0.4977 (2)	0.32605 (11)	0.0622 (7)
C18	−0.00622 (19)	0.6083 (2)	0.31909 (12)	0.0702 (8)
H1	0.78430	0.89560	0.42300	0.0540*
H3	0.52710	0.62120	0.51880	0.0560*
H5A	0.78730	0.61940	0.56590	0.0590*
H5B	0.81810	0.60930	0.47920	0.0590*
H6A	1.03190	0.66930	0.54780	0.0620*
H6B	0.99050	0.78300	0.48870	0.0620*
H7	0.93360	0.79660	0.64560	0.0580*
H8A	0.86290	0.99970	0.53750	0.0590*
H8B	0.83310	1.01070	0.62430	0.0590*
H9A	0.61800	0.95040	0.55750	0.0600*
H9B	0.66110	0.83580	0.61550	0.0600*
H10A	1.17290	0.78150	0.67940	0.1030*
H10B	1.28570	0.89070	0.65330	0.1030*
H10C	1.23840	0.77260	0.59840	0.1030*
H13	0.39640	0.37600	0.25460	0.0630*
H14	0.15190	0.42050	0.24970	0.0620*
H16	0.21370	0.73030	0.39330	0.0550*
H17A	0.63690	0.42140	0.29380	0.0930*
H17B	0.65020	0.47680	0.37670	0.0930*
H17C	0.66960	0.57610	0.30820	0.0930*
H18A	−0.04210	0.60580	0.26780	0.1050*
H18B	−0.02450	0.69660	0.34030	0.1050*
H18C	−0.05480	0.54010	0.34810	0.1050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0669 (8)	0.0706 (8)	0.0493 (7)	−0.0175 (6)	−0.0146 (6)	0.0190 (6)
O2	0.0454 (7)	0.0587 (7)	0.0656 (8)	0.0023 (5)	0.0056 (6)	−0.0174 (6)
O3	0.0560 (7)	0.0530 (7)	0.0590 (7)	−0.0094 (6)	−0.0168 (6)	0.0124 (6)
N1	0.0435 (7)	0.0462 (7)	0.0445 (7)	−0.0098 (6)	−0.0046 (6)	0.0091 (6)
C1	0.0428 (8)	0.0416 (8)	0.0460 (8)	−0.0011 (7)	−0.0061 (7)	0.0053 (7)
C2	0.0392 (8)	0.0400 (8)	0.0477 (8)	0.0023 (6)	0.0018 (7)	−0.0008 (7)
C3	0.0500 (9)	0.0447 (8)	0.0457 (9)	−0.0055 (7)	0.0038 (7)	0.0000 (7)
C4	0.0460 (9)	0.0418 (8)	0.0376 (8)	−0.0044 (7)	−0.0015 (6)	0.0031 (6)
C5	0.0621 (11)	0.0392 (8)	0.0467 (9)	0.0000 (7)	−0.0062 (8)	0.0012 (7)
C6	0.0525 (10)	0.0466 (9)	0.0565 (10)	0.0056 (8)	−0.0084 (8)	−0.0006 (8)
C7	0.0546 (10)	0.0473 (9)	0.0422 (8)	−0.0091 (8)	−0.0077 (7)	0.0068 (7)
C8	0.0597 (10)	0.0428 (8)	0.0447 (8)	−0.0027 (8)	−0.0033 (7)	−0.0049 (7)
C9	0.0516 (10)	0.0507 (9)	0.0473 (9)	−0.0008 (8)	0.0013 (7)	−0.0048 (7)
C10	0.0639 (12)	0.0686 (12)	0.0728 (13)	−0.0008 (10)	−0.0226 (10)	0.0132 (10)
C11	0.0376 (8)	0.0394 (8)	0.0447 (8)	−0.0024 (6)	0.0008 (6)	0.0038 (7)
C12	0.0436 (9)	0.0453 (9)	0.0443 (8)	0.0033 (7)	0.0020 (7)	0.0015 (7)
C13	0.0612 (11)	0.0516 (9)	0.0444 (9)	0.0018 (8)	0.0022 (8)	−0.0059 (8)
C14	0.0548 (10)	0.0572 (10)	0.0421 (8)	−0.0102 (8)	−0.0050 (7)	0.0001 (8)
C15	0.0407 (8)	0.0556 (10)	0.0474 (9)	−0.0055 (7)	−0.0013 (7)	0.0081 (8)
C16	0.0419 (9)	0.0428 (8)	0.0519 (9)	0.0001 (7)	0.0028 (7)	0.0002 (7)
C17	0.0528 (11)	0.0624 (11)	0.0715 (12)	0.0123 (9)	0.0046 (9)	−0.0057 (10)
C18	0.0423 (10)	0.0888 (15)	0.0793 (14)	−0.0067 (10)	−0.0036 (9)	−0.0021 (12)

