endo-3,3-Dimethyl-4-oxobicyclo­[3.1.0]hexan-2-yl methane­sulfonate

Kremer, A.; Norberg, B.; Krief, A.; Wouters, J.

doi:10.1107/S1600536810010901

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o948

doi:10.1107/S1600536810010901

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endo-3,3-Dimethyl-4-oxobicyclo[3.1.0]hexan-2-yl methanesulfonate

Adrian Kremer,^a Bernadette Norberg,^a Alain Krief ^a and Johan Wouters ^a ^*

^aDepartment of Chemistry, University of Namur, 61 Rue de Bruxelles, B-5000 Namur, Belgium
^*Correspondence e-mail: johan.wouters@fundp.ac.be

(Received 19 March 2010; accepted 23 March 2010; online 27 March 2010)

The relative configuration of the endo isomer of the title compound, C₉H₁₄O₄S, has been established and the conformation of the diastereoisomer is discussed. The five-membered ring adopts an envelope conformation. The conformation of the methanesulfonate substituent is stabilized by intermolecular C—H⋯O hydrogen bonds. The crystal packing results in alternating layers of polar methanesulfonates and stacked bicyclohexanyl rings parallel to ab.

Related literature

For related enantioselective syntheses, see: Krief (1994 ); Krief et al. (2000 ). For puckering parameters and theoretical torsion angles, see: Cremer & Pople (1975 ); Dunitz (1979 ).

Experimental

Crystal data

C₉H₁₄O₄S
M_r = 218.27
Triclinic, $[P \overline 1]$
a = 5.8558 (3) Å
b = 7.7497 (4) Å
c = 12.2527 (6) Å
α = 84.290 (4)°
β = 79.531 (4)°
γ = 72.070 (5)°
V = 519.66 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.30 mm⁻¹
T = 293 K
0.35 × 0.14 × 0.12 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini ultra Mo) detector
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.904, T_max = 0.966
6128 measured reflections
3432 independent reflections
2283 reflections with I > 2σ(I)
R_int = 0.019

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.130
S = 0.99
3432 reflections
130 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O4ⁱ	0.98	2.48	3.302 (4)	141
C9—H9B⋯O2ⁱⁱ	0.96	2.54	3.485 (2)	169
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+1, -z+2.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97 .

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810010901/dn2550sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010901/dn2550Isup2.hkl

checkCIF report

Comment top

In the course of a work involving the enantioselective synthesis of didesmethyl-deltametrinic acid (Krief et al., 2000; Krief, 1994) both the exo and endo isomers of 3,3-dimethyl-4-oxobicyclo[3.1.0]hexan-2-yl methanesulfonate were synthesized and characterized.

The X-ray crystallography study reported here determined the relative stereochemistry of the endo diasteroisomer : C(1) S, C(4) R, and C(5) R. The compound crystallizing in a centrosymetric space group, one obtains the racemic mixture S,R,R/R,S,S.

The five-membered ring C1—C5 adopts an envelope conformation. Puckering parameter Phi is 260.1 (8)° and close to the expected value of k x 36° (Cremer & Pople, 1975), suggesting that the presence of a sp² carbon (C2) in the five-membered ring does not significantly distort its conformation. The observed values of torsion angles defining the C1—C5 ring (Table 1) fairly well follow the theoretical sequence of torsion angles -ω1, ω2, -ω2, ω1 and 0 (Dunitz, 1979) characteristic of an envelope conformation.

Atom C6 of the fused three-membered ring deviates by +1.250 (2) Å from the mean plane defined by the five atoms of the C1—C5 ring (Figure 1).

Steric effects resulting from C6 being in cis of the mesylate substituent on O2, constrain the conformation of the methanesulfonate group. Positions of the oxygen atoms O3 and O4 of the sulfonate group are further explained by intra and intermolecular CH···O hydrogen bondings. Indeed O3 forms an intramolecular H bond [O3···H4 = 2.81 Å] with H4 of C4 that carries the mesylate. An intermolecular H bond with H4 further involves O4 [C(4)—H4 ··· O4_i: D···A = 3.302 (4) Å; H···A = 2.48 Å; D - H···A = 141°, i = x-1,y,z].

Packing is also reinforced by van der Waals interactions resulting in alterning layers of polar methanesulfonates and stacked bicyclohexanyl rings parallel to the ab cell planes.

