(3aR*,6S*,7aR*)-7a-Chloro-6-methyl-2-(4-methyl-phenyl-sulfon-yl)-2,3,3a,6,7,7a-hexa-hydro-3a,6-ep-oxy-1H-isoindole.

In the title compound, C(16)H(18)ClNO(3)S, the six-membered ring has a boat conformation. The two five-membered rings with the bridging O atom adopt envelope conformations, whereas the N-containing five-membered ring adopts a twisted conformation. In the crystal, C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

Related literature

For background to the intra­molecular Diels–Alder reaction with furan (IMDAF) as diene partner, see: Lipshutz (1986 ▶); Heiner et al. (1996 ▶); Prajapati et al. (2000 ▶); Kappe et al. (1997 ▶); Padwa et al. (1997 ▶). For our studies of the intra­molecular free radical reaction of furan with a carbon side chain, see: Demircan & Parsons (1998 ▶, 2002 ▶); Demircan et al. (2006 ▶); Karaarslan et al. (2007 ▶). For our investigation of whether the protective group on nitro­gen influences the cyclo­addition process, see: Koşar et al. (2006 ▶); Arslan et al. (2008 ▶); Temel et al. (2011 ▶); Demircan et al. (2011 ▶). For puckering analysis, see: Cremer & Pople (1975 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C16H18ClNO3S

M = 339.82

Monoclinic,

a = 10.0523 (5) Å

b = 15.5135 (6) Å

c = 11.2729 (6) Å

β = 114.800 (4)°

V = 1595.84 (13) Å3

Z = 4

Mo Kα radiation

μ = 0.38 mm−1

T = 296 K

0.78 × 0.72 × 0.60 mm

Data collection

Stoe IPDS 2 diffractometer

Absorption correction: integration (X-RED; Stoe & Cie, 2001 ▶) T min = 0.746, T max = 0.843

18547 measured reflections

3312 independent reflections

2841 reflections with I > 2σ(I)

R int = 0.026

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.101

S = 1.05

3312 reflections

201 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.37 e Å−3

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); 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: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812009658/zq2155sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812009658/zq2155Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812009658/zq2155Isup3.cml

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

C16H18ClNO3S	F(000) = 712
Mr = 339.82	Dx = 1.414 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 18547 reflections
a = 10.0523 (5) Å	θ = 2.0–28.0°
b = 15.5135 (6) Å	µ = 0.38 mm−1
c = 11.2729 (6) Å	T = 296 K
β = 114.800 (4)°	Block, colourless
V = 1595.84 (13) Å3	0.78 × 0.72 × 0.60 mm
Z = 4