Geometric parameters (Å, º) top

O1—C1	1.221 (2)	C15—C16	1.392 (2)
O2—C2	1.454 (2)	C15—C18	1.506 (2)
O2—C3	1.441 (2)	C3—H3	0.9800
O3—C7	1.436 (2)	C5—H5A	0.9700
O3—C10	1.427 (2)	C5—H5B	0.9700
N1—C1	1.348 (2)	C6—H6A	0.9700
N1—C4	1.4703 (19)	C6—H6B	0.9700
N1—H1	0.8600	C7—H7	0.9800
C1—C2	1.520 (2)	C8—H8A	0.9700
C2—C3	1.472 (2)	C8—H8B	0.9700
C2—C11	1.492 (2)	C9—H9A	0.9700
C3—C4	1.512 (2)	C9—H9B	0.9700
C4—C9	1.532 (2)	C10—H10A	0.9600
C4—C5	1.530 (2)	C10—H10B	0.9600
C5—C6	1.526 (2)	C10—H10C	0.9600
C6—C7	1.523 (2)	C13—H13	0.9300
C7—C8	1.511 (2)	C14—H14	0.9300
C8—C9	1.527 (2)	C16—H16	0.9300
C11—C12	1.397 (2)	C17—H17A	0.9600
C11—C16	1.390 (2)	C17—H17B	0.9600
C12—C17	1.508 (2)	C17—H17C	0.9600
C12—C13	1.391 (2)	C18—H18A	0.9600
C13—C14	1.379 (3)	C18—H18B	0.9600
C14—C15	1.385 (2)	C18—H18C	0.9600

C2—O2—C3	61.14 (10)	C4—C5—H5B	109.00
C7—O3—C10	113.52 (13)	C6—C5—H5A	109.00
C1—N1—C4	116.10 (13)	C6—C5—H5B	109.00
C4—N1—H1	122.00	H5A—C5—H5B	108.00
C1—N1—H1	122.00	C5—C6—H6A	109.00
O1—C1—C2	125.77 (15)	C5—C6—H6B	109.00
N1—C1—C2	107.27 (13)	C7—C6—H6A	109.00
O1—C1—N1	126.96 (15)	C7—C6—H6B	109.00
O2—C2—C11	116.94 (12)	H6A—C6—H6B	108.00
O2—C2—C1	108.82 (12)	O3—C7—H7	109.00
O2—C2—C3	58.99 (10)	C6—C7—H7	109.00
C3—C2—C11	128.73 (14)	C8—C7—H7	109.00
C1—C2—C11	121.65 (14)	C7—C8—H8A	109.00
C1—C2—C3	104.93 (13)	C7—C8—H8B	109.00
O2—C3—C4	113.84 (13)	C9—C8—H8A	109.00
C2—C3—C4	110.39 (13)	C9—C8—H8B	109.00
O2—C3—C2	59.87 (10)	H8A—C8—H8B	108.00
N1—C4—C9	111.67 (13)	C4—C9—H9A	109.00
N1—C4—C3	101.10 (12)	C4—C9—H9B	109.00
N1—C4—C5	111.35 (13)	C8—C9—H9A	109.00
C5—C4—C9	109.29 (13)	C8—C9—H9B	109.00
C3—C4—C5	110.70 (13)	H9A—C9—H9B	108.00
C3—C4—C9	112.57 (13)	O3—C10—H10A	109.00
C4—C5—C6	112.11 (13)	O3—C10—H10B	110.00
C5—C6—C7	111.38 (14)	O3—C10—H10C	109.00
O3—C7—C8	107.34 (13)	H10A—C10—H10B	109.00
O3—C7—C6	112.60 (13)	H10A—C10—H10C	109.00
C6—C7—C8	110.52 (13)	H10B—C10—H10C	109.00
C7—C8—C9	111.60 (14)	C12—C13—H13	119.00
C4—C9—C8	111.66 (13)	C14—C13—H13	119.00
C2—C11—C16	119.24 (14)	C13—C14—H14	120.00
C2—C11—C12	120.73 (13)	C15—C14—H14	120.00
C12—C11—C16	120.01 (14)	C11—C16—H16	119.00
C11—C12—C17	121.51 (14)	C15—C16—H16	119.00
C11—C12—C13	117.53 (15)	C12—C17—H17A	109.00
C13—C12—C17	120.96 (15)	C12—C17—H17B	109.00
C12—C13—C14	122.16 (16)	C12—C17—H17C	109.00
C13—C14—C15	120.64 (16)	H17A—C17—H17B	109.00
C14—C15—C16	117.67 (15)	H17A—C17—H17C	109.00
C14—C15—C18	120.83 (15)	H17B—C17—H17C	110.00
C16—C15—C18	121.48 (15)	C15—C18—H18A	109.00
C11—C16—C15	121.98 (15)	C15—C18—H18B	109.00
O2—C3—H3	120.00	C15—C18—H18C	109.00
C2—C3—H3	119.00	H18A—C18—H18B	109.00
C4—C3—H3	120.00	H18A—C18—H18C	109.00
C4—C5—H5A	109.00	H18B—C18—H18C	109.00

