(3aR,6S,7aR)-7a-Bromo-2-[(4-methyl-phen-yl)sulfon-yl]-1,2,3,6,7,7a-hexa-hydro-3a,6-ep-oxy-isoindole.

In the title compound, C(15)H(16)BrNO(3)S, the boat form of the six-membered ring is almost symmetrical with respect to the ep-oxy bridge. The two five-membered rings generated by the ep-oxy bridge of the six-membered ring adopt envelope conformations, whereas the N-containing five-membered ring adopts a twisted conformation. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds.

Related literature

For general background to intra­molecular Diels–Alder reactions and heteroaromatic Diels–Alder reactions, see: Dell (1998 ▶); Kappe et al. (1997 ▶); Arai et al. (2010 ▶); Lohse & Hsung (2009 ▶). For related structures, see: Koşar et al. (2006 ▶, 2007a ▶,b ▶). For the synthesis of the title compound and related compounds, see: Carlini et al. (1997 ▶); Hart et al. (1997 ▶); Shing et al. (1996 ▶); Karaarslan et al. (2007 ▶); Pontén & Magnusson (1997 ▶); Demircan et al. (2006 ▶); Arslan & Demircan (2008 ▶); Demircan & Parsons (1998 ▶). For puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15n class="CellLine">H16BrNO3S

M = 370.26

Monoclinic,

a = 16.5136 (6) Å

b = 6.2186 (3) Å

c = 16.3487 (7) Å

β = 113.802 (3)°

V = 1536.07 (12) Å3

Z = 4

Mo Kα radiation

μ = 2.82 mm−1

T = 296 K

0.58 × 0.44 × 0.31 mm

Data collection

STOE IPDS 2 CCD diffractometer

Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T min = 0.310, T max = 0.495

7305 measured reflections

3163 independent reflections

2353 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.048

wR(F 2) = 0.126

S = 1.07

3163 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.44 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: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶), OLEX2, publCIF (Westrip, 2010 ▶) and Mercury (Macrae et al., 2006 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811010750/zl2354sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811010750/zl2354Isup2.hkl

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

C15H16BrNO3S	F(000) = 752
Mr = 370.26	Dx = 1.601 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 10108 reflections
a = 16.5136 (6) Å	θ = 1.5–28.0°
b = 6.2186 (3) Å	µ = 2.82 mm−1
c = 16.3487 (7) Å	T = 296 K
β = 113.802 (3)°	Prism, colourless
V = 1536.07 (12) Å3	0.58 × 0.44 × 0.31 mm
Z = 4