Related literature top

For related enantioselective syntheses, see : Krief (1994); Krief et al. (2000). For puckering parameters and theoretical torsion angles, see: Cremer & Pople (1975); Dunitz (1979).

Experimental top

Synthesis of the compound will be detailed elsewhere.

Crystals were obtained by evaporation at 5°C of solutions in diethylether.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Conformation (ORTEP view) of the title compound. Only H atoms on chiral carbons have been retained for clarity. Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.

endo-3,3-Dimethyl-4-oxobicyclo[3.1.0]hexan-2-yl methanesulfonate top

Crystal data top

C₉H₁₄O₄S	Z = 2
M_r = 218.27	F(000) = 232
Triclinic, P1	D_x = 1.395 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8558 (3) Å	Cell parameters from 2686 reflections
b = 7.7497 (4) Å	θ = 3.2–32.6°
c = 12.2527 (6) Å	µ = 0.30 mm⁻¹
α = 84.290 (4)°	T = 293 K
β = 79.531 (4)°	Prism, colorless
γ = 72.070 (5)°	0.35 × 0.14 × 0.12 mm
V = 519.66 (5) Å³

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini ultra Mo) detector	3432 independent reflections
Radiation source: fine-focus sealed tube	2283 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 10.3712 pixels mm^-1	θ_max = 32.6°, θ_min = 3.2°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −8→11
T_min = 0.904, T_max = 0.966	l = −18→18
6128 measured reflections

Refinement top

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0721P)²] where P = (F_o² + 2F_c²)/3
3432 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.36 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₉H₁₄O₄S	γ = 72.070 (5)°
M_r = 218.27	V = 519.66 (5) Å³
Triclinic, P1	Z = 2
a = 5.8558 (3) Å	Mo Kα radiation
b = 7.7497 (4) Å	µ = 0.30 mm⁻¹
c = 12.2527 (6) Å	T = 293 K
α = 84.290 (4)°	0.35 × 0.14 × 0.12 mm
β = 79.531 (4)°

Data collection top

Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini ultra Mo) detector	3432 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	2283 reflections with I > 2σ(I)
T_min = 0.904, T_max = 0.966	R_int = 0.019
6128 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 0.99	Δρ_max = 0.36 e Å⁻³
3432 reflections	Δρ_min = −0.31 e Å⁻³
130 parameters

