Crystal structure of 1,3-diallyl-1,3,3a,4,7,7a-hexa-hydro-4,7-methano-2-benzo-thio-phene 2,2-dioxide.

The title compound C15H20O2S, was identified as a product of di-allyl-ation of the meso-isomer of the corresponding norbornene sulfone, and it is an achiral compound. The five-membered heterocycle adopts an envelope conformation with the S atom deviating by 0.795 (3) Å from the other atoms of the ring (r.m.s. deviation = 0.0131). Both allyl groups are anti-oriented relative to the S atom but their double bonds are directed in opposite directions relative to the plane of the heterocycle.

Related literature

For related functionalized sulfones, see: Bloch & Abecassis (1982 ▶, 1983 ▶); Bloch et al. (1983 ▶, 1984 ▶); Yamada et al. (1983 ▶). For the synthesis of the precursor, see: Bloch & Abecassis (1982 ▶). For sulfones as latent diene equivalents, see: Fringuelli & Taticchi (1990 ▶). For X-ray crystal data of related bi­cyclo­[2.2.1]compounds, see: Birney et al. (2002 ▶). For literature on sulfones, see: Bhat (1994 ▶); Fielder et al. (2000 ▶); Nakayama et al. (1997 ▶). For bond lengths in related structures, see: Chandrasekhar (1992 ▶); Pool & White (2000 ▶).

Experimental

Crystal data

C15H20O2S

M = 264.37

Monoclinic,

a = 12.4412 (17) Å

b = 8.8472 (13) Å

c = 12.738 (2) Å

β = 97.069 (8)°

V = 1391.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 100 K

0.27 × 0.22 × 0.11 mm

Data collection

Rigaku Saturn724 diffractometer

Absorption correction: numerical (NUMABS; Rigaku, 1999 ▶) T min = 0.957, T max = 0.976

20804 measured reflections

3702 independent reflections

3231 reflections with I > 2σ(I)

R int = 0.097

Refinement

R[F 2 > 2σ(F 2)] = 0.069

wR(F 2) = 0.141

S = 1.13

3702 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.46 e Å−3

Δρmin = −0.46 e Å−3

Data collection: CrystalClear-SM Expert (Rigaku, 2013 ▶); cell refinement: CrystalClear-SM Expert; data reduction: CrystalClear-SM Expert; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalStructure (Rigaku, 2010 ▶); software used to prepare material for publication: CrystalStructure.

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814022053/ld2131sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814022053/ld2131Isup2.hkl

Click here for additional data file.

. DOI: 10.1107/S1600536814022053/ld2131fig1.tif

The stucture of the title compound showing labeling of non-H atoms.

CCDC reference: 1027850

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

C15H20O2S	F(000) = 568
Mr = 264.37	Dx = 1.262 Mg m−3
Monoclinic, P21/n	Melting point = 349.15–348.15 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71075 Å
a = 12.4412 (17) Å	Cell parameters from 3728 reflections
b = 8.8472 (13) Å	θ = 3.2–29.1°
c = 12.738 (2) Å	µ = 0.23 mm−1
β = 97.069 (8)°	T = 100 K
V = 1391.4 (4) Å3	Prism, colourless
Z = 4	0.27 × 0.22 × 0.11 mm

Rigaku Saturn724 diffractometer	3702 independent reflections
Radiation source: fine-focus sealed tube	3231 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.097
Detector resolution: 7.111 pixels mm-1	θmax = 29.2°, θmin = 3.2°
ω scans	h = −16→16
Absorption correction: numerical (NUMABS; Rigaku, 1999)	k = −12→12
Tmin = 0.957, Tmax = 0.976	l = −17→17
20804 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)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0388P)2 + 1.1426P] where P = (Fo2 + 2Fc2)/3
3702 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.46 e Å−3
0 restraints	Δρmin = −0.46 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. All non-hydrogen atoms are refined anisotropically and all hydrogen atoms are refined using riding model.