STOE IPDS 2 CCD diffractometer	3163 independent reflections
Radiation source: fine-focus sealed tube	2353 reflections with I > 2σ(I)
plane graphite	Rint = 0.042
Detector resolution: 6.67 pixels mm-1	θmax = 26.5°, θmin = 2.5°
rotation method scans	h = −20→20
Absorption correction: integration (X-RED32; Stoe & Cie, 2002)	k = −7→7
Tmin = 0.310, Tmax = 0.495	l = −20→20
7305 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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0617P)2 + 0.5082P] where P = (Fo2 + 2Fc2)/3
3163 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.44 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	0.9623 (3)	0.6757 (7)	0.0923 (3)	0.0640 (11)
H1	1.0211	0.7174	0.0966	0.077*
C2	0.9042 (3)	0.5742 (8)	0.0062 (3)	0.0681 (12)
H2	0.9082	0.5913	−0.0485	0.082*
C3	0.8459 (3)	0.4559 (7)	0.0218 (3)	0.0617 (10)
H3	0.8013	0.3717	−0.0189	0.074*
C4	0.8668 (3)	0.4857 (6)	0.1192 (3)	0.0537 (9)
C5	0.8358 (3)	0.3394 (6)	0.1725 (3)	0.0642 (11)
H5A	0.7765	0.2875	0.1372	0.077*
H5B	0.8753	0.2172	0.1945	0.077*
C6	0.8569 (3)	0.7032 (6)	0.2354 (3)	0.0519 (9)
H6A	0.9170	0.7400	0.2752	0.062*
H6B	0.8163	0.7984	0.2472	0.062*
C7	0.8443 (3)	0.7184 (6)	0.1376 (3)	0.0489 (8)
C8	0.9107 (3)	0.8549 (7)	0.1161 (3)	0.0571 (10)
H8A	0.9488	0.9380	0.1674	0.069*
H8B	0.8812	0.9506	0.0660	0.069*
C9	0.6718 (3)	0.5012 (6)	0.2434 (3)	0.0526 (9)
C10	0.6473 (3)	0.7028 (7)	0.2619 (3)	0.0617 (10)
H10	0.6869	0.7852	0.3082	0.074*
C11	0.5636 (4)	0.7800 (8)	0.2109 (4)	0.0736 (13)
H11	0.5473	0.9149	0.2236	0.088*
C12	0.5033 (3)	0.6607 (9)	0.1410 (3)	0.0724 (12)
C13	0.5291 (3)	0.4605 (9)	0.1249 (3)	0.0725 (12)
H13	0.4891	0.3777	0.0790	0.087*
C14	0.6117 (3)	0.3787 (7)	0.1743 (3)	0.0627 (11)
H14	0.6273	0.2429	0.1617	0.075*
C15	0.4125 (5)	0.7472 (12)	0.0862 (5)	0.117 (2)
H15A	0.3802	0.6448	0.0408	0.175*
H15B	0.4175	0.8799	0.0586	0.175*
H15C	0.3818	0.7722	0.1242	0.175*
N1	0.8373 (2)	0.4748 (5)	0.2466 (2)	0.0526 (8)
O1	0.96199 (18)	0.5098 (4)	0.15645 (19)	0.0589 (7)
O2	0.8163 (2)	0.5198 (5)	0.38595 (19)	0.0729 (8)
O3	0.7776 (2)	0.1766 (5)	0.3018 (2)	0.0707 (8)
S1	0.78021 (8)	0.40698 (16)	0.30290 (6)	0.0559 (3)
Br1	0.71982 (3)	0.78750 (8)	0.06223 (3)	0.06777 (18)

	U11	U22	U33	U12	U13	U23
C1	0.060 (3)	0.068 (3)	0.066 (3)	0.007 (2)	0.028 (2)	0.000 (2)
C2	0.082 (3)	0.067 (3)	0.057 (2)	0.019 (2)	0.030 (2)	−0.001 (2)
C3	0.072 (3)	0.057 (2)	0.055 (2)	0.006 (2)	0.024 (2)	−0.0128 (19)
C4	0.058 (2)	0.043 (2)	0.054 (2)	0.0055 (17)	0.0174 (19)	−0.0063 (17)
C5	0.088 (3)	0.041 (2)	0.069 (3)	−0.003 (2)	0.038 (3)	−0.0124 (19)
C6	0.062 (2)	0.0406 (19)	0.053 (2)	−0.0077 (17)	0.0232 (19)	−0.0103 (17)
C7	0.050 (2)	0.0403 (18)	0.052 (2)	0.0033 (16)	0.0160 (17)	−0.0051 (16)
C8	0.064 (3)	0.047 (2)	0.061 (2)	0.0017 (18)	0.026 (2)	−0.0006 (18)
C9	0.064 (2)	0.044 (2)	0.054 (2)	−0.0029 (18)	0.029 (2)	0.0008 (17)
C10	0.069 (3)	0.052 (2)	0.067 (3)	−0.002 (2)	0.031 (2)	−0.008 (2)
C11	0.084 (3)	0.059 (3)	0.090 (3)	0.013 (2)	0.048 (3)	0.003 (2)
C12	0.063 (3)	0.083 (3)	0.073 (3)	0.007 (2)	0.030 (2)	0.004 (3)
C13	0.066 (3)	0.078 (3)	0.069 (3)	−0.011 (2)	0.022 (2)	−0.009 (2)
C14	0.068 (3)	0.052 (2)	0.069 (3)	−0.006 (2)	0.029 (2)	−0.008 (2)
C15	0.087 (4)	0.140 (6)	0.113 (5)	0.038 (4)	0.029 (4)	0.004 (4)
N1	0.065 (2)	0.0388 (16)	0.0541 (18)	0.0059 (14)	0.0239 (16)	−0.0009 (13)
O1	0.0538 (16)	0.0582 (17)	0.0582 (16)	0.0158 (13)	0.0159 (13)	0.0002 (13)
O2	0.092 (2)	0.077 (2)	0.0429 (14)	−0.0032 (18)	0.0201 (15)	−0.0060 (14)
O3	0.089 (2)	0.0489 (17)	0.0693 (19)	0.0038 (15)	0.0267 (18)	0.0154 (14)
S1	0.0708 (7)	0.0462 (5)	0.0474 (5)	0.0020 (4)	0.0203 (5)	0.0036 (4)
Br1	0.0521 (2)	0.0697 (3)	0.0701 (3)	0.0172 (2)	0.01277 (19)	0.0041 (2)

