5,8-Dimeth-oxy-3,9-dimethyl-3a,4,9,9a-tetra-hydro-4,9-ep-oxy-naphtho-[2,3-d]isoxazole.

The title compound, C15H17NO4, is the exo isomer with a syn arrangement of the O atom in the isoxazole ring to the methyl group of the bicyclic alkene. The dihedral angle between the isoxazole ring and the benzene ring is 7.42 (9)°. In the crystal, weak C-H⋯O hydrogen bonds link mol-ecules, forming a three-dimensional network. The isoxazole O atom is an acceptor for both weak hydrogen bonds.

Related literature

For 1,3-dipolar cyclo­addition reactions of symmetrical and unsymmetrical bicyclic alkenes, see: Yip et al. (2001 ▶); Mayo et al. (2001 ▶). For a related structure, see: Lough et al. (2014 ▶).

Experimental

Crystal data

C15H17NO4

M = 275.29

Monoclinic,

a = 9.0608 (12) Å

b = 14.3998 (17) Å

c = 10.1631 (12) Å

β = 104.835 (3)°

V = 1281.8 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 147 K

0.32 × 0.16 × 0.14 mm

Data collection

Bruker Kappa APEX DUO CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2012 ▶) T min = 0.660, T max = 0.746

11844 measured reflections

2937 independent reflections

2271 reflections with I > 2σ(I)

R int = 0.041

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.097

S = 1.05

2937 reflections

185 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2012 ▶); cell refinement: SAINT (Bruker, 2012 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814007752/is5351sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007752/is5351Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814007752/is5351Isup3.cml

CCDC reference: 995953

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H17NO4	F(000) = 584
Mr = 275.29	Dx = 1.427 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 9.0608 (12) Å	Cell parameters from 2761 reflections
b = 14.3998 (17) Å	θ = 2.5–27.5°
c = 10.1631 (12) Å	µ = 0.10 mm−1
β = 104.835 (3)°	T = 147 K
V = 1281.8 (3) Å3	Needle, colourless
Z = 4	0.32 × 0.16 × 0.14 mm

Bruker Kappa APEX DUO CCD diffractometer	2271 reflections with I > 2σ(I)
Radiation source: sealed tube with Bruker Triumph monochromator	Rint = 0.041
φ and ω scans	θmax = 27.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −11→11
Tmin = 0.660, Tmax = 0.746	k = −18→17
11844 measured reflections	l = −11→13
2937 independent reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.039	H-atom parameters constrained
wR(F2) = 0.097	w = 1/[σ2(Fo2) + (0.0459P)2 + 0.2574P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max < 0.001
2937 reflections	Δρmax = 0.28 e Å−3
185 parameters	Δρmin = −0.22 e Å−3

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.