C2—O2—C3—C4	100.60 (14)	O2—C3—C4—N1	−60.56 (15)
C3—O2—C2—C1	−96.47 (14)	O2—C3—C4—C5	−178.64 (13)
C3—O2—C2—C11	120.88 (16)	C2—C3—C4—C5	−113.55 (15)
C10—O3—C7—C8	169.18 (14)	C2—C3—C4—N1	4.53 (16)
C10—O3—C7—C6	−68.97 (18)	C3—C4—C5—C6	−179.75 (13)
C4—N1—C1—C2	2.84 (18)	N1—C4—C5—C6	68.63 (17)
C4—N1—C1—O1	−177.41 (15)	C3—C4—C9—C8	178.88 (13)
C1—N1—C4—C5	113.01 (15)	C5—C4—C9—C8	55.45 (17)
C1—N1—C4—C9	−124.52 (15)	C9—C4—C5—C6	−55.21 (18)
C1—N1—C4—C3	−4.60 (17)	N1—C4—C9—C8	−68.20 (17)
N1—C1—C2—O2	62.13 (16)	C4—C5—C6—C7	55.95 (18)
O1—C1—C2—C11	22.9 (2)	C5—C6—C7—C8	−55.29 (18)
O1—C1—C2—O2	−117.63 (17)	C5—C6—C7—O3	−175.32 (13)
O1—C1—C2—C3	−179.43 (16)	O3—C7—C8—C9	179.04 (12)
N1—C1—C2—C11	−157.31 (14)	C6—C7—C8—C9	55.90 (17)
N1—C1—C2—C3	0.32 (17)	C7—C8—C9—C4	−56.98 (17)
O2—C2—C11—C16	22.8 (2)	C2—C11—C12—C13	−178.99 (15)
C1—C2—C11—C12	63.6 (2)	C2—C11—C12—C17	1.2 (2)
C1—C2—C3—C4	−3.17 (17)	C16—C11—C12—C13	−0.6 (2)
C3—C2—C11—C12	−88.3 (2)	C16—C11—C12—C17	179.58 (15)
C3—C2—C11—C16	93.3 (2)	C2—C11—C16—C15	178.10 (15)
C1—C2—C3—O2	103.25 (13)	C12—C11—C16—C15	−0.3 (2)
C11—C2—C3—C4	152.30 (15)	C11—C12—C13—C14	1.2 (2)
O2—C2—C11—C12	−158.82 (14)	C17—C12—C13—C14	−179.01 (16)
C1—C2—C11—C16	−114.81 (17)	C12—C13—C14—C15	−0.8 (3)
O2—C2—C3—C4	−106.43 (14)	C13—C14—C15—C16	−0.1 (2)
C11—C2—C3—O2	−101.28 (17)	C13—C14—C15—C18	−178.94 (16)
O2—C3—C4—C9	58.71 (17)	C14—C15—C16—C11	0.7 (2)
C2—C3—C4—C9	123.80 (14)	C18—C15—C16—C11	179.49 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	2.25	3.0760 (17)	160
C9—H9A···O2ⁱⁱ	0.97	2.56	3.413 (2)	147

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

Experimental details

Crystal data
Chemical formula	C₁₈H₂₃NO₃
M_r	301.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	9.1932 (4), 9.8139 (4), 17.6979 (7)
β (°)	91.198 (1)
V (Å³)	1596.38 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.53 × 0.38 × 0.36

Data collection
Diffractometer	Rigaku R-AXIS RAPID/ZJUG diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.946, 0.970
No. of measured, independent and observed [I > 2σ(I)] reflections	15333, 3629, 2407
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.122, 1.00
No. of reflections	3629
No. of parameters	203
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.23

Computer programs: PROCESS-AUTO (Rigaku, 2006), CrystalStructure (Rigaku,2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	2.25	3.0760 (17)	160
C9—H9A···O2ⁱⁱ	0.97	2.56	3.413 (2)	147

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

Acknowledgements

This project was supported by grants from the National Natural Science Foundation of China (No. 31101470) and the Educational Commission of Zhejiang Province (Y201224393). The authors are grateful to Professor Jianming Gu for the crystal analysis.

References

Bruck, E., Elbert, A., Fischer, R. & Krueger, S. (2009). Crop Prot. 28, 838–844. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fischer, R., Bretschneider, T., Lehr, S., Arnold, C., Dittgen, J., Feucht, D., Kehne, H., Malsam, O., Rosinger, C. H., Franken, E. M. & Goergens, U. (2010). US Patent No. 20100279873A1. Google Scholar
Fischer, R. & Weiss, H. C. (2008). Bayer CropSci. J. 61, 127–140. CAS Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Maus, C. (2008). Bayer CropSci. J. 61, 159–180. CAS Google Scholar
Rigaku (2006). PROCESS-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2007). CrystalStructure. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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Volume 69| Part 3| March 2013| Page o453

doi:10.1107/S1600536813005138

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(1′S,4′S)-5-(2,5-Di­methyl­phen­yl)-4′-meth­­oxy-6-oxa-3-aza­spiro­[bi­cyclo­[3.1.0]hexane-2,1′-cyclo­hexa­n]-4-one

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

(1′S,4′S)-5-(2,5-Dimethylphenyl)-4′-methoxy-6-oxa-3-azaspiro[bicyclo[3.1.0]hexane-2,1′-cyclohexan]-4-one