(5R,6S)-6-Methyl-5-(phenyl­sulfonylacet­yl)bicyclo­[2.2.1]hept-2-ene

The title compound, C₁₆H₁₈O₃S, an endo-cyclo­adduct isomer, was obtained from the Diels-Alder reaction of (E)-1-(phenyl­sulfon­yl)pent-3-en-2-one with cyclo­penta­diene catalysed by a chiral titanium reagent. The crystal structure confirms the absolute streochemistry.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.045
• wR factor = 0.138
• Data-to-parameter ratio = 16.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C14    -   C15     ..       6.24 su

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.41
           From the CIF: _reflns_number_total               3074
           Count of symmetry unique reflns         1825
           Completeness (_total/calc)            168.44%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1249
           Fraction of Friedel pairs measured     0.684
           Are heavy atom types Z>Si present        yes
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C2     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3     = .          S
PLAT791_ALERT_1_G Confirm the Absolute Configuration of C6     = .          R

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   4 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: PROCESS-AUTO (Rigaku,1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC,2004); program(s) used to solve structure: SIR97 (Altomare et al.,1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia,1997); software used to prepare material for publication: CrystalStructure.

(I)

Crystal data

C16H18O3S	F(000) = 308.00
Mr = 290.38	Dx = 1.324 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2yb	Cell parameters from 4849 reflections
a = 11.2342 (3) Å	θ = 2.0–27.4°
b = 5.8141 (1) Å	µ = 0.23 mm^−1
c = 12.3584 (3) Å	T = 296 K
β = 115.5233 (8)°	Needle, colorless
V = 728.44 (3) Å^3	0.28 × 0.10 × 0.04 mm
Z = 2

Data collection

Rigaku RAXIS-RAPID diffractometer	2761 reflections with F^2 > 2.0σ(F^2)
Detector resolution: 10.00 pixels mm^-1	Rint = 0.046
ω scans	θmax = 27.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −14→14
Tmin = 0.917, Tmax = 0.991	k = −7→7
7013 measured reflections	l = −15→16
3074 independent reflections

Refinement

Refinement on F^2	w = 1/[σ^2(Fo^2) + (0.105P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.045	(Δ/σ)max = 0.001
wR(F^2) = 0.138	Δρmax = 0.27 e Å^−3
S = 1.00	Δρmin = −0.21 e Å^−3
3074 reflections	Absolute structure: Flack (1983): 1251 Friedel Pairs
183 parameters	Absolute structure parameter: −0.067 (2)
H-atom parameters constrained