	x	y	z	Uiso*/Ueq
S1	0.13583 (4)	0.04117 (7)	−0.17128 (4)	0.01977 (15)
O1	0.17802 (13)	0.0793 (2)	−0.26827 (12)	0.0266 (4)
O2	0.02888 (12)	0.09616 (19)	−0.15801 (13)	0.0248 (4)
C1	0.37378 (18)	−0.1394 (3)	0.04960 (18)	0.0255 (5)
H1A	0.4435	−0.0971	0.0464	0.031*
C2	0.33509 (17)	−0.2638 (3)	0.00116 (18)	0.0233 (5)
H2A	0.3715	−0.3258	−0.0441	0.028*
C3	0.22217 (18)	−0.2896 (3)	0.03084 (18)	0.0227 (5)
H3A	0.1948	−0.3958	0.0236	0.027*
C4	0.14638 (17)	−0.1664 (3)	−0.02595 (17)	0.0199 (4)
H4A	0.0713	−0.1818	−0.0076	0.024*
C5	0.19392 (17)	−0.0161 (3)	0.02751 (17)	0.0203 (5)
H5A	0.1374	0.0338	0.0650	0.024*
C6	0.28701 (18)	−0.0765 (3)	0.11112 (18)	0.0231 (5)
H6A	0.3126	−0.0058	0.1702	0.028*
C7	0.23523 (18)	−0.2246 (3)	0.14310 (17)	0.0240 (5)
H7A	0.2844	−0.2853	0.1936	0.029*
H7B	0.1651	−0.2086	0.1708	0.029*
C8	0.22743 (17)	0.0912 (3)	−0.05690 (17)	0.0214 (5)
H8A	0.3024	0.0636	−0.0706	0.026*
C9	0.22503 (19)	0.2605 (3)	−0.03435 (19)	0.0267 (5)
H9A	0.2466	0.3170	−0.0955	0.032*
H9B	0.1504	0.2912	−0.0245	0.032*
C10	0.3005 (2)	0.2993 (3)	0.0631 (2)	0.0303 (6)
H10A	0.2786	0.2739	0.1298	0.036*
C11	0.3942 (2)	0.3655 (3)	0.0626 (3)	0.0397 (7)
H11A	0.4187	0.3924	−0.0027	0.060*
H11B	0.4379	0.3867	0.1274	0.060*
C12	0.14238 (17)	−0.1576 (3)	−0.14620 (16)	0.0191 (4)
H12A	0.2121	−0.1974	−0.1667	0.023*
C13	0.04834 (18)	−0.2400 (3)	−0.21087 (18)	0.0226 (5)
H13A	−0.0210	−0.2029	−0.1898	0.027*
H13B	0.0489	−0.2167	−0.2868	0.027*
C14	0.05525 (18)	−0.4070 (3)	−0.19523 (18)	0.0257 (5)
H14A	0.1178	−0.4568	−0.2139	0.031*
C15	−0.0184 (2)	−0.4906 (3)	−0.1576 (2)	0.0321 (6)
H15A	−0.0822	−0.4450	−0.1380	0.048*
H15B	−0.0080	−0.5966	−0.1500	0.048*

