Methyl 6-eth-oxy-3-phenyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazole-3a-car-boxylate.

In the title compound, C(20)H(19)NO(5), the dihedral angle between the mean plane of the pyran ring (which has a half-chair conformation) and the benzene ring of the chromeno ring system is 7.21 (7)°. The dihedral angle between the mean plane of the chromeno ring system and the isoxazole ring is 21.78 (6)°, while the isoxazole ring forms a dihedral angle of 72.60 (8)° with the attached phenyl ring. In the crystal, mol-ecules are linked via pairs of C-H⋯O hydrogen bonds, forming inversion dimers with an R(2) (2)(10) ring motif. These dimers are linked via C-H⋯N hydrogen bonds, forming chains along [001].

Related literature

For the biological activity of chromenopyrroles, see: Caine (1993 ▶), and of benzopyran and isoxazolidine derivatives, see: Lin et al. (1996 ▶); Hu et al. (2004 ▶). For uses of isoxazole derivatives, see: Baraldi et al. (1987 ▶); Eddington et al. (2002 ▶). For related structures, see: Gangadharan et al. (2011 ▶); Swaminathan et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C20H19NO5

M = 353.36

Monoclinic,

a = 12.9342 (6) Å

b = 7.5591 (2) Å

c = 18.7138 (8) Å

β = 105.440 (2)°

V = 1763.63 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 298 K

0.25 × 0.20 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.976, T max = 0.990

13064 measured reflections

4245 independent reflections

3253 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.125

S = 1.03

4245 reflections

237 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.22 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812051720/su2543sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051720/su2543Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812051720/su2543Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C20H19NO5	F(000) = 744
Mr = 353.36	Dx = 1.331 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4245 reflections
a = 12.9342 (6) Å	θ = 2.3–28.4°
b = 7.5591 (2) Å	µ = 0.10 mm−1
c = 18.7138 (8) Å	T = 298 K
β = 105.440 (2)°	Monoclinic, colourless
V = 1763.63 (12) Å3	0.25 × 0.20 × 0.10 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	4245 independent reflections
Radiation source: fine-focus sealed tube	3253 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ω and φ scans	θmax = 28.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −13→17
Tmin = 0.976, Tmax = 0.990	k = −9→6
13064 measured reflections	l = −24→25

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.125	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0578P)2 + 0.5069P] where P = (Fo2 + 2Fc2)/3
4245 reflections	(Δ/σ)max = 0.002
237 parameters	Δρmax = 0.35 e Å−3
0 restraints	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.

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.

