Crystal structure of methyl 3-(3-fluoro-phen-yl)-1-methyl-1,3a,4,9b-tetra-hydro-3H-thio-chromeno[4,3-c]isoxazole-3a-carboxyl-ate.

In the title compound, C19H18FNO3S, the five-membered oxazolidine ring adopts an envelope conformation with the methine C atom of the fused bond as the flap. Its mean plane is oriented at a dihedral angle of 50.38 (1)° with respect to the fluoro-phenyl ring. The six-membered thio-pyran ring has a half-chair conformation and its mean plane is almost coplanar with the fused benzene ring, making a dihedral angle of 4.94 (10)°. The two aromatic rings are inclined to one another by 85.96 (11)°, and the mean planes of the oxazolidine and thio-pyran rings are inclined to one another by 57.64 (12)°. In the crystal, mol-ecules are linked by C-H⋯π inter-actions, forming a three-dimensional structure.

Related literature

For background on thio-containing heterocyclic rings and for related structures, see for example: Khan et al. (2008a ▸,b ▸).

Experimental

Crystal data

C19H18FNO3S

M = 359.40

Monoclinic,

a = 10.7729 (8) Å

b = 12.6361 (8) Å

c = 12.625 (1) Å

β = 92.992 (3)°

V = 1716.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.22 mm−1

T = 293 K

0.30 × 0.30 × 0.25 mm

Data collection

Bruker Kappa APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▸) T min = 0.938, T max = 0.948

18645 measured reflections

3024 independent reflections

2456 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.123

S = 0.99

3024 reflections

243 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.52 e Å−3

Δρmin = −0.24 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: APEX2 and SAINT (Bruker, 2004 ▸); data reduction: SAINT and XPREP (Bruker, 2004 ▸); 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: SHELXL97 and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015013651/su5169sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015013651/su5169Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015013651/su5169Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015013651/su5169fig1.tif

The mol­ecular structure of the title compound, with the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

CCDC reference: 1413525

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

C19H18FNO3S	F(000) = 752
Mr = 359.40	Dx = 1.391 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3024 reflections
a = 10.7729 (8) Å	θ = 2.3–25.0°
b = 12.6361 (8) Å	µ = 0.22 mm−1
c = 12.625 (1) Å	T = 293 K
β = 92.992 (3)°	Block, colourless
V = 1716.3 (2) Å3	0.30 × 0.30 × 0.25 mm
Z = 4

Bruker Kappa APEXII CCD diffractometer	3024 independent reflections
Radiation source: fine-focus sealed tube	2456 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ω and φ scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −12→12
Tmin = 0.938, Tmax = 0.948	k = −15→15
18645 measured reflections	l = −15→13

