(1R,2R,3R,4S,5S)-3-Methyl-8-oxa-bicyclo-[3.2.1]oct-6-ene-2,4-diyl diacetate.

The mol-ecule of the title compound, C(12)H(16)O(5), has crystallographically imposed mirror symmetry with the mirror plane passing through the endocyclic O atom and the mid-point of the double bond. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming chains running along the a axis.

Related literature

Compounds containing the 8-oxabicyclo­[3.2.1]octane framework have shown broad utility as chiral building blocks for synthesis of polyketides, see: Coste & Gerber-Lemaire (2005 ▶); Meilert et al. (2003 ▶); Schwenter & Vogel (2001 ▶); Gerber-Lemaire & Vogel (2003 ▶); Gerber & Vogel (1999 ▶, 2001 ▶); Re et al. (2009 ▶); Pascual et al. (2004 ▶); Derwick (1998 ▶). For the inhibitory activity of calystegines and other tropane alkaloids against several glycosidase enzymes, see: Asano et al. (2000 ▶); Drager (2004 ▶). Several 8-oxabicyclo­[3.2.1] octane derivatives possess moderate anti-HIV activity, see: Montana et al. (2009 ▶). For the syntheses of a full set of hybrid d- and l-C-glycosides and thymine polyoxin C starting with the unsaturated 8-oxabicyclo­[3.2.1]octane framework, see: Gethin & Simpkins (1997 ▶); Hoffmann et al. (2001 ▶). For the synthesis of an 8-oxabicyclo­[3.2.1]octane from tetra­chloro­cyclo­propene and furan, see: Batson et al. (2004 ▶). For a synthetic approach to 8-oxabicyclo­[3.2.1]octane derivatives based on the reaction of tetra­chloro­cyclo­propene with furan, see: Law & Tobey (1968 ▶). For structures of related 8-oxabicyclo­[3.2.1]octa­nes, see: Kreiselmeier et al. (2006 ▶); Hoffmann et al. (2001 ▶). For a report of prior research, see: Tafeenko et al. (2009 ▶).

Experimental

Crystal data

C12H16O5

M = 240.25

Orthorhombic,

a = 6.8680 (12) Å

b = 12.295 (4) Å

c = 14.120 (3) Å

V = 1192.3 (5) Å3

Z = 4

Ag Kα radiation

λ = 0.56085 Å

μ = 0.06 mm−1

T = 296 K

0.1 × 0.07 × 0.05 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

1974 measured reflections

1974 independent reflections

1085 reflections with I > 2s(I)

2 standard reflections every 120 min intensity decay: none

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.138

S = 1.02

1974 reflections

91 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.17 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2000 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811027292/mw2015sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027292/mw2015Isup2.hkl

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

C12H16O5	Dx = 1.338 Mg m−3
Mr = 240.25	Melting point: 428 K
Orthorhombic, Pnma	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -P 2ac 2n	Cell parameters from 25 reflections
a = 6.8680 (12) Å	θ = 11–14°
b = 12.295 (4) Å	µ = 0.06 mm−1
c = 14.120 (3) Å	T = 296 K
V = 1192.3 (5) Å3	Prism, colorless
Z = 4	0.1 × 0.07 × 0.05 mm
F(000) = 512

Enraf–Nonius CAD-4 diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 24.0°, θmin = 1.7°
graphite	h = −9→0
non–profiled ω scans	k = −17→0
1974 measured reflections	l = −20→0
1974 independent reflections	2 standard reflections every 120 min
1085 reflections with I > 2s(I)	intensity decay: none

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.055	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.138	w = 1/[σ2(Fo2) + (0.0492P)2 + 0.2946P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
1974 reflections	Δρmax = 0.24 e Å−3
91 parameters	Δρmin = −0.17 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.031 (4)

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
O1	0.74430 (17)	0.55206 (10)	0.09878 (9)	0.0459 (4)
O2	1.06414 (18)	0.53353 (12)	0.12399 (11)	0.0604 (4)
O8	0.6552 (3)	0.7500	−0.08400 (12)	0.0550 (5)
C1	0.6076 (3)	0.65913 (15)	−0.02489 (13)	0.0479 (5)
H1	0.5863	0.5928	−0.0619	0.057*
C2	0.7802 (2)	0.64791 (14)	0.04233 (12)	0.0409 (4)
H2	0.8972	0.6349	0.0042	0.049*
C3	0.8160 (3)	0.7500	0.10391 (17)	0.0382 (6)
H3	0.9552	0.7500	0.1193	0.046*
C6	0.4243 (3)	0.69639 (16)	0.02399 (13)	0.0510 (5)
H6	0.3285	0.6518	0.0496	0.061*
C8	0.7082 (5)	0.7500	0.19833 (19)	0.0494 (7)
C9	0.9005 (3)	0.50142 (15)	0.13532 (13)	0.0451 (4)
C10	0.8443 (3)	0.40349 (17)	0.18986 (17)	0.0647 (6)
H10A	0.9539	0.3554	0.1947	0.097*
H10B	0.7395	0.3669	0.1581	0.097*
H10C	0.8029	0.4246	0.2521	0.097*
H8	0.749 (3)	0.8125 (16)	0.2358 (16)	0.071 (7)*
H81	0.575 (5)	0.7500	0.194 (3)	0.092 (12)*

