The 2-exo,7-exo,9-exo,10-exo isomer of 11-oxatricyclo­[6.2.1.0^2,7]undec-4-ene-9,10-di­yl diacetate

The title compound, (2-exo,7-exo,9-exo,10-exo)-11-oxa­tri­cyclo­[6.2.1.0^2,7]undec-4-ene-9,10-di­yl diacetate, C₁₄H₁₈O₅, was synthesized in the same way as its 9-endo,10-endo isomer. The X-ray study showed that the Diels–Alder reaction of 5-exo,6-exo-diacetato-7-oxabicylclo[2.2.1]hepta-2-ene with 3-sulfolene, a protected 1,3-butadiene, yields the 2-exo,7-exo product, i.e. reacts in the same way as the 5-endo,6-endo isomer of the starting compound. Inter­molecular C—H...O inter­actions link the mol­ecules into infinite chains extending along the b axis of the monoclinic crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 150 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.045
• wR factor = 0.127
• Data-to-parameter ratio = 11.4

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSMU01_ALERT_1_C  The ratio of given/expected absorption coefficient lies
               outside the range 0.99 <> 1.01
            Calculated value of mu =     0.103
            Value of mu given      =     0.100
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.86 Ratio

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

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

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Computing details

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

(2-exo,7-exo,9-exo,10-exo)-11-oxatricyclo[6.2.1.0^2,7]undec-4-ene-9,10-diyl diacetate

Crystal data

C14H18O5	F(000) = 568
Mr = 266.28	Dx = 1.363 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9643 reflections
a = 13.9144 (13) Å	θ = 1.5–27.6°
b = 5.5055 (4) Å	µ = 0.10 mm^−1
c = 17.8016 (17) Å	T = 150 K
β = 107.858 (8)°	Prism, colourless
V = 1298.0 (2) Å^3	0.55 × 0.50 × 0.44 mm
Z = 4