Special details

Geometry. The geometry of the title compound is bicyclic

Refinement. Refinement using all reflections. The weighted R-factor (wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.22422 (5)	0.32895 (12)	0.52300 (5)	0.03286 (17)
O1	0.1958 (2)	0.2445 (4)	0.4053 (2)	0.0499 (5)
O2	0.1721 (2)	0.5490 (3)	0.5349 (2)	0.0459 (5)
O3	0.2948 (2)	−0.0431 (4)	0.7826 (2)	0.0577 (6)
C1	0.2075 (2)	0.3295 (5)	0.7907 (2)	0.0326 (4)
C2	0.2735 (2)	0.3208 (6)	0.9300 (2)	0.0359 (5)
C3	0.1530 (2)	0.3717 (5)	0.9586 (2)	0.0421 (6)
C4	0.0681 (3)	0.1616 (6)	0.9180 (3)	0.0505 (7)
C5	0.0109 (2)	0.1576 (6)	0.7996 (3)	0.0477 (7)
C6	0.0574 (2)	0.3697 (5)	0.7582 (2)	0.0423 (7)
C7	0.0736 (3)	0.5397 (5)	0.8580 (3)	0.0466 (7)
C8	0.3850 (3)	0.4954 (7)	0.9860 (3)	0.0565 (8)
C9	0.2310 (2)	0.1229 (5)	0.7305 (2)	0.0347 (5)
C10	0.1677 (2)	0.1156 (4)	0.5936 (2)	0.0349 (5)
C11	0.3970 (2)	0.3360 (6)	0.6076 (2)	0.0341 (4)
C12	0.4720 (3)	0.1563 (6)	0.5950 (2)	0.0465 (7)
C13	0.6059 (3)	0.1606 (7)	0.6613 (3)	0.0594 (9)
C14	0.6647 (2)	0.3402 (9)	0.7389 (3)	0.0638 (9)
C15	0.5898 (3)	0.5167 (7)	0.7504 (3)	0.0581 (9)
C16	0.4544 (2)	0.5152 (5)	0.6854 (2)	0.0429 (6)
H1	0.2408	0.4651	0.7654	0.039*
H2	0.3069	0.1655	0.9571	0.043*
H3	0.1745	0.4241	1.0403	0.050*
H4	0.0574	0.0520	0.9680	0.061*
H5	−0.0468	0.0461	0.7512	0.057*
H6	0.0022	0.4208	0.6761	0.051*
H12	0.4319	0.0356	0.5424	0.056*
H13	0.6575	0.0418	0.6540	0.071*
H14	0.7557	0.3418	0.7837	0.077*
H15	0.6305	0.6379	0.8024	0.070*
H16	0.4031	0.6330	0.6941	0.051*
H71	−0.0096	0.5844	0.8581	0.056*
H72	0.1228	0.6765	0.8574	0.056*
H81	0.3508	0.6478	0.9622	0.068*
H82	0.4519	0.4650	0.9592	0.068*
H83	0.4222	0.4831	1.0717	0.068*
H101	0.0733	0.1351	0.5655	0.042*
H102	0.1854	−0.0342	0.5692	0.042*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0312 (2)	0.0333 (3)	0.0300 (2)	0.0005 (2)	0.0094 (2)	0.0011 (2)
O1	0.0543 (12)	0.0595 (14)	0.0317 (10)	−0.0063 (9)	0.0146 (9)	−0.0033 (8)
O2	0.0396 (10)	0.0365 (11)	0.0552 (13)	0.0074 (8)	0.0142 (10)	0.0055 (9)
O3	0.0727 (15)	0.0460 (13)	0.0508 (13)	0.0293 (11)	0.0232 (12)	0.0097 (10)
C1	0.0329 (10)	0.0313 (11)	0.0333 (10)	0.0039 (13)	0.0139 (8)	0.0064 (13)
C2	0.0327 (10)	0.0367 (12)	0.0349 (11)	−0.0002 (14)	0.0113 (9)	−0.0014 (14)
C3	0.0506 (14)	0.0428 (18)	0.0360 (13)	0.0008 (13)	0.0217 (12)	−0.0025 (11)
C4	0.0510 (17)	0.0553 (19)	0.0568 (19)	−0.0049 (15)	0.0342 (16)	0.0005 (16)
C5	0.0317 (13)	0.0532 (18)	0.0584 (19)	−0.0048 (13)	0.0195 (13)	−0.0091 (15)
C6	0.0366 (12)	0.050 (2)	0.0370 (13)	0.0159 (12)	0.0126 (11)	0.0047 (12)
C7	0.0442 (16)	0.0438 (17)	0.0554 (19)	0.0101 (13)	0.0248 (15)	−0.0021 (14)
C8	0.0440 (16)	0.057 (2)	0.057 (2)	−0.0113 (16)	0.0107 (15)	−0.0091 (16)
C9	0.0314 (11)	0.0356 (14)	0.0393 (13)	−0.0006 (10)	0.0172 (10)	0.0038 (11)
C10	0.0344 (12)	0.0308 (13)	0.0390 (14)	−0.0041 (10)	0.0154 (11)	−0.0027 (10)
C11	0.0308 (10)	0.0373 (12)	0.0352 (11)	0.0033 (14)	0.0152 (9)	0.0014 (13)
C12	0.0463 (15)	0.0474 (17)	0.0483 (17)	0.0043 (14)	0.0227 (14)	−0.0046 (14)
C13	0.0439 (17)	0.074 (2)	0.066 (2)	0.0199 (17)	0.0283 (17)	0.001 (2)
C14	0.0315 (12)	0.094 (2)	0.0597 (19)	−0.006 (2)	0.0139 (13)	0.002 (2)
C15	0.0379 (15)	0.068 (2)	0.060 (2)	−0.0098 (16)	0.0134 (15)	−0.0127 (18)
C16	0.0367 (13)	0.0433 (16)	0.0474 (16)	−0.0031 (13)	0.0169 (12)	−0.0064 (13)

Geometric parameters (Å, º)