	x	y	z	Uiso*/Ueq
O1	0.50314 (11)	0.25637 (7)	0.36251 (9)	0.0158 (2)
O2	0.59142 (11)	0.27152 (7)	0.66027 (10)	0.0199 (2)
O3	0.27204 (11)	0.49102 (7)	0.15675 (10)	0.0217 (2)
O4	0.89378 (11)	0.43196 (7)	0.37701 (10)	0.0205 (2)
N1	0.44029 (14)	0.24274 (9)	0.65909 (12)	0.0200 (3)
C1	0.39743 (15)	0.33293 (10)	0.34640 (13)	0.0147 (3)
H1A	0.2909	0.3190	0.2927	0.018*
C2	0.63942 (15)	0.30606 (9)	0.43544 (13)	0.0147 (3)
C3	0.77661 (17)	0.24375 (10)	0.46760 (15)	0.0201 (3)
H3A	0.8081	0.2309	0.3841	0.030*
H3B	0.7510	0.1853	0.5060	0.030*
H3C	0.8603	0.2743	0.5338	0.030*
C4	0.58557 (15)	0.34340 (10)	0.55933 (13)	0.0148 (3)
H4A	0.6418	0.4007	0.5992	0.018*
C5	0.41454 (15)	0.36162 (10)	0.49764 (13)	0.0141 (3)
H5A	0.3833	0.4272	0.5086	0.017*
C6	0.34470 (16)	0.29242 (10)	0.57416 (14)	0.0162 (3)
C7	0.17703 (16)	0.27995 (11)	0.55319 (15)	0.0203 (3)
H7A	0.1580	0.2282	0.6092	0.030*
H7B	0.1300	0.2665	0.4570	0.030*
H7C	0.1328	0.3369	0.5795	0.030*
C8	0.47998 (16)	0.40647 (10)	0.28645 (13)	0.0145 (3)
C9	0.42749 (16)	0.48105 (10)	0.20091 (14)	0.0163 (3)
C10	0.53678 (17)	0.53792 (10)	0.16776 (14)	0.0178 (3)
H10A	0.5052	0.5885	0.1070	0.021*
C11	0.69228 (17)	0.52157 (10)	0.22265 (14)	0.0182 (3)
H11A	0.7647	0.5609	0.1976	0.022*
C12	0.74383 (16)	0.44869 (10)	0.31354 (13)	0.0153 (3)
C13	0.63422 (15)	0.39029 (9)	0.34279 (13)	0.0144 (3)
C14	0.21634 (18)	0.57380 (10)	0.08270 (15)	0.0220 (3)
H14A	0.1046	0.5751	0.0622	0.033*
H14B	0.2481	0.5748	−0.0025	0.033*
H14C	0.2581	0.6282	0.1376	0.033*
C15	1.00530 (17)	0.47219 (11)	0.31725 (16)	0.0227 (3)
H15A	1.1070	0.4499	0.3652	0.034*
H15B	1.0019	0.5400	0.3244	0.034*
H15C	0.9835	0.4543	0.2212	0.034*

	U11	U22	U33	U12	U13	U23
O1	0.0159 (5)	0.0130 (5)	0.0180 (5)	−0.0010 (4)	0.0035 (4)	−0.0021 (4)
O2	0.0152 (5)	0.0255 (6)	0.0188 (5)	0.0024 (4)	0.0042 (4)	0.0073 (4)
O3	0.0169 (5)	0.0212 (6)	0.0255 (5)	0.0018 (4)	0.0029 (4)	0.0078 (4)
O4	0.0145 (5)	0.0259 (6)	0.0217 (5)	−0.0024 (4)	0.0057 (4)	0.0032 (4)
N1	0.0188 (6)	0.0216 (7)	0.0211 (6)	−0.0009 (5)	0.0077 (5)	0.0020 (5)
C1	0.0149 (7)	0.0139 (7)	0.0149 (6)	−0.0003 (5)	0.0031 (5)	−0.0003 (5)
C2	0.0140 (7)	0.0143 (7)	0.0161 (6)	−0.0012 (5)	0.0044 (5)	−0.0019 (5)
C3	0.0192 (8)	0.0183 (7)	0.0240 (7)	0.0035 (6)	0.0077 (6)	0.0010 (6)
C4	0.0161 (7)	0.0142 (7)	0.0144 (6)	0.0005 (5)	0.0043 (5)	0.0010 (5)
C5	0.0140 (7)	0.0133 (7)	0.0153 (6)	−0.0003 (5)	0.0044 (5)	−0.0005 (5)
C6	0.0197 (7)	0.0140 (7)	0.0159 (6)	−0.0006 (6)	0.0065 (5)	−0.0013 (5)
C7	0.0180 (8)	0.0220 (8)	0.0228 (7)	−0.0016 (6)	0.0088 (6)	0.0004 (6)
C8	0.0171 (7)	0.0139 (7)	0.0135 (6)	−0.0013 (5)	0.0055 (5)	−0.0025 (5)
C9	0.0171 (7)	0.0177 (7)	0.0140 (6)	0.0011 (6)	0.0035 (5)	−0.0008 (5)
C10	0.0241 (8)	0.0148 (7)	0.0149 (6)	0.0005 (6)	0.0058 (6)	0.0009 (5)
C11	0.0219 (8)	0.0173 (7)	0.0176 (7)	−0.0046 (6)	0.0092 (6)	−0.0027 (6)
C12	0.0151 (7)	0.0175 (7)	0.0144 (6)	−0.0007 (6)	0.0060 (5)	−0.0031 (5)
C13	0.0178 (7)	0.0133 (7)	0.0127 (6)	0.0007 (5)	0.0048 (5)	−0.0026 (5)
C14	0.0232 (8)	0.0204 (8)	0.0209 (7)	0.0060 (6)	0.0029 (6)	0.0048 (6)
C15	0.0165 (7)	0.0279 (8)	0.0256 (8)	−0.0038 (6)	0.0091 (6)	0.0005 (6)