	x	y	z	Uiso*/Ueq
C1	0.34469 (12)	0.7365 (2)	0.84801 (8)	0.0408 (3)
H1	0.3280	0.7202	0.7969	0.049*
C2	0.44803 (13)	0.7149 (2)	0.89052 (9)	0.0497 (4)
H2	0.5013	0.6828	0.8680	0.060*
C3	0.47417 (12)	0.7405 (2)	0.96675 (9)	0.0467 (4)
H3	0.5449	0.7270	0.9945	0.056*
C4	0.39633 (11)	0.78572 (19)	1.00188 (8)	0.0365 (3)
C5	0.28961 (10)	0.80410 (17)	0.95890 (7)	0.0299 (3)
C6	0.10418 (10)	0.81790 (19)	0.95728 (7)	0.0331 (3)
H6A	0.0582	0.8683	0.9853	0.040*
H6B	0.0895	0.6921	0.9516	0.040*
C7	0.08137 (10)	0.90610 (17)	0.88085 (7)	0.0290 (3)
C8	−0.02921 (11)	0.87517 (19)	0.82484 (7)	0.0341 (3)
H8	−0.0613	0.9908	0.8088	0.041*
C9	0.15362 (10)	0.81458 (16)	0.84177 (7)	0.0291 (3)
C10	0.26470 (11)	0.78305 (17)	0.88215 (7)	0.0308 (3)
C11	0.51955 (13)	0.7982 (3)	1.12204 (9)	0.0539 (4)
H11A	0.5661	0.8839	1.1076	0.065*
H11B	0.5473	0.6806	1.1177	0.065*
C12	0.51486 (19)	0.8317 (4)	1.20010 (11)	0.0856 (7)
H12A	0.4827	0.9451	1.2029	0.128*
H12B	0.5862	0.8302	1.2326	0.128*
H12C	0.4727	0.7413	1.2149	0.128*
C13	0.10049 (11)	1.10449 (19)	0.89314 (7)	0.0338 (3)
C14	0.20504 (14)	1.3490 (2)	0.87993 (12)	0.0608 (5)
H14A	0.1388	1.4113	0.8606	0.091*
H14B	0.2550	1.3815	0.8524	0.091*
H14C	0.2342	1.3792	0.9312	0.091*
C15	−0.10961 (10)	0.76672 (18)	0.85102 (7)	0.0331 (3)
C16	−0.18456 (12)	0.8534 (2)	0.87901 (9)	0.0437 (4)
H16	−0.1854	0.9764	0.8802	0.052*
C17	−0.25822 (14)	0.7588 (3)	0.90523 (10)	0.0565 (4)
H17	−0.3079	0.8180	0.9244	0.068*
C18	−0.25809 (14)	0.5775 (3)	0.90297 (10)	0.0565 (4)
H18	−0.3081	0.5139	0.9202	0.068*
C19	−0.18410 (14)	0.4897 (2)	0.87527 (10)	0.0550 (4)
H19	−0.1840	0.3667	0.8740	0.066*
C20	−0.10973 (13)	0.5836 (2)	0.84930 (9)	0.0452 (4)
H20	−0.0598	0.5236	0.8307	0.054*
N1	0.10693 (10)	0.75033 (17)	0.77828 (6)	0.0376 (3)
O1	0.21512 (7)	0.84634 (13)	0.99612 (5)	0.0351 (2)
O2	−0.00309 (9)	0.79042 (16)	0.76155 (5)	0.0456 (3)
O3	0.41260 (8)	0.81419 (16)	1.07581 (6)	0.0473 (3)
O4	0.04263 (10)	1.19594 (15)	0.91752 (7)	0.0560 (3)
O5	0.18555 (8)	1.16068 (13)	0.87330 (6)	0.0442 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0428 (8)	0.0401 (8)	0.0440 (7)	0.0001 (6)	0.0196 (6)	−0.0057 (6)
C2	0.0400 (8)	0.0554 (10)	0.0602 (10)	0.0050 (7)	0.0244 (7)	−0.0042 (8)
C3	0.0295 (7)	0.0533 (10)	0.0561 (9)	0.0037 (6)	0.0093 (6)	0.0042 (7)
C4	0.0342 (7)	0.0344 (8)	0.0398 (7)	−0.0005 (5)	0.0081 (6)	0.0035 (6)
C5	0.0305 (6)	0.0247 (6)	0.0359 (6)	0.0000 (5)	0.0110 (5)	0.0013 (5)
C6	0.0304 (6)	0.0377 (7)	0.0326 (6)	0.0001 (5)	0.0106 (5)	0.0037 (5)
C7	0.0292 (6)	0.0276 (7)	0.0306 (6)	−0.0009 (5)	0.0087 (5)	0.0015 (5)
C8	0.0335 (7)	0.0340 (7)	0.0331 (6)	−0.0002 (5)	0.0057 (5)	0.0031 (5)
C9	0.0353 (7)	0.0228 (6)	0.0312 (6)	−0.0029 (5)	0.0125 (5)	0.0008 (5)
C10	0.0343 (7)	0.0228 (6)	0.0368 (6)	−0.0021 (5)	0.0121 (5)	−0.0019 (5)
C11	0.0421 (9)	0.0584 (11)	0.0511 (9)	−0.0016 (7)	−0.0051 (7)	0.0071 (8)
C12	0.0797 (15)	0.118 (2)	0.0469 (10)	−0.0033 (14)	−0.0051 (10)	0.0057 (12)
C13	0.0363 (7)	0.0312 (7)	0.0323 (6)	0.0019 (5)	0.0062 (5)	−0.0006 (5)
C14	0.0486 (10)	0.0267 (8)	0.0982 (14)	−0.0065 (7)	0.0038 (9)	0.0070 (8)
C15	0.0287 (6)	0.0345 (7)	0.0333 (6)	−0.0011 (5)	0.0033 (5)	0.0003 (5)
C16	0.0376 (8)	0.0377 (8)	0.0557 (9)	−0.0017 (6)	0.0124 (7)	−0.0071 (7)
C17	0.0406 (9)	0.0671 (12)	0.0677 (11)	−0.0065 (8)	0.0247 (8)	−0.0119 (9)
C18	0.0463 (9)	0.0633 (12)	0.0616 (10)	−0.0185 (8)	0.0177 (8)	0.0046 (9)
C19	0.0575 (10)	0.0367 (9)	0.0691 (11)	−0.0102 (7)	0.0139 (9)	0.0050 (8)
C20	0.0449 (8)	0.0344 (8)	0.0581 (9)	0.0015 (6)	0.0168 (7)	−0.0015 (7)
N1	0.0399 (7)	0.0405 (7)	0.0332 (5)	−0.0065 (5)	0.0112 (5)	−0.0032 (5)
O1	0.0313 (5)	0.0444 (6)	0.0297 (4)	0.0024 (4)	0.0082 (4)	−0.0010 (4)
O2	0.0386 (5)	0.0654 (7)	0.0316 (5)	−0.0081 (5)	0.0073 (4)	−0.0052 (5)
O3	0.0377 (6)	0.0623 (7)	0.0381 (5)	0.0015 (5)	0.0036 (4)	0.0023 (5)
O4	0.0714 (8)	0.0398 (6)	0.0659 (7)	0.0076 (6)	0.0343 (6)	−0.0079 (5)
O5	0.0364 (5)	0.0245 (5)	0.0706 (7)	−0.0013 (4)	0.0123 (5)	0.0041 (4)