Stoe IPDS 2 diffractometer	3312 independent reflections
Radiation source: fine-focus sealed tube	2841 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 6.67 pixels mm-1	θmax = 26.5°, θmin = 2.2°
rotation method scans	h = −12→12
Absorption correction: integration (X-RED; Stoe & Cie, 2001)	k = −19→19
Tmin = 0.746, Tmax = 0.843	l = −14→14
18547 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.101	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.051P)2 + 0.5399P] where P = (Fo2 + 2Fc2)/3
3312 reflections	(Δ/σ)max = 0.001
201 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.37 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
C10	0.4256 (2)	0.89806 (12)	0.5996 (2)	0.0456 (4)
H10A	0.4404	0.9512	0.5614	0.055*
H10B	0.4544	0.9065	0.6923	0.055*
C11	0.2649 (2)	0.86575 (12)	0.52936 (19)	0.0454 (4)
C12	0.2241 (2)	0.86741 (15)	0.3842 (2)	0.0569 (5)
H12	0.1614	0.9066	0.3244	0.068*
C13	0.2935 (2)	0.80336 (14)	0.35758 (19)	0.0524 (5)
H13	0.2893	0.7876	0.2765	0.063*
C16	0.1574 (3)	0.90085 (17)	0.5776 (3)	0.0670 (6)
H16A	0.0624	0.8764	0.5276	0.101*
H16B	0.1522	0.9624	0.5680	0.101*
H16C	0.1888	0.8862	0.6681	0.101*
O1	0.61916 (15)	0.52146 (9)	0.65522 (14)	0.0526 (3)
O2	0.79916 (16)	0.62551 (11)	0.80370 (14)	0.0587 (4)
O3	0.28849 (13)	0.77360 (8)	0.55435 (12)	0.0413 (3)
C1	0.77799 (19)	0.60653 (11)	0.56803 (19)	0.0411 (4)
C2	0.7250 (2)	0.55616 (12)	0.4569 (2)	0.0460 (4)
H2	0.6428	0.5217	0.4375	0.055*
C3	0.7952 (2)	0.55757 (13)	0.3748 (2)	0.0520 (5)
H3	0.7594	0.5236	0.2999	0.062*
C4	0.9179 (2)	0.60826 (14)	0.4013 (2)	0.0530 (5)
C5	0.9670 (2)	0.65924 (15)	0.5121 (3)	0.0627 (6)
H5	1.0481	0.6945	0.5308	0.075*
C6	0.8985 (2)	0.65894 (14)	0.5953 (2)	0.0562 (5)
H6	0.9331	0.6937	0.6693	0.067*
C7	0.9952 (3)	0.60749 (19)	0.3123 (3)	0.0746 (7)
H7A	1.0581	0.5580	0.3314	0.112*
H7B	1.0526	0.6590	0.3257	0.112*
H7C	0.9241	0.6050	0.2230	0.112*
C8	0.5981 (2)	0.76445 (12)	0.68794 (18)	0.0433 (4)
H8A	0.7017	0.7778	0.7207	0.052*
H8B	0.5676	0.7709	0.7585	0.052*
C9	0.50862 (19)	0.82243 (11)	0.57366 (17)	0.0388 (4)
C14	0.38083 (19)	0.76143 (11)	0.48755 (16)	0.0377 (4)
C15	0.4437 (2)	0.67277 (12)	0.5043 (2)	0.0465 (4)
H15A	0.3726	0.6299	0.5025	0.056*
H15B	0.4764	0.6595	0.4367	0.056*
Cl1	0.61872 (6)	0.85248 (4)	0.48951 (6)	0.06283 (18)
N1	0.56832 (16)	0.67646 (10)	0.63391 (15)	0.0429 (4)
S1	0.69313 (5)	0.60262 (3)	0.67681 (5)	0.04233 (14)

	U11	U22	U33	U12	U13	U23
C10	0.0524 (11)	0.0356 (9)	0.0507 (11)	−0.0016 (8)	0.0233 (9)	−0.0048 (8)
C11	0.0477 (10)	0.0396 (9)	0.0482 (10)	0.0060 (8)	0.0194 (9)	−0.0017 (8)
C12	0.0608 (13)	0.0518 (12)	0.0460 (11)	0.0136 (10)	0.0106 (10)	0.0068 (9)
C13	0.0617 (12)	0.0560 (12)	0.0343 (9)	0.0062 (10)	0.0150 (9)	−0.0004 (8)
C16	0.0531 (12)	0.0716 (15)	0.0790 (16)	0.0095 (11)	0.0304 (12)	−0.0167 (13)
O1	0.0568 (8)	0.0384 (7)	0.0644 (9)	−0.0005 (6)	0.0272 (7)	0.0103 (6)
O2	0.0523 (8)	0.0646 (10)	0.0461 (8)	0.0066 (7)	0.0079 (7)	0.0030 (7)
O3	0.0394 (6)	0.0404 (7)	0.0464 (7)	−0.0014 (5)	0.0202 (6)	0.0000 (5)
C1	0.0347 (9)	0.0351 (9)	0.0498 (10)	0.0034 (7)	0.0141 (8)	0.0043 (8)
C2	0.0425 (9)	0.0377 (10)	0.0560 (11)	−0.0035 (8)	0.0191 (9)	0.0003 (8)
C3	0.0515 (11)	0.0491 (12)	0.0552 (11)	0.0028 (9)	0.0222 (10)	−0.0006 (9)
C4	0.0419 (10)	0.0527 (12)	0.0673 (13)	0.0126 (9)	0.0258 (10)	0.0169 (10)
C5	0.0428 (11)	0.0602 (13)	0.0863 (17)	−0.0092 (10)	0.0282 (12)	0.0013 (12)
C6	0.0413 (10)	0.0536 (12)	0.0699 (14)	−0.0096 (9)	0.0195 (10)	−0.0109 (10)
C7	0.0634 (14)	0.0879 (19)	0.0885 (18)	0.0160 (13)	0.0475 (14)	0.0213 (15)
C8	0.0438 (10)	0.0382 (9)	0.0429 (9)	−0.0027 (7)	0.0132 (8)	−0.0068 (7)
C9	0.0436 (9)	0.0352 (9)	0.0428 (9)	−0.0058 (7)	0.0233 (8)	−0.0024 (7)
C14	0.0386 (9)	0.0379 (9)	0.0357 (9)	−0.0002 (7)	0.0148 (7)	−0.0035 (7)
C15	0.0402 (9)	0.0401 (10)	0.0494 (11)	0.0012 (8)	0.0094 (8)	−0.0076 (8)
Cl1	0.0688 (3)	0.0623 (3)	0.0770 (4)	−0.0109 (3)	0.0498 (3)	0.0005 (3)
N1	0.0385 (8)	0.0383 (8)	0.0441 (8)	0.0008 (6)	0.0097 (7)	−0.0032 (6)
S1	0.0401 (2)	0.0385 (2)	0.0444 (3)	0.00261 (18)	0.01385 (19)	0.00562 (19)