	U11	U22	U33	U12	U13	U23
O1	0.0411 (6)	0.0396 (7)	0.0569 (8)	−0.0008 (6)	0.0002 (6)	0.0067 (6)
O2	0.0422 (8)	0.0569 (9)	0.0820 (10)	0.0018 (7)	0.0016 (7)	0.0071 (8)
O8	0.0746 (13)	0.0542 (11)	0.0362 (9)	0.000	−0.0022 (10)	0.000
C1	0.0580 (11)	0.0423 (10)	0.0434 (9)	−0.0048 (9)	−0.0061 (9)	−0.0032 (8)
C2	0.0420 (9)	0.0387 (9)	0.0420 (9)	−0.0002 (7)	0.0056 (8)	0.0006 (8)
C3	0.0330 (11)	0.0392 (13)	0.0425 (13)	0.000	0.0001 (10)	0.000
C6	0.0403 (9)	0.0602 (11)	0.0524 (11)	−0.0044 (8)	−0.0128 (8)	0.0003 (10)
C8	0.0507 (17)	0.0601 (18)	0.0374 (14)	0.000	0.0003 (13)	0.000
C9	0.0494 (10)	0.0372 (9)	0.0487 (10)	0.0021 (9)	0.0002 (8)	−0.0051 (9)
C10	0.0650 (13)	0.0516 (12)	0.0775 (15)	−0.0036 (11)	−0.0095 (12)	0.0119 (11)

O1—C9	1.344 (2)	C3—C2i	1.547 (2)
O1—C2	1.444 (2)	C3—H3	0.9800
O2—C9	1.202 (2)	C6—C6i	1.318 (4)
O8—C1	1.432 (2)	C6—H6	0.9300
C1—C6	1.507 (2)	C8—H8	0.97 (2)
C1—C2	1.525 (2)	C8—H81	0.92 (4)
C1—H1	0.9800	C9—C10	1.481 (3)
C2—C3	1.547 (2)	C10—H10A	0.9600
C2—H2	0.9800	C10—H10B	0.9600
C3—C8	1.525 (4)	C10—H10C	0.9600
C9—O1—C2	116.98 (13)	C2—C3—H3	106.2
C1i—O8—C1	102.51 (19)	C2i—C3—H3	106.2
O8—C1—C6	102.74 (16)	C6i—C6—C1	107.70 (10)
O8—C1—C2	104.80 (15)	C6i—C6—H6	126.1
C6—C1—C2	113.07 (14)	C1—C6—H6	126.1
O8—C1—H1	111.9	C3—C8—H8	109.7 (13)
C6—C1—H1	111.9	C3—C8—H81	115 (2)
C2—C1—H1	111.9	H8—C8—H81	108.8 (18)
O1—C2—C1	106.53 (14)	O2—C9—O1	122.91 (17)
O1—C2—C3	112.28 (14)	O2—C9—C10	125.48 (18)
C1—C2—C3	113.59 (15)	O1—C9—C10	111.60 (16)
O1—C2—H2	108.1	C9—C10—H10A	109.5
C1—C2—H2	108.1	C9—C10—H10B	109.5
C3—C2—H2	108.1	H10A—C10—H10B	109.5
C8—C3—C2	114.47 (13)	C9—C10—H10C	109.5
C8—C3—C2i	114.47 (13)	H10A—C10—H10C	109.5
C2—C3—C2i	108.50 (19)	H10B—C10—H10C	109.5
C8—C3—H3	106.2
C1i—O8—C1—C6	38.7 (2)	O1—C2—C3—C8	−30.9 (2)
C1i—O8—C1—C2	−79.64 (19)	C1—C2—C3—C8	90.0 (2)
C9—O1—C2—C1	154.76 (15)	O1—C2—C3—C2i	−160.12 (11)
C9—O1—C2—C3	−80.30 (19)	C1—C2—C3—C2i	−39.2 (2)
O8—C1—C2—O1	−175.93 (13)	O8—C1—C6—C6i	−24.28 (13)
C6—C1—C2—O1	72.93 (19)	C2—C1—C6—C6i	88.12 (14)
O8—C1—C2—C3	59.93 (19)	C2—O1—C9—O2	1.2 (3)
C6—C1—C2—C3	−51.2 (2)	C2—O1—C9—C10	−178.85 (15)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···O2ii	0.93	2.55	3.482 (2)	178

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯O2i	0.93	2.55	3.482 (2)	178

Symmetry code: (i) .