C1—C2	1.371 (2)	C11—C12	1.500 (3)
C1—C10	1.3980 (19)	C11—H11A	0.9700
C1—H1	0.9300	C11—H11B	0.9700
C2—C3	1.389 (2)	C12—H12A	0.9600
C2—H2	0.9300	C12—H12B	0.9600
C3—C4	1.384 (2)	C12—H12C	0.9600
C3—H3	0.9300	C13—O4	1.1949 (17)
C4—O3	1.3600 (17)	C13—O5	1.3215 (17)
C4—C5	1.4073 (18)	C14—O5	1.4451 (19)
C5—O1	1.3685 (16)	C14—H14A	0.9600
C5—C10	1.3948 (18)	C14—H14B	0.9600
C6—O1	1.4416 (16)	C14—H14C	0.9600
C6—C7	1.5337 (17)	C15—C16	1.383 (2)
C6—H6A	0.9700	C15—C20	1.385 (2)
C6—H6B	0.9700	C16—C17	1.382 (2)
C7—C9	1.5003 (18)	C16—H16	0.9300
C7—C13	1.5273 (19)	C17—C18	1.371 (3)
C7—C8	1.5494 (17)	C17—H17	0.9300
C8—O2	1.4630 (17)	C18—C19	1.375 (3)
C8—C15	1.5049 (19)	C18—H18	0.9300
C8—H8	0.9800	C19—C20	1.384 (2)
C9—N1	1.2767 (17)	C19—H19	0.9300
C9—C10	1.4540 (18)	C20—H20	0.9300
C11—O3	1.4281 (18)	N1—O2	1.4063 (16)
C2—C1—C10	119.37 (14)	O3—C11—H11B	110.3
C2—C1—H1	120.3	C12—C11—H11B	110.3
C10—C1—H1	120.3	H11A—C11—H11B	108.6
C1—C2—C3	120.84 (14)	C11—C12—H12A	109.5
C1—C2—H2	119.6	C11—C12—H12B	109.5
C3—C2—H2	119.6	H12A—C12—H12B	109.5
C4—C3—C2	120.88 (14)	C11—C12—H12C	109.5
C4—C3—H3	119.6	H12A—C12—H12C	109.5
C2—C3—H3	119.6	H12B—C12—H12C	109.5
O3—C4—C3	125.96 (13)	O4—C13—O5	125.05 (14)
O3—C4—C5	115.37 (12)	O4—C13—C7	122.19 (13)
C3—C4—C5	118.67 (13)	O5—C13—C7	112.76 (11)
O1—C5—C10	123.36 (12)	O5—C14—H14A	109.5
O1—C5—C4	116.64 (11)	O5—C14—H14B	109.5
C10—C5—C4	119.98 (12)	H14A—C14—H14B	109.5
O1—C6—C7	108.90 (10)	O5—C14—H14C	109.5
O1—C6—H6A	109.9	H14A—C14—H14C	109.5
C7—C6—H6A	109.9	H14B—C14—H14C	109.5
O1—C6—H6B	109.9	C16—C15—C20	119.08 (14)
C7—C6—H6B	109.9	C16—C15—C8	118.66 (13)
H6A—C6—H6B	108.3	C20—C15—C8	122.25 (13)
C9—C7—C13	115.42 (11)	C17—C16—C15	120.52 (15)
C9—C7—C6	105.31 (10)	C17—C16—H16	119.7
C13—C7—C6	107.65 (11)	C15—C16—H16	119.7
C9—C7—C8	100.56 (10)	C18—C17—C16	120.00 (16)
C13—C7—C8	109.47 (10)	C18—C17—H17	120.0
C6—C7—C8	118.62 (11)	C16—C17—H17	120.0
O2—C8—C15	110.70 (11)	C17—C18—C19	120.09 (16)
O2—C8—C7	104.08 (10)	C17—C18—H18	120.0
C15—C8—C7	117.10 (10)	C19—C18—H18	120.0
O2—C8—H8	108.2	C18—C19—C20	120.22 (16)
C15—C8—H8	108.2	C18—C19—H19	119.9
C7—C8—H8	108.2	C20—C19—H19	119.9
N1—C9—C10	125.34 (12)	C19—C20—C15	120.09 (15)