C1—O1	1.472 (5)	C8—H8A	0.9700
C1—C2	1.487 (7)	C8—H8B	0.9700
C1—C8	1.544 (6)	C9—C10	1.388 (6)
C1—H1	0.9800	C9—C14	1.392 (6)
C2—C3	1.316 (7)	C9—S1	1.757 (4)
C2—H2	0.9300	C10—C11	1.380 (7)
C3—C4	1.498 (5)	C10—H10	0.9300
C3—H3	0.9300	C11—C12	1.390 (8)
C4—O1	1.446 (5)	C11—H11	0.9300
C4—C5	1.487 (6)	C12—C13	1.375 (7)
C4—C7	1.553 (5)	C12—C15	1.502 (8)
C5—N1	1.467 (5)	C13—C14	1.373 (7)
C5—H5A	0.9700	C13—H13	0.9300
C5—H5B	0.9700	C14—H14	0.9300
C6—N1	1.484 (5)	C15—H15A	0.9600
C6—C7	1.530 (5)	C15—H15B	0.9600
C6—H6A	0.9700	C15—H15C	0.9600
C6—H6B	0.9700	N1—S1	1.616 (3)
C7—C8	1.535 (6)	O2—S1	1.427 (3)
C7—Br1	1.971 (4)	O3—S1	1.433 (3)
O1—C1—C2	101.0 (4)	C1—C8—H8A	111.7
O1—C1—C8	99.5 (3)	C7—C8—H8B	111.7
C2—C1—C8	109.5 (4)	C1—C8—H8B	111.7
O1—C1—H1	115.0	H8A—C8—H8B	109.5
C2—C1—H1	115.0	C10—C9—C14	119.7 (4)
C8—C1—H1	115.0	C10—C9—S1	120.1 (3)
C3—C2—C1	107.2 (4)	C14—C9—S1	120.1 (3)
C3—C2—H2	126.4	C11—C10—C9	119.5 (4)
C1—C2—H2	126.4	C11—C10—H10	120.3
C2—C3—C4	105.3 (4)	C9—C10—H10	120.3
C2—C3—H3	127.3	C10—C11—C12	121.4 (4)
C4—C3—H3	127.3	C10—C11—H11	119.3
O1—C4—C5	112.9 (3)	C12—C11—H11	119.3
O1—C4—C3	101.9 (3)	C13—C12—C11	117.8 (5)
C5—C4—C3	124.1 (4)	C13—C12—C15	121.5 (5)
O1—C4—C7	97.3 (3)	C11—C12—C15	120.7 (5)
C5—C4—C7	106.9 (3)	C14—C13—C12	122.3 (5)
C3—C4—C7	110.5 (3)	C14—C13—H13	118.8
N1—C5—C4	103.8 (3)	C12—C13—H13	118.8
N1—C5—H5A	111.0	C13—C14—C9	119.3 (4)
C4—C5—H5A	111.0	C13—C14—H14	120.4
N1—C5—H5B	111.0	C9—C14—H14	120.4
C4—C5—H5B	111.0	C12—C15—H15A	109.5
H5A—C5—H5B	109.0	C12—C15—H15B	109.5
N1—C6—C7	104.1 (3)	H15A—C15—H15B	109.5
N1—C6—H6A	110.9	C12—C15—H15C	109.5
C7—C6—H6A	110.9	H15A—C15—H15C	109.5
N1—C6—H6B	110.9	H15B—C15—H15C	109.5
C7—C6—H6B	110.9	C5—N1—C6	112.2 (3)
H6A—C6—H6B	108.9	C5—N1—S1	120.1 (3)
C6—C7—C8	117.7 (3)	C6—N1—S1	121.8 (2)
