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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, C
14H
18O
5, 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.
Supporting information
CCDC reference: 274672
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (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
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
top
Crystal data top
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) Å3 | 0.55 × 0.50 × 0.44 mm |
Z = 4 | |
Data collection top
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 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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.127 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0754P)2 + 0.3715P] where P = (Fo2 + 2Fc2)/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 top
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 (Å2) top | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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···H14Bii | 3.0700 |
O1···C3i | 3.2468 (15) | H1···O4 | 2.43 (2) |
O2···O1 | 2.9145 (15) | H1···H3 | 2.41 (3) |
O2···O3 | 2.5745 (15) | H2···O1iii | 2.782 (17) |
O3···O1 | 2.9602 (16) | H2···C2iii | 2.967 (17) |
O3···C11 | 2.8373 (19) | H2···H2iii | 2.43 (2) |
O3···O2 | 2.5745 (15) | H2···H4Aix | 2.51 (2) |
O3···O4 | 3.0991 (16) | H2···H4Biii | 2.36 (3) |
O4···C13 | 3.381 (2) | H3···O1iv | 2.352 (17) |
O4···O3 | 3.0991 (16) | H3···H1 | 2.41 (3) |
O4···C10 | 3.1669 (19) | H3···H4Aix | 2.41 (3) |
O5···C13ii | 3.2689 (19) | H4A···C2ix | 2.843 (17) |
O1···H3i | 2.352 (17) | H4A···C3ix | 2.815 (18) |
O1···H4B | 2.73 (2) | H4A···C4ix | 3.081 (19) |
O1···H7B | 2.851 (18) | H4A···H2ix | 2.51 (2) |
O1···H2iii | 2.782 (17) | H4A···H3ix | 2.41 (3) |
O2···H4Biii | 2.92 (2) | H4A···H4Aix | 2.45 (3) |
O4···H12Biv | 2.9200 | H4B···O1 | 2.73 (2) |
O4···H14Aiv | 2.5900 | H4B···C7 | 2.77 (2) |
O4···H1 | 2.43 (2) | H4B···H7B | 2.45 (3) |
O4···H14Cv | 2.6800 | H4B···O2iii | 2.92 (2) |
O5···H10 | 2.231 (17) | H4B···C2iii | 3.09 (2) |
O5···H14Biv | 2.8600 | H4B···H2iii | 2.36 (3) |
O5···H8vi | 2.647 (17) | H5···C6vii | 2.78 (2) |
O5···H10vi | 2.840 (17) | H5···C7vii | 2.98 (2) |
O5···H14Bii | 2.8200 | H5···H6vii | 2.51 (3) |
O5···H12Cv | 2.8000 | H6···H5viii | 2.51 (3) |
C3···O1iv | 3.2468 (15) | H6···H12Ax | 2.3900 |
C5···C6vii | 3.535 (2) | H7B···O1 | 2.851 (18) |
C6···C5viii | 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···O5ii | 2.647 (17) |
C13···O5vi | 3.2689 (19) | H10···O5 | 2.231 (17) |
C13···O4 | 3.381 (2) | H10···H8 | 2.32 (2) |
C13···C11 | 3.472 (2) | H10···O5ii | 2.840 (17) |
C2···H4Aix | 2.843 (17) | H12A···C6xi | 3.0700 |
C2···H2iii | 2.967 (17) | H12A···H6xi | 2.3900 |
C2···H4Biii | 3.09 (2) | H12B···O4i | 2.9200 |
C3···H4Aix | 2.815 (18) | H12C···O5v | 2.8000 |
C4···H4Aix | 3.081 (19) | H14A···O4i | 2.5900 |
C4···H7B | 2.780 (17) | H14B···O5i | 2.8600 |
C6···H5viii | 2.78 (2) | H14B···O5vi | 2.8200 |
C6···H12Ax | 3.0700 | H14B···C9vi | 3.0700 |
C7···H5viii | 2.98 (2) | H14C···O4v | 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) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1iv | 0.971 (17) | 2.352 (17) | 3.2468 (15) | 153.0 (15) |
C14—H14A···O4i | 0.96 | 2.59 | 3.460 (2) | 151 |
Symmetry codes: (i) x, y+1, z; (iv) x, y−1, z. |
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