organic compounds
Tetramethyl 1,4-dimethyl-13,14-dioxapentacyclo[8.2.1.14,7.02,9.03,8]tetradeca-5,11-diene-5,6,11,12-tetracarboxylate
aDepartment of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6, and bDepartment of Chemistry, University of Guelph, Guelph, Ontario, Canada N1G 2W1
*Correspondence e-mail: alough@chem.utoronto.ca
In the title compound, C22H24O14, the relative stereochemistry at the cyclobutane ring is cis-anti-cis and the methyl groups in the bicyclic rings are syn to each other. The two carboxylate groups attached to the same —C=C— bond are disordered over two sets of sites in a 0.603 (2):0.397 (2) ratio. In the crystal, weak C—H⋯O hydrogen bonds connect molecules into C(12) chains along [001] incorporating R222(10) rings.
Related literature
For related structures, see: Lough et al. (2012a,b). For the synthetic background, see: Ballantine et al. (2009). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
https://doi.org/10.1107/S1600536812039219/hb6952sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039219/hb6952Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812039219/hb6952Isup3.cml
1-Methyl-2,3-dimethyl-7-oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylate (45 mg, 0.20 mmol) was weighed into an oven-dried vial, purged with nitrogen and transferred into a Dry Box. In the Dry Box, Cp*Ru(COD)Cl (10 mol%) was added to another oven dried vial and dissolved in 1,2-dichloroethane (0.3 ml). The Ru-catalyst was then transferred into the vial containing the 7-oxanorbornadiene. The vial was sealed with a screw cap and removed from the Dry Box. The reaction was heated at 333 K with stirring for 18 h. The crude product was purified by
(EtOAc:hexanes=2:3) followed by recrystallization in hexanes to give the dimer (I). Slow evapotation of a solution of (I) in hexanes gave colourless plates.Hydrogen atoms were placed in calculated positions with C—H distances of 0.98 and 1.00 Å. They were included in the
in a riding-model approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(Cmethyl). Constraints were applied to both the geometry and displacement parameters of the atoms in the disorder components using the FLAT, SADI and EADP instructions in SHELXL (Sheldrick, 2008).We have recently investigated the Ru-catalyzed isomerization and dimerization reaction of oxanorbornadiene compounds (Ballantine et al., 2009). When dissolved in 1,2-dichloroethane in the presence of Cp*Ru(COD)Cl, 1-methyl-2,3-dimethyl-7-oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylate will dimerize into (I) (Fig. 1). The desired product was resolved using fractional crystallization in methanol. The stereochemistry and regioschemistry of the product was determined by this single-crystal X-ray analysis. The only dimer product obtained was found to have a cis-anti-cis stereochemistry at the cyclobutane ring of the dimer, and the two Me groups in the bicyclic rings were found to be syn to each other.
The molecular structure of (I) is shown in Fig. 2. Two of the carboxylate groups attached to the same –C═C– bond were refined as disordered over two sets of sites with refined occupancies 0.603 (2) and 0.397 (2). In the crystal, weak C—H···O hydrogen bonds connect molecules into C(12) chains (Bernstein et al., 1995) along [001] (Fig. 3) incorporating R22(10) rings.
Related structures (Lough et al., 2012a,b) are reported in the two following papers.
For related structures, see: Lough et al. (2012a,b). For the synthetic background, see: Ballantine et al. (2009). For hydrogen-bond motifs, see: Bernstein et al. (1995).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C22H24O10 | F(000) = 1888 |
Mr = 448.41 | Dx = 1.403 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 5611 reflections |
a = 11.5170 (14) Å | θ = 2.4–27.4° |
b = 13.9586 (15) Å | µ = 0.11 mm−1 |
c = 26.413 (3) Å | T = 147 K |
V = 4246.1 (8) Å3 | Plate, colourless |
Z = 8 | 0.33 × 0.22 × 0.06 mm |
Bruker Kappa APEX DUO CCD diffractometer | 4850 independent reflections |
Radiation source: fine-focus sealed tube | 2974 reflections with I > 2σ(I) |
Bruker Triumph monochromator | Rint = 0.055 |