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)] = 0.041	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.123	w = 1/[σ2(Fo2) + (0.0547P)2 + 1.7913P] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max < 0.001
3024 reflections	Δρmax = 0.52 e Å−3
243 parameters	Δρmin = −0.24 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: 0.0079 (14)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
S1	0.38912 (6)	−0.09256 (5)	0.73827 (6)	0.0484 (2)
O3	0.14448 (16)	0.08198 (17)	0.72833 (14)	0.0580 (6)
O1	0.44199 (15)	0.19965 (17)	0.95772 (13)	0.0560 (5)
F1	−0.09742 (14)	0.14114 (17)	1.01633 (15)	0.0759 (6)
C7	0.54244 (19)	0.08164 (16)	0.70941 (16)	0.0285 (5)
C2	0.5127 (2)	−0.02335 (18)	0.68520 (17)	0.0344 (5)
C10	0.34366 (18)	0.10865 (17)	0.81229 (16)	0.0288 (5)
C9	0.3219 (2)	0.18273 (19)	0.90866 (17)	0.0342 (5)
C8	0.47396 (19)	0.14639 (17)	0.78729 (16)	0.0285 (5)
C17	0.25020 (19)	0.13405 (18)	0.72143 (16)	0.0331 (5)
C11	0.2322 (2)	0.14500 (17)	0.98805 (16)	0.0314 (5)
C1	0.3454 (2)	−0.00741 (18)	0.84444 (18)	0.0344 (5)
C16	0.1063 (2)	0.16036 (18)	0.96619 (18)	0.0370 (5)
H16	0.0780	0.1928	0.9034	0.044*
C14	0.0609 (3)	0.0799 (2)	1.1315 (2)	0.0494 (7)
H14	0.0030	0.0583	1.1791	0.059*
C6	0.6370 (2)	0.12968 (19)	0.65535 (18)	0.0359 (5)
H6	0.6571	0.1999	0.6700	0.043*
C12	0.2719 (2)	0.0969 (2)	1.08214 (19)	0.0435 (6)
H12	0.3562	0.0861	1.0977	0.052*
C4	0.6718 (2)	−0.0280 (2)	0.55821 (19)	0.0455 (6)
H4	0.7149	−0.0649	0.5081	0.055*
C5	0.7016 (2)	0.0757 (2)	0.58066 (19)	0.0426 (6)
H5	0.7647	0.1091	0.5459	0.051*
C3	0.5789 (2)	−0.0770 (2)	0.60926 (19)	0.0442 (6)
H3	0.5594	−0.1472	0.5933	0.053*
C15	0.0242 (2)	0.1273 (2)	1.0381 (2)	0.0443 (6)
C13	0.1858 (3)	0.0649 (2)	1.1532 (2)	0.0525 (7)
H13	0.2130	0.0328	1.2165	0.063*
C19	0.6429 (2)	0.2148 (2)	0.9055 (2)	0.0502 (7)
H19A	0.6781	0.2105	0.9768	0.075*
H19B	0.6183	0.2864	0.8902	0.075*
H19C	0.7036	0.1929	0.8570	0.075*
C18	0.0474 (3)	0.1068 (3)	0.6484 (3)	0.0771 (11)
H18A	−0.0251	0.0652	0.6606	0.116*
H18B	0.0759	0.0911	0.5794	0.116*
H18C	0.0270	0.1806	0.6524	0.116*
N1	0.53515 (17)	0.14612 (15)	0.89425 (14)	0.0357 (5)
O2	0.26780 (16)	0.19605 (16)	0.65350 (14)	0.0534 (5)
H1B	0.264 (2)	−0.0329 (19)	0.8609 (18)	0.038 (6)*
H1A	0.403 (2)	−0.0170 (19)	0.902 (2)	0.039 (6)*
H8	0.469 (2)	0.2167 (19)	0.7624 (17)	0.030 (6)*
H9	0.294 (2)	0.249 (2)	0.8768 (19)	0.037 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0561 (4)	0.0372 (4)	0.0531 (4)	−0.0166 (3)	0.0129 (3)	−0.0116 (3)
O3	0.0359 (9)	0.0920 (15)	0.0446 (10)	−0.0205 (9)	−0.0129 (8)	0.0205 (10)
O1	0.0364 (9)	0.0935 (15)	0.0382 (10)	−0.0165 (9)	0.0046 (7)	−0.0286 (10)
F1	0.0360 (9)	0.1030 (15)	0.0885 (13)	0.0088 (9)	0.0031 (8)	−0.0189 (11)
C7	0.0278 (10)	0.0316 (11)	0.0257 (10)	0.0021 (8)	−0.0016 (8)	0.0039 (8)
C2	0.0364 (12)	0.0367 (12)	0.0299 (11)	0.0004 (10)	−0.0013 (9)	−0.0009 (9)
C10	0.0277 (11)	0.0351 (11)	0.0234 (10)	−0.0018 (9)	0.0002 (8)	0.0002 (9)
C9	0.0367 (12)	0.0381 (13)	0.0276 (11)	0.0003 (10)	−0.0007 (9)	−0.0011 (10)
C8	0.0299 (11)	0.0270 (11)	0.0283 (11)	−0.0015 (8)	−0.0019 (9)	0.0013 (9)
C17	0.0294 (11)	0.0443 (13)	0.0255 (11)	0.0005 (9)	0.0013 (9)	−0.0022 (10)
C11	0.0343 (11)	0.0336 (11)	0.0263 (11)	0.0049 (9)	0.0027 (9)	−0.0032 (9)
C1	0.0346 (12)	0.0361 (12)	0.0325 (12)	−0.0065 (10)	0.0030 (10)	0.0011 (10)
C16	0.0376 (12)	0.0389 (13)	0.0342 (12)	0.0084 (10)	−0.0017 (10)	−0.0039 (10)
C14	0.0585 (17)	0.0457 (15)	0.0462 (15)	−0.0087 (12)	0.0220 (13)	−0.0039 (12)
C6	0.0331 (11)	0.0378 (12)	0.0368 (12)	0.0033 (9)	0.0017 (9)	0.0067 (10)
C12	0.0433 (14)	0.0528 (15)	0.0343 (13)	0.0136 (11)	0.0031 (10)	0.0062 (11)
C4	0.0452 (14)	0.0588 (16)	0.0329 (13)	0.0151 (12)	0.0067 (11)	−0.0033 (11)
C5	0.0375 (13)	0.0552 (15)	0.0358 (13)	0.0082 (11)	0.0084 (10)	0.0105 (11)
C3	0.0521 (15)	0.0423 (14)	0.0382 (13)	0.0043 (11)	0.0015 (11)	−0.0095 (11)
C15	0.0309 (12)	0.0481 (14)	0.0545 (16)	0.0000 (10)	0.0071 (11)	−0.0169 (12)
C13	0.0671 (18)	0.0536 (16)	0.0377 (14)	0.0109 (14)	0.0107 (13)	0.0133 (12)
C19	0.0375 (13)	0.0671 (18)	0.0456 (15)	−0.0126 (12)	−0.0028 (11)	−0.0141 (13)
C18	0.0421 (16)	0.127 (3)	0.0600 (19)	−0.0163 (18)	−0.0212 (14)	0.0236 (19)
N1	0.0334 (10)	0.0433 (11)	0.0299 (10)	−0.0046 (8)	−0.0039 (8)	−0.0046 (8)
O2	0.0442 (10)	0.0722 (13)	0.0432 (10)	−0.0029 (9)	−0.0048 (8)	0.0240 (9)