N1—C9—C7	115.30 (12)	C19—C20—H20	120.0
C10—C9—C7	118.67 (11)	C15—C20—H20	120.0
C5—C10—C1	120.21 (13)	C9—N1—O2	108.97 (11)
C5—C10—C9	116.22 (11)	C5—O1—C6	116.72 (10)
C1—C10—C9	123.56 (12)	N1—O2—C8	110.62 (9)
O3—C11—C12	106.98 (16)	C4—O3—C11	117.75 (12)
O3—C11—H11A	110.3	C13—O5—C14	115.58 (13)
C12—C11—H11A	110.3
C10—C1—C2—C3	−0.6 (2)	C7—C9—C10—C1	−165.09 (13)
C1—C2—C3—C4	1.0 (3)	C9—C7—C13—O4	173.18 (13)
C2—C3—C4—O3	−179.88 (15)	C6—C7—C13—O4	−69.56 (16)
C2—C3—C4—C5	0.5 (2)	C8—C7—C13—O4	60.65 (17)
O3—C4—C5—O1	−0.61 (18)	C9—C7—C13—O5	−6.14 (16)
C3—C4—C5—O1	179.04 (13)	C6—C7—C13—O5	111.12 (12)
O3—C4—C5—C10	178.04 (12)	C8—C7—C13—O5	−118.67 (12)
C3—C4—C5—C10	−2.3 (2)	O2—C8—C15—C16	−146.00 (12)
O1—C6—C7—C9	61.42 (13)	C7—C8—C15—C16	94.96 (15)
O1—C6—C7—C13	−62.23 (13)	O2—C8—C15—C20	35.24 (17)
O1—C6—C7—C8	172.88 (11)	C7—C8—C15—C20	−83.80 (17)
C9—C7—C8—O2	−5.46 (12)	C20—C15—C16—C17	0.3 (2)
C13—C7—C8—O2	116.48 (12)	C8—C15—C16—C17	−178.49 (14)
C6—C7—C8—O2	−119.52 (12)	C15—C16—C17—C18	−0.6 (3)
C9—C7—C8—C15	117.06 (12)	C16—C17—C18—C19	0.6 (3)
C13—C7—C8—C15	−121.00 (13)	C17—C18—C19—C20	−0.2 (3)
C6—C7—C8—C15	3.00 (18)	C18—C19—C20—C15	−0.1 (2)
C13—C7—C9—N1	−115.20 (13)	C16—C15—C20—C19	0.0 (2)
C6—C7—C9—N1	126.23 (12)	C8—C15—C20—C19	178.80 (13)
C8—C7—C9—N1	2.45 (15)	C10—C9—N1—O2	172.22 (12)
C13—C7—C9—C10	73.79 (14)	C7—C9—N1—O2	1.90 (16)
C6—C7—C9—C10	−44.78 (15)	C10—C5—O1—C6	18.01 (17)
C8—C7—C9—C10	−168.57 (11)	C4—C5—O1—C6	−163.39 (12)
O1—C5—C10—C1	−178.77 (13)	C7—C6—O1—C5	−50.96 (15)
C4—C5—C10—C1	2.7 (2)	C9—N1—O2—C8	−5.87 (15)
O1—C5—C10—C9	2.05 (18)	C15—C8—O2—N1	−119.54 (12)
C4—C5—C10—C9	−176.51 (12)	C7—C8—O2—N1	7.10 (14)
C2—C1—C10—C5	−1.2 (2)	C3—C4—O3—C11	0.7 (2)
C2—C1—C10—C9	177.92 (14)	C5—C4—O3—C11	−179.68 (13)
N1—C9—C10—C5	−155.97 (13)	C12—C11—O3—C4	−178.77 (16)
C7—C9—C10—C5	14.06 (17)	O4—C13—O5—C14	−2.3 (2)
N1—C9—C10—C1	24.9 (2)	C7—C13—O5—C14	176.95 (12)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O4i	0.97	2.55	3.3875 (19)	145
C8—H8···N1ii	0.98	2.52	3.4269 (19)	154

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O4i	0.97	2.55	3.3875 (19)	145
C8—H8⋯N1ii	0.98	2.52	3.4269 (19)	154

Symmetry codes: (i) ; (ii) .