O1—C1	1.4420 (16)	C5—C6	1.5001 (19)
O1—C2	1.4550 (16)	C5—H5A	1.0000
O2—N1	1.4278 (16)	C6—C7	1.490 (2)
O2—C4	1.4487 (16)	C7—H7A	0.9800
O3—C9	1.3719 (17)	C7—H7B	0.9800
O3—C14	1.4309 (17)	C7—H7C	0.9800
O4—C12	1.3680 (17)	C8—C9	1.387 (2)
O4—C15	1.4282 (17)	C8—C13	1.3877 (19)
N1—C6	1.2744 (19)	C9—C10	1.391 (2)
C1—C8	1.5118 (18)	C10—C11	1.396 (2)
C1—C5	1.5605 (18)	C10—H10A	0.9500
C1—H1A	1.0000	C11—C12	1.397 (2)
C2—C3	1.4997 (19)	C11—H11A	0.9500
C2—C13	1.5288 (19)	C12—C13	1.3903 (19)
C2—C4	1.5580 (18)	C14—H14A	0.9800
C3—H3A	0.9800	C14—H14B	0.9800
C3—H3B	0.9800	C14—H14C	0.9800
C3—H3C	0.9800	C15—H15A	0.9800
C4—C5	1.5381 (18)	C15—H15B	0.9800
C4—H4A	1.0000	C15—H15C	0.9800
C1—O1—C2	97.72 (10)	C7—C6—C5	123.78 (12)
N1—O2—C4	109.89 (10)	C6—C7—H7A	109.5
C9—O3—C14	116.97 (11)	C6—C7—H7B	109.5
C12—O4—C15	116.97 (11)	H7A—C7—H7B	109.5
C6—N1—O2	109.07 (11)	C6—C7—H7C	109.5
O1—C1—C8	101.45 (10)	H7A—C7—H7C	109.5
O1—C1—C5	101.24 (10)	H7B—C7—H7C	109.5
C8—C1—C5	106.07 (11)	C9—C8—C13	122.42 (13)
O1—C1—H1A	115.4	C9—C8—C1	132.02 (13)
C8—C1—H1A	115.4	C13—C8—C1	105.43 (12)
C5—C1—H1A	115.4	O3—C9—C8	116.40 (12)
O1—C2—C3	111.39 (11)	O3—C9—C10	126.44 (13)
O1—C2—C13	100.84 (10)	C8—C9—C10	117.16 (13)
C3—C2—C13	120.13 (12)	C9—C10—C11	120.80 (13)
O1—C2—C4	100.42 (10)	C9—C10—H10A	119.6
C3—C2—C4	116.36 (11)	C11—C10—H10A	119.6
C13—C2—C4	104.91 (11)	C10—C11—C12	121.55 (13)
C2—C3—H3A	109.5	C10—C11—H11A	119.2
C2—C3—H3B	109.5	C12—C11—H11A	119.2
H3A—C3—H3B	109.5	O4—C12—C13	118.06 (12)
C2—C3—H3C	109.5	O4—C12—C11	124.58 (13)
H3A—C3—H3C	109.5	C13—C12—C11	117.35 (13)
H3B—C3—H3C	109.5	C8—C13—C12	120.62 (13)
O2—C4—C5	105.12 (11)	C8—C13—C2	104.85 (12)
O2—C4—C2	111.31 (11)	C12—C13—C2	134.47 (13)
C5—C4—C2	102.75 (10)	O3—C14—H14A	109.5
O2—C4—H4A	112.3	O3—C14—H14B	109.5
C5—C4—H4A	112.3	H14A—C14—H14B	109.5
C2—C4—H4A	112.3	O3—C14—H14C	109.5
C6—C5—C4	100.96 (11)	H14A—C14—H14C	109.5
C6—C5—C1	112.71 (11)	H14B—C14—H14C	109.5
C4—C5—C1	101.07 (11)	O4—C15—H15A	109.5