S1—O1	1.435 (2)	C14—C15	1.373 (6)
S1—O2	1.441 (2)	C15—C16	1.381 (4)
S1—C10	1.783 (3)	C1—H1	0.980
S1—C11	1.765 (2)	C2—H2	0.980
O3—C9	1.209 (3)	C3—H3	0.980
C1—C2	1.554 (3)	C4—H4	0.930
C1—C6	1.573 (3)	C5—H5	0.930
C1—C9	1.496 (4)	C6—H6	0.980
C2—C3	1.568 (4)	C7—H71	0.970
C2—C8	1.527 (4)	C7—H72	0.970
C3—C4	1.497 (4)	C8—H81	0.960
C3—C7	1.530 (4)	C8—H82	0.960
C4—C5	1.321 (5)	C8—H83	0.960
C5—C6	1.512 (5)	C10—H101	0.970
C6—C7	1.529 (4)	C10—H102	0.970
C9—C10	1.527 (4)	C12—H12	0.930
C11—C12	1.393 (4)	C13—H13	0.930
C11—C16	1.375 (4)	C14—H14	0.930
C12—C13	1.368 (4)	C15—H15	0.930
C13—C14	1.378 (6)	C16—H16	0.930
O1—S1—O2	118.98 (14)	C8—C2—H2	109.8
O1—S1—C10	106.70 (14)	C2—C3—H3	115.9
O1—S1—C11	108.44 (14)	C4—C3—H3	115.9
O2—S1—C10	108.77 (16)	C7—C3—H3	115.9
O2—S1—C11	108.09 (14)	C3—C4—H4	125.6
C10—S1—C11	105.01 (13)	C5—C4—H4	125.6
C2—C1—C6	103.6 (2)	C4—C5—H5	126.7
C2—C1—C9	115.0 (2)	C6—C5—H5	126.7
C6—C1—C9	113.0 (2)	C1—C6—H6	116.1
C1—C2—C3	101.41 (18)	C5—C6—H6	116.1
C1—C2—C8	112.8 (2)	C7—C6—H6	116.1
C3—C2—C8	113.1 (2)	C3—C7—H71	113.2
C2—C3—C4	105.0 (2)	C3—C7—H72	113.2
C2—C3—C7	101.2 (2)	C6—C7—H71	113.2
C4—C3—C7	100.6 (2)	C6—C7—H72	113.2
C3—C4—C5	108.7 (3)	H71—C7—H72	109.5
C4—C5—C6	106.6 (2)	C2—C8—H81	109.5
C1—C6—C5	106.4 (2)	C2—C8—H82	109.5
C1—C6—C7	98.5 (2)	C2—C8—H83	109.5
C5—C6—C7	101.1 (2)	H81—C8—H82	109.5
C3—C7—C6	93.9 (2)	H81—C8—H83	109.5
O3—C9—C1	124.5 (2)	H82—C8—H83	109.5
O3—C9—C10	117.0 (2)	S1—C10—H101	108.0
C1—C9—C10	118.4 (2)	S1—C10—H102	108.0
S1—C10—C9	115.38 (19)	C9—C10—H101	108.0
S1—C11—C12	118.7 (2)	C9—C10—H102	108.0
S1—C11—C16	119.8 (2)	H101—C10—H102	109.5
C12—C11—C16	121.5 (2)	C11—C12—H12	120.6
C11—C12—C13	118.8 (3)	C13—C12—H12	120.6
C12—C13—C14	120.3 (3)	C12—C13—H13	119.9
C13—C14—C15	120.5 (2)	C14—C13—H13	119.9
C14—C15—C16	120.4 (3)	C13—C14—H14	119.8
C11—C16—C15	118.6 (3)	C15—C14—H14	119.8
C2—C1—H1	108.3	C14—C15—H15	119.8
C6—C1—H1	108.3	C16—C15—H15	119.8
C9—C1—H1	108.3	C11—C16—H16	120.7
C1—C2—H2	109.8	C15—C16—H16	120.7
C3—C2—H2	109.8
O1—S1—C10—C9	158.2 (2)	C1—C2—C3—C7	−34.5 (2)
O1—S1—C11—C12	−39.6 (3)	C8—C2—C3—C4	−169.2 (2)
O1—S1—C11—C16	141.4 (2)	C8—C2—C3—C7	86.5 (2)
O2—S1—C10—C9	−72.3 (2)	C2—C3—C4—C5	−72.1 (3)
O2—S1—C11—C12	−169.8 (2)	C2—C3—C7—C6	59.1 (2)
O2—S1—C11—C16	11.1 (3)	C4—C3—C7—C6	−48.7 (3)
C10—S1—C11—C12	74.2 (2)	C7—C3—C4—C5	32.7 (4)
C10—S1—C11—C16	−104.9 (2)	C3—C4—C5—C6	−0.1 (3)
C11—S1—C10—C9	43.2 (2)	C4—C5—C6—C1	69.8 (3)
C2—C1—C6—C5	−64.7 (3)	C4—C5—C6—C7	−32.6 (3)
C2—C1—C6—C7	39.6 (3)	C1—C6—C7—C3	−59.7 (2)
C6—C1—C2—C3	−3.2 (3)	C5—C6—C7—C3	48.9 (2)
C6—C1—C2—C8	−124.4 (2)	O3—C9—C10—S1	−117.1 (3)
C2—C1—C9—O3	0.7 (4)	C1—C9—C10—S1	64.4 (3)
C2—C1—C9—C10	179.0 (2)	S1—C11—C12—C13	−179.5 (3)
C9—C1—C2—C3	−127.0 (2)	S1—C11—C16—C15	−179.9 (2)
C9—C1—C2—C8	111.8 (3)	C12—C11—C16—C15	1.1 (5)
C6—C1—C9—O3	−118.1 (3)	C16—C11—C12—C13	−0.4 (5)
C6—C1—C9—C10	60.3 (3)	C11—C12—C13—C14	−0.1 (4)
C9—C1—C6—C5	60.4 (3)	C12—C13—C14—C15	−0.0 (5)
C9—C1—C6—C7	164.7 (2)	C13—C14—C15—C16	0.7 (6)
C1—C2—C3—C4	69.8 (3)	C14—C15—C16—C11	−1.2 (6)