Data collection

Stoe IPDS-II diffractometer	2247 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	Rint = 0.075
Plane graphite monochromator	θmax = 26.0°, θmin = 1.6°
Detector resolution: 6.67 pixels mm^-1	h = −17→17
ω scans	k = −6→6
9038 measured reflections	l = −21→21
2534 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.127	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0754P)^2 + 0.3715P] where P = (Fo^2 + 2Fc^2)/3
2534 reflections	(Δ/σ)max = 0.012
222 parameters	Δρmax = 0.33 e Å^−3
0 restraints	Δρmin = −0.37 e Å^−3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F² for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating -R-factor-obs 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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.55155 (7)	0.57577 (17)	0.40458 (6)	0.0218 (3)
O2	0.75128 (7)	0.48878 (19)	0.51571 (6)	0.0252 (3)
O3	0.75031 (8)	0.64905 (18)	0.37962 (6)	0.0250 (3)
O4	0.89286 (8)	0.3155 (2)	0.50554 (8)	0.0399 (4)
O5	0.82928 (8)	0.5045 (2)	0.29562 (7)	0.0338 (3)
C1	0.69316 (10)	0.3330 (2)	0.45333 (8)	0.0215 (4)
C2	0.58242 (10)	0.3566 (2)	0.44961 (8)	0.0204 (4)
C3	0.51975 (10)	0.1605 (2)	0.39522 (8)	0.0209 (4)
C4	0.41319 (11)	0.1406 (3)	0.40322 (9)	0.0280 (4)
C5	0.34472 (11)	0.0124 (3)	0.33280 (9)	0.0289 (4)
C6	0.34344 (11)	0.0862 (3)	0.26182 (9)	0.0284 (4)
C7	0.41035 (11)	0.2956 (3)	0.25629 (9)	0.0270 (4)
C8	0.51825 (10)	0.2577 (2)	0.31258 (8)	0.0210 (4)
C9	0.57758 (10)	0.4958 (2)	0.33601 (8)	0.0218 (4)
C10	0.68971 (10)	0.4330 (2)	0.37033 (8)	0.0213 (4)
C11	0.85288 (11)	0.4702 (3)	0.53274 (9)	0.0279 (4)
C12	0.90552 (12)	0.6688 (3)	0.58726 (10)	0.0362 (5)
C13	0.81956 (10)	0.6594 (3)	0.34039 (8)	0.0233 (4)
C14	0.88125 (11)	0.8854 (3)	0.36127 (9)	0.0290 (4)
H1	0.7194 (14)	0.170 (4)	0.4608 (11)	0.028 (4)*
H2	0.5722 (12)	0.376 (3)	0.4997 (10)	0.019 (4)*
H3	0.5524 (13)	0.003 (3)	0.4061 (10)	0.022 (4)*
H4A	0.4175 (14)	0.056 (3)	0.4543 (11)	0.032 (5)*
H4B	0.3862 (16)	0.311 (4)	0.4050 (13)	0.044 (5)*
H5	0.3033 (15)	−0.124 (4)	0.3404 (12)	0.039 (5)*
H6	0.3024 (14)	0.009 (3)	0.2122 (11)	0.028 (4)*
H7A	0.4142 (14)	0.315 (4)	0.2012 (11)	0.033 (5)*
H7B	0.3831 (13)	0.444 (3)	0.2732 (10)	0.027 (4)*
H8	0.5530 (12)	0.146 (3)	0.2881 (9)	0.014 (4)*
H9	0.5645 (13)	0.622 (3)	0.2963 (11)	0.026 (4)*
H10	0.7126 (12)	0.318 (3)	0.3372 (10)	0.022 (4)*
H12A	0.86760	0.70880	0.62240	0.0540*
H12B	0.91090	0.80960	0.55700	0.0540*
H12C	0.97180	0.61530	0.61730	0.0540*
H14A	0.86810	0.96250	0.40550	0.0430*
H14B	0.86370	0.99410	0.31700	0.0430*
H14C	0.95160	0.84490	0.37480	0.0430*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0230 (5)	0.0165 (5)	0.0267 (5)	0.0018 (4)	0.0088 (4)	−0.0010 (4)
O2	0.0205 (5)	0.0293 (6)	0.0241 (5)	−0.0036 (4)	0.0042 (4)	−0.0045 (4)
O3	0.0237 (5)	0.0234 (5)	0.0307 (5)	−0.0060 (4)	0.0127 (4)	−0.0040 (4)
O4	0.0231 (6)	0.0416 (7)	0.0504 (7)	0.0014 (5)	0.0045 (5)	−0.0092 (6)
O5	0.0351 (6)	0.0342 (6)	0.0387 (6)	−0.0070 (5)	0.0211 (5)	−0.0069 (5)
C1	0.0196 (7)	0.0191 (7)	0.0242 (7)	−0.0005 (5)	0.0045 (5)	−0.0025 (5)
C2	0.0203 (7)	0.0189 (7)	0.0222 (7)	0.0002 (5)	0.0068 (5)	0.0000 (5)
C3	0.0200 (6)	0.0179 (7)	0.0233 (6)	−0.0004 (5)	0.0045 (5)	0.0001 (5)
C4	0.0234 (7)	0.0340 (8)	0.0269 (7)	−0.0072 (6)	0.0080 (6)	0.0002 (6)
C5	0.0215 (7)	0.0279 (8)	0.0350 (8)	−0.0053 (6)	0.0054 (6)	−0.0005 (6)
C6	0.0199 (6)	0.0303 (8)	0.0312 (7)	−0.0005 (6)	0.0024 (6)	−0.0053 (6)
C7	0.0217 (7)	0.0311 (8)	0.0254 (7)	0.0008 (6)	0.0030 (5)	0.0021 (6)
C8	0.0188 (6)	0.0217 (7)	0.0221 (6)	0.0004 (5)	0.0056 (5)	−0.0021 (5)
C9	0.0230 (7)	0.0202 (7)	0.0230 (7)	0.0003 (5)	0.0081 (5)	0.0014 (5)
C10	0.0202 (7)	0.0194 (6)	0.0253 (7)	−0.0032 (5)	0.0085 (5)	−0.0028 (5)
C11	0.0216 (7)	0.0319 (8)	0.0272 (7)	−0.0027 (6)	0.0031 (6)	0.0017 (6)
C12	0.0299 (8)	0.0424 (9)	0.0317 (8)	−0.0109 (7)	0.0025 (6)	−0.0052 (7)
C13	0.0191 (6)	0.0282 (7)	0.0228 (7)	0.0001 (5)	0.0066 (5)	0.0035 (5)
C14	0.0256 (7)	0.0311 (8)	0.0307 (7)	−0.0059 (6)	0.0093 (6)	−0.0003 (6)