C6—C7—C4	101.7 (3)	C4—O1—C1	95.1 (3)
C8—C7—C4	102.9 (3)	O2—S1—O3	120.16 (19)
C6—C7—Br1	109.5 (3)	O2—S1—N1	107.28 (19)
C8—C7—Br1	113.4 (3)	O3—S1—N1	105.97 (18)
C4—C7—Br1	110.7 (3)	O2—S1—C9	107.7 (2)
C7—C8—C1	100.1 (3)	O3—S1—C9	107.9 (2)
C7—C8—H8A	111.7	N1—S1—C9	107.18 (17)
O1—C1—C2—C3	31.5 (4)	C10—C11—C12—C13	1.0 (7)
C8—C1—C2—C3	−72.9 (5)	C10—C11—C12—C15	−180.0 (5)
C1—C2—C3—C4	0.8 (5)	C11—C12—C13—C14	−1.0 (7)
C2—C3—C4—O1	−33.6 (4)	C15—C12—C13—C14	−180.0 (5)
C2—C3—C4—C5	−162.1 (4)	C12—C13—C14—C9	0.2 (7)
C2—C3—C4—C7	68.9 (4)	C10—C9—C14—C13	0.6 (6)
O1—C4—C5—N1	80.2 (4)	S1—C9—C14—C13	−176.0 (3)
C3—C4—C5—N1	−156.0 (4)	C4—C5—N1—C6	7.1 (5)
C7—C4—C5—N1	−25.6 (4)	C4—C5—N1—S1	160.4 (3)
N1—C6—C7—C8	−139.8 (3)	C7—C6—N1—C5	14.3 (5)
N1—C6—C7—C4	−28.3 (4)	C7—C6—N1—S1	−138.6 (3)
N1—C6—C7—Br1	88.8 (3)	C5—C4—O1—C1	−174.3 (3)
O1—C4—C7—C6	−82.6 (3)	C3—C4—O1—C1	50.3 (3)
C5—C4—C7—C6	34.1 (4)	C7—C4—O1—C1	−62.5 (3)
C3—C4—C7—C6	171.8 (3)	C2—C1—O1—C4	−49.4 (3)
O1—C4—C7—C8	39.7 (4)	C8—C1—O1—C4	62.7 (3)
C5—C4—C7—C8	156.4 (4)	C5—N1—S1—O2	160.6 (3)
C3—C4—C7—C8	−65.9 (4)	C6—N1—S1—O2	−48.6 (4)
O1—C4—C7—Br1	161.2 (2)	C5—N1—S1—O3	31.1 (4)
C5—C4—C7—Br1	−82.2 (4)	C6—N1—S1—O3	−178.1 (3)
C3—C4—C7—Br1	55.6 (4)	C5—N1—S1—C9	−83.9 (3)
C6—C7—C8—C1	108.8 (4)	C6—N1—S1—C9	66.9 (3)
C4—C7—C8—C1	−2.0 (4)	C10—C9—S1—O2	23.2 (4)
Br1—C7—C8—C1	−121.5 (3)	C14—C9—S1—O2	−160.2 (3)
O1—C1—C8—C7	−35.8 (4)	C10—C9—S1—O3	154.3 (3)
C2—C1—C8—C7	69.5 (4)	C14—C9—S1—O3	−29.1 (4)
C14—C9—C10—C11	−0.6 (6)	C10—C9—S1—N1	−92.0 (3)
S1—C9—C10—C11	176.1 (3)	C14—C9—S1—N1	84.6 (3)
C9—C10—C11—C12	−0.3 (7)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6A···O1i	0.97	2.50	3.382 (6)	151
C10—H10···O2	0.93	2.59	2.937 (6)	103

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6A⋯O1i	0.97	2.50	3.382 (6)	151

Symmetry code: (i) .