C6—C5—H5A	113.6	O4—C15—H15B	109.5
C4—C5—H5A	113.6	H15A—C15—H15B	109.5
C1—C5—H5A	113.6	O4—C15—H15C	109.5
N1—C6—C7	121.36 (13)	H15A—C15—H15C	109.5
N1—C6—C5	114.85 (13)	H15B—C15—H15C	109.5
C4—O2—N1—C6	−3.33 (15)	O1—C1—C8—C13	−32.41 (13)
C2—O1—C1—C8	51.19 (11)	C5—C1—C8—C13	72.97 (13)
C2—O1—C1—C5	−57.97 (11)	C14—O3—C9—C8	172.37 (12)
C1—O1—C2—C3	−179.30 (11)	C14—O3—C9—C10	−8.0 (2)
C1—O1—C2—C13	−50.69 (11)	C13—C8—C9—O3	−177.44 (12)
C1—O1—C2—C4	56.86 (11)	C1—C8—C9—O3	−2.2 (2)
N1—O2—C4—C5	2.76 (13)	C13—C8—C9—C10	2.9 (2)
N1—O2—C4—C2	−107.78 (12)	C1—C8—C9—C10	178.11 (13)
O1—C2—C4—O2	78.42 (12)	O3—C9—C10—C11	178.30 (13)
C3—C2—C4—O2	−41.92 (16)	C8—C9—C10—C11	−2.1 (2)
C13—C2—C4—O2	−177.29 (11)	C9—C10—C11—C12	−0.8 (2)
O1—C2—C4—C5	−33.63 (12)	C15—O4—C12—C13	161.27 (12)
C3—C2—C4—C5	−153.97 (12)	C15—O4—C12—C11	−19.88 (19)
C13—C2—C4—C5	70.66 (12)	C10—C11—C12—O4	−176.08 (12)
O2—C4—C5—C6	−1.30 (13)	C10—C11—C12—C13	2.8 (2)
C2—C4—C5—C6	115.27 (11)	C9—C8—C13—C12	−0.9 (2)
O2—C4—C5—C1	−117.31 (11)	C1—C8—C13—C12	−177.18 (12)
C2—C4—C5—C1	−0.74 (13)	C9—C8—C13—C2	176.63 (12)
O1—C1—C5—C6	−71.58 (13)	C1—C8—C13—C2	0.31 (13)
C8—C1—C5—C6	−177.12 (11)	O4—C12—C13—C8	176.95 (12)
O1—C1—C5—C4	35.38 (12)	C11—C12—C13—C8	−1.98 (19)
C8—C1—C5—C4	−70.15 (13)	O4—C12—C13—C2	0.3 (2)
O2—N1—C6—C7	−178.46 (12)	C11—C12—C13—C2	−178.59 (14)
O2—N1—C6—C5	2.48 (16)	O1—C2—C13—C8	31.49 (13)
C4—C5—C6—N1	−0.72 (15)	C3—C2—C13—C8	154.22 (12)
C1—C5—C6—N1	106.32 (14)	C4—C2—C13—C8	−72.49 (13)
C4—C5—C6—C7	−179.75 (13)	O1—C2—C13—C12	−151.53 (15)
C1—C5—C6—C7	−72.71 (17)	C3—C2—C13—C12	−28.8 (2)
O1—C1—C8—C9	151.77 (14)	C4—C2—C13—C12	104.49 (17)
C5—C1—C8—C9	−102.85 (16)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···O2i	1.00	2.35	3.2928 (17)	156
C14—H14C···O2ii	0.98	2.59	3.5340 (19)	161

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯O2i	1.00	2.35	3.2928 (17)	156
C14—H14C⋯O2ii	0.98	2.59	3.5340 (19)	161

Symmetry codes: (i) ; (ii) .