Geometric parameters (Å, º)

O1—C2	1.4394 (15)	C13—C14	1.493 (2)
O1—C9	1.4444 (17)	C1—H1	0.96 (2)
O2—C1	1.4394 (16)	C2—H2	0.951 (17)
O2—C11	1.3558 (19)	C3—H3	0.971 (17)
O3—C10	1.4379 (16)	C4—H4A	1.007 (18)
O3—C13	1.3536 (18)	C4—H4B	1.02 (2)
O4—C11	1.198 (2)	C5—H5	0.98 (2)
O5—C13	1.2029 (19)	C6—H6	0.989 (18)
C1—C2	1.527 (2)	C7—H7A	1.004 (19)
C1—C10	1.5637 (19)	C7—H7B	0.986 (17)
C2—C3	1.5316 (18)	C8—H8	0.965 (17)
C3—C4	1.536 (2)	C9—H9	0.968 (18)
C3—C8	1.5596 (19)	C10—H10	0.983 (17)
C4—C5	1.498 (2)	C12—H12A	0.9600
C5—C6	1.322 (2)	C12—H12B	0.9600
C6—C7	1.504 (2)	C12—H12C	0.9600
C7—C8	1.542 (2)	C14—H14A	0.9600
C8—C9	1.5371 (17)	C14—H14B	0.9600
C9—C10	1.531 (2)	C14—H14C	0.9600
C11—C12	1.496 (2)
O1···O2	2.9145 (15)	C7···H4B	2.77 (2)
O1···O3	2.9602 (16)	C9···H14B^ii	3.0700
O1···C3^i	3.2468 (15)	H1···O4	2.43 (2)
O2···O1	2.9145 (15)	H1···H3	2.41 (3)
O2···O3	2.5745 (15)	H2···O1^iii	2.782 (17)
O3···O1	2.9602 (16)	H2···C2^iii	2.967 (17)
O3···C11	2.8373 (19)	H2···H2^iii	2.43 (2)
O3···O2	2.5745 (15)	H2···H4A^ix	2.51 (2)
O3···O4	3.0991 (16)	H2···H4B^iii	2.36 (3)
O4···C13	3.381 (2)	H3···O1^iv	2.352 (17)
O4···O3	3.0991 (16)	H3···H1	2.41 (3)
O4···C10	3.1669 (19)	H3···H4A^ix	2.41 (3)
O5···C13^ii	3.2689 (19)	H4A···C2^ix	2.843 (17)
O1···H3^i	2.352 (17)	H4A···C3^ix	2.815 (18)
O1···H4B	2.73 (2)	H4A···C4^ix	3.081 (19)
O1···H7B	2.851 (18)	H4A···H2^ix	2.51 (2)
O1···H2^iii	2.782 (17)	H4A···H3^ix	2.41 (3)
O2···H4B^iii	2.92 (2)	H4A···H4A^ix	2.45 (3)
O4···H12B^iv	2.9200	H4B···O1	2.73 (2)
O4···H14A^iv	2.5900	H4B···C7	2.77 (2)
O4···H1	2.43 (2)	H4B···H7B	2.45 (3)
O4···H14C^v	2.6800	H4B···O2^iii	2.92 (2)
O5···H10	2.231 (17)	H4B···C2^iii	3.09 (2)
O5···H14B^iv	2.8600	H4B···H2^iii	2.36 (3)
O5···H8^vi	2.647 (17)	H5···C6^vii	2.78 (2)
O5···H10^vi	2.840 (17)	H5···C7^vii	2.98 (2)
O5···H14B^ii	2.8200	H5···H6^vii	2.51 (3)
O5···H12C^v	2.8000	H6···H5^viii	2.51 (3)
C3···O1^iv	3.2468 (15)	H6···H12A^x	2.3900