Special details top

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 > 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.1819 (3)	0.4668 (2)	0.66360 (15)	0.0492 (4)
H1	0.0668	0.4050	0.6508	0.059*
C2	0.1965 (3)	0.6346 (2)	0.59887 (13)	0.0422 (3)
C3	0.2668 (3)	0.75983 (19)	0.66753 (13)	0.0377 (3)
C4	0.2405 (3)	0.6746 (2)	0.78727 (12)	0.0383 (3)
H4	0.0950	0.7502	0.8323	0.046*
C5	0.2143 (3)	0.4885 (2)	0.78131 (14)	0.0474 (4)
H5	0.1187	0.4400	0.8439	0.057*
C6	0.4088 (4)	0.3618 (2)	0.70955 (15)	0.0534 (4)
H6A	0.4345	0.2330	0.7265	0.064*
H6B	0.5558	0.3956	0.6814	0.064*
C7	0.5212 (3)	0.7725 (3)	0.61787 (15)	0.0556 (5)
H7A	0.6366	0.6539	0.6194	0.083*
H7B	0.5646	0.8515	0.6606	0.083*
H7C	0.5216	0.8202	0.5425	0.083*
C8	0.0812 (4)	0.9504 (2)	0.66350 (19)	0.0642 (5)
H8A	0.1226	1.0300	0.7066	0.096*
H8B	−0.0787	0.9425	0.6935	0.096*
H8C	0.0843	0.9972	0.5879	0.096*
C9	0.2608 (3)	0.7738 (2)	1.04091 (14)	0.0503 (4)
H9A	0.2548	0.8619	1.0920	0.075*
H9B	0.3173	0.6540	1.0740	0.075*
H9C	0.1012	0.7930	1.0235	0.075*
O1	0.1502 (3)	0.67456 (18)	0.50596 (10)	0.0606 (4)
O2	0.4535 (2)	0.64888 (14)	0.84223 (9)	0.0421 (3)
O3	0.3691 (3)	0.97232 (17)	0.87030 (11)	0.0717 (4)
O4	0.7018 (2)	0.7375 (2)	0.94357 (12)	0.0761 (5)
S1	0.45905 (8)	0.79673 (6)	0.91953 (3)	0.04398 (14)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0598 (11)	0.0458 (9)	0.0546 (10)	−0.0288 (8)	−0.0180 (8)	−0.0019 (7)
C2	0.0405 (8)	0.0438 (8)	0.0452 (8)	−0.0140 (7)	−0.0116 (6)	−0.0025 (7)
C3	0.0408 (8)	0.0344 (7)	0.0426 (8)	−0.0156 (6)	−0.0133 (6)	0.0027 (6)
C4	0.0353 (7)	0.0398 (8)	0.0421 (8)	−0.0143 (6)	−0.0058 (6)	−0.0031 (6)
C5	0.0589 (10)	0.0487 (9)	0.0438 (9)	−0.0314 (8)	−0.0089 (7)	0.0059 (7)
C6	0.0680 (12)	0.0369 (8)	0.0601 (11)	−0.0172 (8)	−0.0211 (9)	0.0017 (7)
C7	0.0600 (11)	0.0673 (12)	0.0508 (10)	−0.0390 (10)	−0.0052 (8)	0.0036 (9)
C8	0.0767 (14)	0.0400 (9)	0.0783 (13)	−0.0074 (9)	−0.0359 (11)	−0.0025 (9)
C9	0.0526 (10)	0.0515 (10)	0.0414 (8)	−0.0116 (8)	0.0001 (7)	−0.0030 (7)
O1	0.0771 (9)	0.0638 (8)	0.0499 (7)	−0.0244 (7)	−0.0290 (6)	0.0015 (6)
O2	0.0476 (6)	0.0399 (6)	0.0409 (6)	−0.0116 (5)	−0.0131 (5)	−0.0061 (4)
O3	0.1261 (14)	0.0447 (7)	0.0544 (8)	−0.0425 (8)	−0.0113 (8)	0.0004 (6)
O4	0.0484 (8)	0.1248 (13)	0.0661 (9)	−0.0348 (8)	−0.0039 (6)	−0.0363 (9)
S1	0.0507 (3)	0.0491 (2)	0.0385 (2)	−0.02405 (19)	−0.00324 (16)	−0.00920 (16)

Geometric parameters (Å, º) top

C1—C2	1.472 (2)	C6—H6B	0.9700
C1—C6	1.503 (2)	C7—H7A	0.9600
C1—C5	1.521 (2)	C7—H7B	0.9600
C1—H1	0.9800	C7—H7C	0.9600
C2—O1	1.2066 (19)	C8—H8A	0.9600
C2—C3	1.534 (2)	C8—H8B	0.9600
C3—C7	1.532 (2)	C8—H8C	0.9600
C3—C8	1.543 (2)	C9—S1	1.7429 (17)
C3—C4	1.549 (2)	C9—H9A	0.9600
C4—O2	1.4747 (17)	C9—H9B	0.9600
C4—C5	1.506 (2)	C9—H9C	0.9600
C4—H4	0.9800	O2—S1	1.5687 (11)
C5—C6	1.467 (3)	O3—S1	1.4156 (14)
C5—H5	0.9800	O4—S1	1.4287 (14)
C6—H6A	0.9700