S1—C2	1.755 (2)	C1—H1A	0.94 (3)
S1—C1	1.801 (2)	C16—C15	1.366 (3)
O3—C17	1.322 (3)	C16—H16	0.9300
O3—C18	1.449 (3)	C14—C15	1.363 (4)
O1—C9	1.422 (3)	C14—C13	1.372 (4)
O1—N1	1.480 (2)	C14—H14	0.9300
F1—C15	1.336 (3)	C6—C5	1.381 (3)
C7—C6	1.395 (3)	C6—H6	0.9300
C7—C2	1.395 (3)	C12—C13	1.383 (4)
C7—C8	1.502 (3)	C12—H12	0.9300
C2—C3	1.400 (3)	C4—C3	1.367 (4)
C10—C17	1.520 (3)	C4—C5	1.375 (4)
C10—C1	1.522 (3)	C4—H4	0.9300
C10—C8	1.531 (3)	C5—H5	0.9300
C10—C9	1.562 (3)	C3—H3	0.9300
C9—C11	1.505 (3)	C13—H13	0.9300
C9—H9	0.97 (3)	C19—N1	1.450 (3)
C8—N1	1.471 (3)	C19—H19A	0.9600
C8—H8	0.94 (2)	C19—H19B	0.9600
C17—O2	1.184 (3)	C19—H19C	0.9600
C11—C12	1.382 (3)	C18—H18A	0.9600
C11—C16	1.384 (3)	C18—H18B	0.9600
C1—H1B	0.97 (2)	C18—H18C	0.9600
C2—S1—C1	102.68 (11)	C11—C16—H16	120.4
C17—O3—C18	116.1 (2)	C15—C14—C13	118.1 (2)
C9—O1—N1	108.84 (15)	C15—C14—H14	121.0
C6—C7—C2	118.2 (2)	C13—C14—H14	121.0
C6—C7—C8	118.65 (19)	C5—C6—C7	121.7 (2)
C2—C7—C8	123.12 (19)	C5—C6—H6	119.1
C7—C2—C3	119.4 (2)	C7—C6—H6	119.1
C7—C2—S1	124.10 (17)	C11—C12—C13	119.9 (2)
C3—C2—S1	116.34 (18)	C11—C12—H12	120.1
C17—C10—C1	113.77 (18)	C13—C12—H12	120.1
C17—C10—C8	110.91 (17)	C3—C4—C5	120.3 (2)
C1—C10—C8	110.89 (18)	C3—C4—H4	119.9
C17—C10—C9	109.91 (17)	C5—C4—H4	119.9
C1—C10—C9	111.71 (17)	C4—C5—C6	119.4 (2)
C8—C10—C9	98.67 (16)	C4—C5—H5	120.3
O1—C9—C11	111.01 (18)	C6—C5—H5	120.3
O1—C9—C10	105.01 (17)	C4—C3—C2	121.0 (2)
C11—C9—C10	117.17 (19)	C4—C3—H3	119.5
O1—C9—H9	108.1 (14)	C2—C3—H3	119.5
C11—C9—H9	110.6 (14)	F1—C15—C14	118.2 (2)
C10—C9—H9	104.4 (14)	F1—C15—C16	119.1 (2)
N1—C8—C7	112.81 (17)	C14—C15—C16	122.7 (2)
N1—C8—C10	100.47 (16)	C14—C13—C12	120.9 (2)
C7—C8—C10	116.89 (17)	C14—C13—H13	119.5
N1—C8—H8	108.8 (13)	C12—C13—H13	119.5
C7—C8—H8	108.5 (13)	N1—C19—H19A	109.5
C10—C8—H8	109.0 (13)	N1—C19—H19B	109.5
O2—C17—O3	123.2 (2)	H19A—C19—H19B	109.5
O2—C17—C10	124.1 (2)	N1—C19—H19C	109.5
O3—C17—C10	112.58 (19)	H19A—C19—H19C	109.5
C12—C11—C16	119.3 (2)	H19B—C19—H19C	109.5
C12—C11—C9	122.1 (2)	O3—C18—H18A	109.5
C16—C11—C9	118.6 (2)	O3—C18—H18B	109.5
C10—C1—S1	112.17 (15)	H18A—C18—H18B	109.5