C5···C6^vii	3.535 (2)	H7B···O1	2.851 (18)
C6···C5^viii	3.535 (2)	H7B···C4	2.780 (17)
C10···O4	3.1669 (19)	H7B···H4B	2.45 (3)
C11···C13	3.472 (2)	H8···H10	2.32 (2)
C11···O3	2.8373 (19)	H8···O5^ii	2.647 (17)
C13···O5^vi	3.2689 (19)	H10···O5	2.231 (17)
C13···O4	3.381 (2)	H10···H8	2.32 (2)
C13···C11	3.472 (2)	H10···O5^ii	2.840 (17)
C2···H4A^ix	2.843 (17)	H12A···C6^xi	3.0700
C2···H2^iii	2.967 (17)	H12A···H6^xi	2.3900
C2···H4B^iii	3.09 (2)	H12B···O4^i	2.9200
C3···H4A^ix	2.815 (18)	H12C···O5^v	2.8000
C4···H4A^ix	3.081 (19)	H14A···O4^i	2.5900
C4···H7B	2.780 (17)	H14B···O5^i	2.8600
C6···H5^viii	2.78 (2)	H14B···O5^vi	2.8200
C6···H12A^x	3.0700	H14B···C9^vi	3.0700
C7···H5^viii	2.98 (2)	H14C···O4^v	2.6800
C2—O1—C9	96.07 (9)	C4—C3—H3	108.9 (11)
C1—O2—C11	115.35 (11)	C8—C3—H3	111.4 (10)
C10—O3—C13	117.43 (11)	C3—C4—H4A	109.0 (12)
O2—C1—C2	107.66 (10)	C3—C4—H4B	108.3 (13)
O2—C1—C10	111.49 (10)	C5—C4—H4A	112.6 (10)
C2—C1—C10	101.00 (11)	C5—C4—H4B	108.4 (13)
O1—C2—C1	102.72 (10)	H4A—C4—H4B	108.6 (16)
O1—C2—C3	102.95 (10)	C4—C5—H5	119.7 (12)
C1—C2—C3	109.80 (11)	C6—C5—H5	122.1 (12)
C2—C3—C4	111.73 (11)	C5—C6—H6	123.8 (11)
C2—C3—C8	101.23 (10)	C7—C6—H6	118.1 (11)
C4—C3—C8	112.20 (12)	C6—C7—H7A	111.4 (12)
C3—C4—C5	109.89 (12)	C6—C7—H7B	108.2 (11)
C4—C5—C6	118.27 (15)	C8—C7—H7A	108.4 (12)
C5—C6—C7	118.10 (14)	C8—C7—H7B	107.6 (10)
C6—C7—C8	110.64 (12)	H7A—C7—H7B	110.5 (16)
C3—C8—C7	112.83 (12)	C3—C8—H8	110.1 (9)
C3—C8—C9	100.72 (10)	C7—C8—H8	108.4 (10)
C7—C8—C9	113.31 (11)	C9—C8—H8	111.4 (10)
O1—C9—C8	103.67 (11)	O1—C9—H9	111.0 (11)
O1—C9—C10	102.75 (11)	C8—C9—H9	116.7 (11)
C8—C9—C10	108.22 (10)	C10—C9—H9	113.2 (11)
O3—C10—C1	109.61 (10)	O3—C10—H10	108.4 (10)
O3—C10—C9	110.43 (10)	C1—C10—H10	114.8 (10)
C1—C10—C9	100.89 (11)	C9—C10—H10	112.6 (10)
O2—C11—O4	123.02 (15)	C11—C12—H12A	109.00
O2—C11—C12	111.07 (13)	C11—C12—H12B	109.00
O4—C11—C12	125.90 (15)	C11—C12—H12C	109.00