C10—C9	1.537 (2)	C3—C4	1.385 (3)
C10—C11	1.554 (3)	C3—H3	0.9300
C10—H10A	0.9700	C4—C5	1.383 (3)
C10—H10B	0.9700	C4—C7	1.505 (3)
C11—O3	1.457 (2)	C5—C6	1.377 (3)
C11—C16	1.501 (3)	C5—H5	0.9300
C11—C12	1.511 (3)	C6—H6	0.9300
C12—C13	1.319 (3)	C7—H7A	0.9600
C12—H12	0.9300	C7—H7B	0.9600
C13—C14	1.504 (3)	C7—H7C	0.9600
C13—H13	0.9300	C8—N1	1.473 (2)
C16—H16A	0.9600	C8—C9	1.518 (3)
C16—H16B	0.9600	C8—H8A	0.9700
C16—H16C	0.9600	C8—H8B	0.9700
O1—S1	1.4302 (14)	C9—C14	1.563 (2)
O2—S1	1.4245 (15)	C9—Cl1	1.7952 (17)
O3—C14	1.432 (2)	C14—C15	1.492 (2)
C1—C2	1.380 (3)	C15—N1	1.473 (2)
C1—C6	1.382 (3)	C15—H15A	0.9700
C1—S1	1.7643 (19)	C15—H15B	0.9700
C2—C3	1.380 (3)	N1—S1	1.6159 (16)
C2—H2	0.9300
C9—C10—C11	100.86 (14)	C5—C6—H6	120.3
C9—C10—H10A	111.6	C1—C6—H6	120.3
C11—C10—H10A	111.6	C4—C7—H7A	109.5
C9—C10—H10B	111.6	C4—C7—H7B	109.5
C11—C10—H10B	111.6	H7A—C7—H7B	109.5
H10A—C10—H10B	109.4	C4—C7—H7C	109.5
O3—C11—C16	111.69 (17)	H7A—C7—H7C	109.5
O3—C11—C12	100.03 (15)	H7B—C7—H7C	109.5
C16—C11—C12	118.48 (19)	N1—C8—C9	104.64 (14)
O3—C11—C10	99.65 (14)	N1—C8—H8A	110.8
C16—C11—C10	116.82 (17)	C9—C8—H8A	110.8
C12—C11—C10	107.31 (17)	N1—C8—H8B	110.8
C13—C12—C11	107.74 (18)	C9—C8—H8B	110.8
C13—C12—H12	126.1	H8A—C8—H8B	108.9
C11—C12—H12	126.1	C8—C9—C10	117.81 (15)
C12—C13—C14	104.62 (17)	C8—C9—C14	102.03 (13)
C12—C13—H13	127.7	C10—C9—C14	102.13 (14)
C14—C13—H13	127.7	C8—C9—Cl1	108.97 (13)
C11—C16—H16A	109.5	C10—C9—Cl1	113.96 (13)
C11—C16—H16B	109.5	C14—C9—Cl1	110.94 (12)
H16A—C16—H16B	109.5	O3—C14—C15	112.85 (15)
C11—C16—H16C	109.5	O3—C14—C13	102.29 (14)
H16A—C16—H16C	109.5	C15—C14—C13	124.43 (16)
H16B—C16—H16C	109.5	O3—C14—C9	97.98 (12)
C14—O3—C11	96.70 (13)	C15—C14—C9	106.57 (14)
C2—C1—C6	120.26 (19)	C13—C14—C9	109.59 (15)
C2—C1—S1	119.75 (14)	N1—C15—C14	103.22 (14)
C6—C1—S1	119.98 (16)	N1—C15—H15A	111.1
C3—C2—C1	119.22 (18)	C14—C15—H15A	111.1
C3—C2—H2	120.4	N1—C15—H15B	111.1
C1—C2—H2	120.4	C14—C15—H15B	111.1
C2—C3—C4	121.6 (2)	H15A—C15—H15B	109.1
C2—C3—H3	119.2	C15—N1—C8	112.74 (14)
C4—C3—H3	119.2	C15—N1—S1	119.98 (12)
C5—C4—C3	117.9 (2)	C8—N1—S1	122.37 (12)