C10—C1—H1B	112.2 (14)	O3—C18—H18C	109.5
S1—C1—H1B	103.7 (14)	H18A—C18—H18C	109.5
C10—C1—H1A	109.2 (15)	H18B—C18—H18C	109.5
S1—C1—H1A	108.2 (15)	C19—N1—C8	113.99 (19)
H1B—C1—H1A	111 (2)	C19—N1—O1	103.60 (17)
C15—C16—C11	119.1 (2)	C8—N1—O1	102.23 (15)
C15—C16—H16	120.4
C6—C7—C2—C3	0.8 (3)	O1—C9—C11—C12	−22.1 (3)
C8—C7—C2—C3	178.1 (2)	C10—C9—C11—C12	98.5 (3)
C6—C7—C2—S1	−175.09 (16)	O1—C9—C11—C16	157.1 (2)
C8—C7—C2—S1	2.2 (3)	C10—C9—C11—C16	−82.3 (3)
C1—S1—C2—C7	−12.6 (2)	C17—C10—C1—S1	61.9 (2)
C1—S1—C2—C3	171.40 (18)	C8—C10—C1—S1	−63.9 (2)
N1—O1—C9—C11	130.75 (19)	C9—C10—C1—S1	−172.93 (15)
N1—O1—C9—C10	3.2 (2)	C2—S1—C1—C10	42.50 (19)
C17—C10—C9—O1	−146.89 (19)	C12—C11—C16—C15	−0.2 (3)
C1—C10—C9—O1	85.8 (2)	C9—C11—C16—C15	−179.4 (2)
C8—C10—C9—O1	−30.8 (2)	C2—C7—C6—C5	−0.9 (3)
C17—C10—C9—C11	89.4 (2)	C8—C7—C6—C5	−178.3 (2)
C1—C10—C9—C11	−37.9 (3)	C16—C11—C12—C13	−0.1 (4)
C8—C10—C9—C11	−154.55 (19)	C9—C11—C12—C13	179.1 (2)
C6—C7—C8—N1	−87.2 (2)	C3—C4—C5—C6	0.1 (4)
C2—C7—C8—N1	95.5 (2)	C7—C6—C5—C4	0.4 (3)
C6—C7—C8—C10	157.06 (19)	C5—C4—C3—C2	−0.1 (4)
C2—C7—C8—C10	−20.2 (3)	C7—C2—C3—C4	−0.3 (4)
C17—C10—C8—N1	162.34 (17)	S1—C2—C3—C4	175.88 (19)
C1—C10—C8—N1	−70.2 (2)	C13—C14—C15—F1	179.4 (2)
C9—C10—C8—N1	47.06 (19)	C13—C14—C15—C16	−0.2 (4)
C17—C10—C8—C7	−75.3 (2)	C11—C16—C15—F1	−179.3 (2)
C1—C10—C8—C7	52.1 (2)	C11—C16—C15—C14	0.3 (4)
C9—C10—C8—C7	169.45 (17)	C15—C14—C13—C12	−0.1 (4)
C18—O3—C17—O2	−1.6 (4)	C11—C12—C13—C14	0.2 (4)
C18—O3—C17—C10	176.2 (2)	C7—C8—N1—C19	77.3 (2)
C1—C10—C17—O2	−142.9 (2)	C10—C8—N1—C19	−157.50 (19)
C8—C10—C17—O2	−17.1 (3)	C7—C8—N1—O1	−171.62 (16)
C9—C10—C17—O2	90.9 (3)	C10—C8—N1—O1	−46.41 (19)
C1—C10—C17—O3	39.4 (3)	C9—O1—N1—C19	146.0 (2)
C8—C10—C17—O3	165.18 (19)	C9—O1—N1—C8	27.3 (2)
C9—C10—C17—O3	−86.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···Cg4i	0.93	2.75	3.479 (3)	136
C13—H13···Cg3ii	0.93	2.74	3.599 (3)	153

Table 1

Hydrogen-bond geometry (, )

Cg3 and Cg4 are the centroids of rings C2C7 and C11C16, respectively.

DHA	DH	HA	D A	DHA
C6H6Cg4i	0.93	2.75	3.479(3)	136
C13H13Cg3ii	0.93	2.74	3.599(3)	153

Symmetry codes: (i) ; (ii) .