O3—C13—O5	123.68 (14)	H12A—C12—H12B	109.00
O3—C13—C14	110.65 (13)	H12A—C12—H12C	110.00
O5—C13—C14	125.67 (14)	H12B—C12—H12C	109.00
O2—C1—H1	110.5 (12)	C13—C14—H14A	109.00
C2—C1—H1	114.9 (12)	C13—C14—H14B	109.00
C10—C1—H1	111.1 (11)	C13—C14—H14C	109.00
O1—C2—H2	108.9 (10)	H14A—C14—H14B	109.00
C1—C2—H2	114.1 (11)	H14A—C14—H14C	109.00
C3—C2—H2	116.9 (10)	H14B—C14—H14C	110.00
C2—C3—H3	111.3 (10)
C2—O1—C9—C8	55.66 (11)	O1—C2—C3—C8	36.14 (13)
C2—O1—C9—C10	−56.98 (10)	O1—C2—C3—C4	−83.45 (13)
C9—O1—C2—C1	57.32 (11)	C4—C3—C8—C7	−3.70 (15)
C9—O1—C2—C3	−56.77 (12)	C8—C3—C4—C5	48.47 (15)
C11—O2—C1—C10	−76.85 (14)	C2—C3—C8—C7	−122.96 (12)
C1—O2—C11—O4	−9.1 (2)	C4—C3—C8—C9	117.40 (12)
C1—O2—C11—C12	169.64 (12)	C2—C3—C8—C9	−1.85 (13)
C11—O2—C1—C2	173.23 (11)	C2—C3—C4—C5	161.37 (12)
C10—O3—C13—C14	−175.51 (12)	C3—C4—C5—C6	−49.21 (19)
C13—O3—C10—C1	129.10 (12)	C4—C5—C6—C7	−0.4 (2)
C13—O3—C10—C9	−120.62 (13)	C5—C6—C7—C8	47.9 (2)
C10—O3—C13—O5	3.9 (2)	C6—C7—C8—C3	−42.87 (15)
O2—C1—C10—O3	2.80 (15)	C6—C7—C8—C9	−156.52 (12)
C10—C1—C2—O1	−35.36 (11)	C3—C8—C9—C10	75.78 (13)
C2—C1—C10—C9	0.45 (11)	C7—C8—C9—C10	−163.45 (12)
C10—C1—C2—C3	73.63 (11)	C7—C8—C9—O1	87.94 (13)
O2—C1—C2—O1	81.61 (12)	C3—C8—C9—O1	−32.83 (12)
C2—C1—C10—O3	116.93 (11)	C8—C9—C10—O3	169.33 (11)
O2—C1—C10—C9	−113.68 (11)	O1—C9—C10—C1	34.44 (10)
O2—C1—C2—C3	−169.40 (10)	O1—C9—C10—O3	−81.43 (12)
C1—C2—C3—C4	167.71 (11)	C8—C9—C10—C1	−74.80 (12)
C1—C2—C3—C8	−72.70 (12)

Symmetry codes: (i) x, y+1, z; (ii) −x+3/2, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z; (v) −x+2, −y+1, −z+1; (vi) −x+3/2, y+1/2, −z+1/2; (vii) −x+1/2, y−1/2, −z+1/2; (viii) −x+1/2, y+1/2, −z+1/2; (ix) −x+1, −y, −z+1; (x) x−1/2, −y+1/2, z−1/2; (xi) x+1/2, −y+1/2, z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1^iv	0.971 (17)	2.352 (17)	3.2468 (15)	153.0 (15)
C14—H14A···O4^i	0.96	2.59	3.460 (2)	151

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