	U11	U22	U33	U12	U13	U23
S1	0.0159 (3)	0.0258 (3)	0.0175 (3)	−0.0011 (2)	0.00159 (19)	0.0028 (2)
O1	0.0258 (8)	0.0346 (10)	0.0197 (8)	−0.0032 (7)	0.0045 (6)	0.0060 (7)
O2	0.0173 (8)	0.0308 (9)	0.0258 (9)	0.0009 (6)	0.0013 (6)	0.0032 (7)
C1	0.0146 (10)	0.0360 (14)	0.0253 (12)	0.0017 (9)	−0.0001 (8)	0.0075 (10)
C2	0.0194 (10)	0.0302 (13)	0.0205 (11)	0.0071 (9)	0.0027 (8)	0.0036 (10)
C3	0.0201 (11)	0.0255 (12)	0.0220 (11)	0.0001 (9)	0.0001 (8)	0.0031 (9)
C4	0.0145 (9)	0.0264 (12)	0.0188 (10)	−0.0009 (8)	0.0023 (8)	0.0010 (9)
C5	0.0161 (10)	0.0274 (12)	0.0174 (10)	0.0008 (8)	0.0023 (8)	−0.0026 (9)
C6	0.0204 (11)	0.0290 (13)	0.0192 (11)	0.0006 (9)	−0.0010 (8)	0.0003 (9)
C7	0.0203 (11)	0.0328 (13)	0.0188 (11)	0.0003 (9)	0.0019 (8)	0.0030 (10)
C8	0.0158 (10)	0.0274 (12)	0.0206 (11)	−0.0003 (8)	0.0007 (8)	−0.0008 (9)
C9	0.0234 (11)	0.0269 (13)	0.0285 (12)	0.0026 (9)	−0.0018 (9)	−0.0012 (10)
C10	0.0342 (13)	0.0273 (13)	0.0283 (13)	0.0012 (10)	−0.0002 (10)	−0.0022 (11)
C11	0.0337 (14)	0.0323 (15)	0.0504 (17)	−0.0011 (11)	−0.0054 (12)	−0.0059 (13)
C12	0.0162 (10)	0.0240 (11)	0.0173 (10)	−0.0001 (8)	0.0025 (8)	0.0006 (9)
C13	0.0203 (10)	0.0268 (12)	0.0196 (11)	−0.0033 (9)	−0.0016 (8)	0.0005 (9)
C14	0.0214 (11)	0.0314 (13)	0.0238 (12)	−0.0032 (9)	0.0006 (9)	−0.0044 (10)
C15	0.0264 (12)	0.0335 (14)	0.0349 (14)	−0.0044 (10)	−0.0023 (10)	0.0031 (11)