C5—C4—C7	121.2 (2)	O2—S1—O1	120.46 (9)
C3—C4—C7	120.9 (2)	O2—S1—N1	106.49 (9)
C6—C5—C4	121.5 (2)	O1—S1—N1	106.87 (8)
C6—C5—H5	119.3	O2—S1—C1	108.24 (9)
C4—C5—H5	119.3	O1—S1—C1	106.29 (9)
C5—C6—C1	119.5 (2)	N1—S1—C1	107.98 (8)
C9—C10—C11—O3	34.16 (17)	C12—C13—C14—C15	162.03 (19)
C9—C10—C11—C16	154.56 (19)	C12—C13—C14—C9	−70.3 (2)
C9—C10—C11—C12	−69.61 (18)	C8—C9—C14—O3	83.30 (14)
O3—C11—C12—C13	−30.6 (2)	C10—C9—C14—O3	−38.96 (16)
C16—C11—C12—C13	−152.2 (2)	Cl1—C9—C14—O3	−160.76 (11)
C10—C11—C12—C13	72.9 (2)	C8—C9—C14—C15	−33.50 (18)
C11—C12—C13—C14	−0.8 (2)	C10—C9—C14—C15	−155.76 (15)
C16—C11—O3—C14	174.89 (17)	Cl1—C9—C14—C15	82.44 (16)
C12—C11—O3—C14	48.62 (16)	C8—C9—C14—C13	−170.56 (15)
C10—C11—O3—C14	−61.04 (15)	C10—C9—C14—C13	67.19 (17)
C6—C1—C2—C3	1.2 (3)	Cl1—C9—C14—C13	−54.62 (17)
S1—C1—C2—C3	−177.82 (15)	O3—C14—C15—N1	−80.61 (17)
C1—C2—C3—C4	0.0 (3)	C13—C14—C15—N1	154.70 (18)
C2—C3—C4—C5	−1.2 (3)	C9—C14—C15—N1	25.80 (18)
C2—C3—C4—C7	178.6 (2)	C14—C15—N1—C8	−8.4 (2)
C3—C4—C5—C6	1.1 (3)	C14—C15—N1—S1	−164.23 (13)
C7—C4—C5—C6	−178.7 (2)	C9—C8—N1—C15	−12.7 (2)
C4—C5—C6—C1	0.1 (3)	C9—C8—N1—S1	142.44 (13)
C2—C1—C6—C5	−1.3 (3)	C15—N1—S1—O2	178.27 (15)
S1—C1—C6—C5	177.75 (17)	C8—N1—S1—O2	24.88 (17)
N1—C8—C9—C10	137.96 (16)	C15—N1—S1—O1	−51.77 (16)
N1—C8—C9—C14	27.15 (17)	C8—N1—S1—O1	154.84 (15)
N1—C8—C9—Cl1	−90.22 (14)	C15—N1—S1—C1	62.21 (16)
C11—C10—C9—C8	−108.28 (17)	C8—N1—S1—C1	−91.18 (16)
C11—C10—C9—C14	2.47 (17)	C2—C1—S1—O2	153.66 (15)
C11—C10—C9—Cl1	122.17 (14)	C6—C1—S1—O2	−25.36 (19)
C11—O3—C14—C15	173.57 (15)	C2—C1—S1—O1	22.93 (17)
C11—O3—C14—C13	−50.39 (16)	C6—C1—S1—O1	−156.09 (16)
C11—O3—C14—C9	61.76 (14)	C2—C1—S1—N1	−91.44 (16)
C12—C13—C14—O3	32.9 (2)	C6—C1—S1—N1	89.54 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1i	0.93	2.48	3.368 (2)	159
C5—H5···O3ii	0.93	2.62	3.539 (2)	169
C13—H13···O3iii	0.93	2.67	3.601 (2)	174

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1i	0.93	2.48	3.368 (2)	159
C5—H5⋯O3ii	0.93	2.62	3.539 (2)	169
C13—H13⋯O3iii	0.93	2.67	3.601 (2)	174

Symmetry codes: (i) ; (ii) ; (iii) .