C2—C1—C6	114.72 (14)	C1—C6—H6A	117.6
C2—C1—C5	107.13 (13)	C5—C6—H6B	117.6
C6—C1—C5	58.06 (11)	C1—C6—H6B	117.6
C2—C1—H1	120.3	H6A—C6—H6B	114.7
C6—C1—H1	120.3	C3—C7—H7A	109.5
C5—C1—H1	120.3	C3—C7—H7B	109.5
O1—C2—C1	125.52 (15)	H7A—C7—H7B	109.5
O1—C2—C3	123.47 (14)	C3—C7—H7C	109.5
C1—C2—C3	110.94 (13)	H7A—C7—H7C	109.5
C7—C3—C2	109.53 (13)	H7B—C7—H7C	109.5
C7—C3—C8	109.33 (15)	C3—C8—H8A	109.5
C2—C3—C8	108.62 (13)	C3—C8—H8B	109.5
C7—C3—C4	115.62 (13)	H8A—C8—H8B	109.5
C2—C3—C4	103.93 (11)	C3—C8—H8C	109.5
C8—C3—C4	109.53 (14)	H8A—C8—H8C	109.5
O2—C4—C5	106.44 (12)	H8B—C8—H8C	109.5
O2—C4—C3	113.84 (11)	S1—C9—H9A	109.5
C5—C4—C3	108.08 (12)	S1—C9—H9B	109.5
O2—C4—H4	109.5	H9A—C9—H9B	109.5
C5—C4—H4	109.5	S1—C9—H9C	109.5
C3—C4—H4	109.5	H9A—C9—H9C	109.5
C6—C5—C4	116.56 (15)	H9B—C9—H9C	109.5
C6—C5—C1	60.38 (11)	C4—O2—S1	120.23 (9)
C4—C5—C1	108.34 (13)	O3—S1—O4	119.56 (10)
C6—C5—H5	119.1	O3—S1—O2	110.12 (7)
C4—C5—H5	119.1	O4—S1—O2	103.74 (8)
C1—C5—H5	119.1	O3—S1—C9	108.61 (9)
C5—C6—C1	61.56 (12)	O4—S1—C9	108.62 (9)
C5—C6—H6A	117.6	O2—S1—C9	105.24 (8)

C6—C1—C2—O1	127.22 (19)	C8—C3—C4—C5	128.36 (15)
C5—C1—C2—O1	−170.65 (18)	O2—C4—C5—C6	−66.42 (17)
C6—C1—C2—C3	−55.74 (19)	C3—C4—C5—C6	56.24 (18)
C5—C1—C2—C3	6.39 (18)	O2—C4—C5—C1	−131.81 (14)
O1—C2—C3—C7	−70.5 (2)	C3—C4—C5—C1	−9.15 (18)
C1—C2—C3—C7	112.43 (15)	C2—C1—C5—C6	−108.87 (16)
O1—C2—C3—C8	48.9 (2)	C2—C1—C5—C4	1.83 (19)
C1—C2—C3—C8	−128.22 (16)	C6—C1—C5—C4	110.70 (16)
O1—C2—C3—C4	165.44 (17)	C4—C5—C6—C1	−96.92 (16)
C1—C2—C3—C4	−11.67 (17)	C2—C1—C6—C5	95.46 (16)
C7—C3—C4—O2	10.41 (18)	C5—C4—O2—S1	−146.30 (11)
C2—C3—C4—O2	130.47 (12)	C3—C4—O2—S1	94.74 (13)
C8—C3—C4—O2	−113.62 (15)	C4—O2—S1—O3	−42.98 (13)
C7—C3—C4—C5	−107.61 (15)	C4—O2—S1—O4	−172.07 (11)
C2—C3—C4—C5	12.45 (16)	C4—O2—S1—C9	73.90 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4ⁱ	0.98	2.48	3.302 (4)	141
C9—H9B···O2ⁱⁱ	0.96	2.54	3.485 (2)	169

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₉H₁₄O₄S
M_r	218.27
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	5.8558 (3), 7.7497 (4), 12.2527 (6)
α, β, γ (°)	84.290 (4), 79.531 (4), 72.070 (5)
V (Å³)	519.66 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.35 × 0.14 × 0.12

Data collection
Diffractometer	Oxford Diffraction Xcalibur diffractometer with a Ruby (Gemini ultra Mo) detector
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.904, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	6128, 3432, 2283
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.759

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.130, 0.99
No. of reflections	3432
No. of parameters	130
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.31

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and PLATON (Spek, 2009).

Selected torsion angles (º) top

C5—C1—C2—C3	6.39 (18)	C2—C1—C5—C4	1.83 (19)
C1—C2—C3—C4	−11.67 (17)	C3—C4—O2—S1	94.74 (13)
C2—C3—C4—C5	12.45 (16)	C4—O2—S1—C9	73.90 (12)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O4ⁱ	0.98	2.48	3.302 (4)	141
C9—H9B···O2ⁱⁱ	0.96	2.54	3.485 (2)	169

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y+1, −z+2.

Acknowledgements

This work was supported in part by the Fonds National de la Recherche Scientifique (FNRS, Belgium).

References

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