S1—O1	1.4406 (16)	C7—H7A	0.9900
S1—O2	1.4461 (16)	C7—H7B	0.9900
S1—C12	1.788 (2)	C8—C9	1.527 (3)
S1—C8	1.791 (2)	C8—H8A	1.0000
C1—C2	1.323 (3)	C9—C10	1.502 (3)
C1—C6	1.516 (3)	C9—H9A	0.9900
C1—H1A	0.9500	C9—H9B	0.9900
C2—C3	1.516 (3)	C10—C11	1.305 (4)
C2—H2A	0.9500	C10—H10A	0.9500
C3—C7	1.531 (3)	C11—H11A	0.9500
C3—C4	1.559 (3)	C11—H11B	0.9500
C3—H3A	1.0000	C12—C13	1.530 (3)
C4—C12	1.528 (3)	C12—H12A	1.0000
C4—C5	1.576 (3)	C13—C14	1.492 (3)
C4—H4A	1.0000	C13—H13A	0.9900
C5—C8	1.530 (3)	C13—H13B	0.9900
C5—C6	1.568 (3)	C14—C15	1.313 (3)
C5—H5A	1.0000	C14—H14A	0.9500
C6—C7	1.537 (3)	C15—H15A	0.9500
C6—H6A	1.0000	C15—H15B	0.9500
O1—S1—O2	117.32 (10)	C3—C7—H7B	112.9
O1—S1—C12	111.75 (10)	C6—C7—H7B	112.9
O2—S1—C12	109.42 (10)	H7A—C7—H7B	110.3
O1—S1—C8	112.16 (10)	C9—C8—C5	117.59 (19)
O2—S1—C8	108.92 (10)	C9—C8—S1	111.73 (16)
C12—S1—C8	95.00 (10)	C5—C8—S1	102.55 (15)
C2—C1—C6	107.8 (2)	C9—C8—H8A	108.2
C2—C1—H1A	126.1	C5—C8—H8A	108.2
C6—C1—H1A	126.1	S1—C8—H8A	108.2
C1—C2—C3	107.7 (2)	C10—C9—C8	110.8 (2)
C1—C2—H2A	126.2	C10—C9—H9A	109.5
C3—C2—H2A	126.2	C8—C9—H9A	109.5
C2—C3—C7	100.44 (18)	C10—C9—H9B	109.5
C2—C3—C4	107.77 (18)	C8—C9—H9B	109.5
C7—C3—C4	99.18 (18)	H9A—C9—H9B	108.1
C2—C3—H3A	115.7	C11—C10—C9	124.5 (3)
C7—C3—H3A	115.7	C11—C10—H10A	117.8
C4—C3—H3A	115.7	C9—C10—H10A	117.8
C12—C4—C3	116.35 (18)	C10—C11—H11A	120.0
C12—C4—C5	110.74 (18)	C10—C11—H11B	120.0
C3—C4—C5	102.46 (17)	H11A—C11—H11B	120.0
C12—C4—H4A	109.0	C4—C12—C13	116.34 (18)
C3—C4—H4A	109.0	C4—C12—S1	102.97 (15)
C5—C4—H4A	109.0	C13—C12—S1	110.95 (15)
C8—C5—C6	116.52 (18)	C4—C12—H12A	108.8
C8—C5—C4	109.88 (17)	C13—C12—H12A	108.8
C6—C5—C4	102.26 (18)	S1—C12—H12A	108.8
C8—C5—H5A	109.3	C14—C13—C12	111.85 (19)
C6—C5—H5A	109.3	C14—C13—H13A	109.2
C4—C5—H5A	109.3	C12—C13—H13A	109.2
C1—C6—C7	99.92 (19)	C14—C13—H13B	109.2
C1—C6—C5	106.71 (18)	C12—C13—H13B	109.2
C7—C6—C5	99.91 (17)	H13A—C13—H13B	107.9
C1—C6—H6A	116.0	C15—C14—C13	125.1 (2)
C7—C6—H6A	116.0	C15—C14—H14A	117.5
C5—C6—H6A	116.0	C13—C14—H14A	117.5
C3—C7—C6	94.14 (17)	C14—C15—H15A	120.0
C3—C7—H7A	112.9	C14—C15—H15B	120.0
C6—C7—H7A	112.9	H15A—C15—H15B	120.0
C6—C1—C2—C3	−1.2 (3)	C4—C5—C8—S1	29.21 (19)
C1—C2—C3—C7	−32.1 (2)	O1—S1—C8—C9	77.19 (18)
C1—C2—C3—C4	71.2 (2)	O2—S1—C8—C9	−54.37 (19)
C2—C3—C4—C12	56.1 (2)	C12—S1—C8—C9	−166.88 (16)
C7—C3—C4—C12	160.25 (18)	O1—S1—C8—C5	−155.97 (14)
C2—C3—C4—C5	−64.9 (2)	O2—S1—C8—C5	72.46 (16)
C7—C3—C4—C5	39.31 (19)	C12—S1—C8—C5	−40.04 (15)
C12—C4—C5—C8	−2.9 (2)	C5—C8—C9—C10	60.6 (3)
C3—C4—C5—C8	121.84 (18)	S1—C8—C9—C10	178.75 (17)
C12—C4—C5—C6	−127.26 (18)	C8—C9—C10—C11	105.1 (3)
C3—C4—C5—C6	−2.5 (2)	C3—C4—C12—C13	97.1 (2)
C2—C1—C6—C7	33.9 (2)	C5—C4—C12—C13	−146.51 (19)
C2—C1—C6—C5	−69.7 (2)	C3—C4—C12—S1	−141.38 (16)
C8—C5—C6—C1	−51.2 (3)	C5—C4—C12—S1	−24.95 (19)
C4—C5—C6—C1	68.6 (2)	O1—S1—C12—C4	154.63 (13)
C8—C5—C6—C7	−154.80 (19)	O2—S1—C12—C4	−73.72 (15)
C4—C5—C6—C7	−35.0 (2)	C8—S1—C12—C4	38.37 (15)
C2—C3—C7—C6	49.4 (2)	O1—S1—C12—C13	−80.22 (17)
C4—C3—C7—C6	−60.77 (18)	O2—S1—C12—C13	51.43 (18)
C1—C6—C7—C3	−49.91 (19)	C8—S1—C12—C13	163.51 (16)
C5—C6—C7—C3	59.17 (19)	C4—C12—C13—C14	−65.6 (3)
C6—C5—C8—C9	−92.2 (2)	S1—C12—C13—C14	177.17 (16)
C4—C5—C8—C9	152.19 (19)	C12—C13—C14—C15	120.0 (3)
C6—C5—C8—S1	144.85 (17)