φ and ω scans | θmax = 27.5°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | h = −14→14 |
Tmin = 0.964, Tmax = 0.993 | k = −10→18 |
19411 measured reflections | l = −34→18 |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 0.90 | w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3 |
4850 reflections | (Δ/σ)max = 0.001 |
322 parameters | Δρmax = 0.26 e Å−3 |
32 restraints | Δρmin = −0.20 e Å−3 |
C22H24O10 | V = 4246.1 (8) Å3 |
Mr = 448.41 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 11.5170 (14) Å | µ = 0.11 mm−1 |
b = 13.9586 (15) Å | T = 147 K |
c = 26.413 (3) Å | 0.33 × 0.22 × 0.06 mm |
Bruker Kappa APEX DUO CCD diffractometer | 4850 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2007) | 2974 reflections with I > 2σ(I) |
Tmin = 0.964, Tmax = 0.993 | Rint = 0.055 |
19411 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 32 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 0.90 | Δρmax = 0.26 e Å−3 |
4850 reflections | Δρmin = −0.20 e Å−3 |
322 parameters |
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 | Occ. (<1) | |
O1 | 0.81775 (11) | 0.24086 (8) | −0.04639 (4) | 0.0228 (3) | |
O2 | 0.87040 (10) | 0.50450 (8) | 0.06438 (4) | 0.0202 (3) | |
O3 | 0.77858 (13) | 0.36303 (10) | −0.19294 (4) | 0.0398 (4) | |
O4 | 0.85192 (11) | 0.49305 (9) | −0.15417 (4) | 0.0263 (3) | |
O5 | 1.15910 (11) | 0.28111 (9) | −0.10455 (4) | 0.0268 (3) | |
O6 | 1.06300 (11) | 0.35923 (9) | −0.16646 (4) | 0.0269 (3) | |
O7 | 0.6189 (2) | 0.3994 (2) | 0.18885 (7) | 0.0503 (7) | 0.603 (2) |
O8 | 0.5320 (9) | 0.4330 (6) | 0.1139 (5) | 0.0327 (14) | 0.603 (2) |
O9 | 0.8653 (3) | 0.3827 (2) | 0.22013 (8) | 0.0435 (8) | 0.603 (2) |
O10 | 0.9341 (6) | 0.2732 (5) | 0.1670 (5) | 0.0290 (14) | 0.603 (2) |
C17 | 0.6234 (3) | 0.4210 (2) | 0.14455 (12) | 0.0264 (8) | 0.603 (2) |
C19 | 0.8778 (3) | 0.3546 (3) | 0.17727 (10) | 0.0249 (6) | 0.603 (2) |
C18 | 0.4202 (12) | 0.4196 (9) | 0.1391 (6) | 0.0454 (6) | 0.603 (2) |
H18A | 0.3578 | 0.4217 | 0.1139 | 0.068* | 0.603 (2) |
H18B | 0.4085 | 0.4706 | 0.1640 | 0.068* | 0.603 (2) |
H18C | 0.4193 | 0.3573 | 0.1562 | 0.068* | 0.603 (2) |
C20 | 0.9776 (10) | 0.2224 (9) | 0.2114 (6) | 0.0436 (9) | 0.603 (2) |
H20A | 1.0204 | 0.1653 | 0.2006 | 0.065* | 0.603 (2) |
H20B | 0.9123 | 0.2033 | 0.2329 | 0.065* | 0.603 (2) |
H20C | 1.0295 | 0.2646 | 0.2306 | 0.065* | 0.603 (2) |
O7A | 0.6002 (3) | 0.4831 (3) | 0.18225 (12) | 0.0503 (7) | 0.397 (2) |
O8A | 0.5296 (14) | 0.4105 (11) | 0.1152 (8) | 0.0327 (14) | 0.397 (2) |
O9A | 0.7972 (4) | 0.3518 (3) | 0.21445 (14) | 0.0435 (8) | 0.397 (2) |
O10A | 0.9507 (10) | 0.2917 (9) | 0.1692 (8) | 0.0290 (14) | 0.397 (2) |
C17A | 0.6182 (4) | 0.4469 (4) | 0.14155 (16) | 0.0264 (8) | 0.397 (2) |
C19A | 0.8570 (5) | 0.3462 (4) | 0.17719 (13) | 0.0249 (6) | 0.397 (2) |
C18A | 0.4166 (19) | 0.4198 (14) | 0.1398 (10) | 0.0454 (6) | 0.397 (2) |
H18D | 0.3558 | 0.3959 | 0.1171 | 0.068* | 0.397 (2) |
H18E | 0.4020 | 0.4873 | 0.1477 | 0.068* | 0.397 (2) |
H18F | 0.4163 | 0.3823 | 0.1712 | 0.068* | 0.397 (2) |
C20A | 0.9845 (17) | 0.2309 (13) | 0.2116 (8) | 0.0436 (9) | 0.397 (2) |
H20D | 1.0628 | 0.2059 | 0.2058 | 0.065* | 0.397 (2) |
H20E | 0.9297 | 0.1775 | 0.2146 | 0.065* | 0.397 (2) |
H20F | 0.9836 | 0.2686 | 0.2429 | 0.065* | 0.397 (2) |
C1 | 0.85556 (16) | 0.34792 (12) | −0.11010 (5) | 0.0196 (4) | |
C2 | 0.77038 (16) | 0.32925 (12) | −0.06633 (5) | 0.0200 (4) | |
C3 | 0.80888 (15) | 0.40228 (12) | −0.02535 (5) | 0.0170 (4) | |
H3A | 0.8102 | 0.4708 | −0.0364 | 0.020* | |
C4 | 0.75885 (15) | 0.38416 (12) | 0.02843 (5) | 0.0172 (4) | |
H4A | 0.6914 | 0.3392 | 0.0302 | 0.021* | |
C5 | 0.74926 (15) | 0.47494 (12) | 0.06159 (5) | 0.0190 (4) | |
C6 | 0.73289 (15) | 0.43738 (12) | 0.11604 (5) | 0.0200 (4) | |
C7 | 0.83590 (16) | 0.40288 (12) | 0.13030 (5) | 0.0201 (4) | |
C8 | 0.91584 (16) | 0.41679 (12) | 0.08511 (5) | 0.0190 (4) | |
H8A | 1.0007 | 0.4176 | 0.0931 | 0.023* | |
C9 | 0.87811 (15) | 0.34188 (12) | 0.04533 (5) | 0.0175 (4) | |
H9A | 0.8773 | 0.2737 | 0.0569 | 0.021* | |
C10 | 0.92895 (15) | 0.36020 (12) | −0.00825 (5) | 0.0173 (4) | |
H10A | 0.9962 | 0.4054 | −0.0098 | 0.021* | |
C11 | 0.93701 (15) | 0.27200 (12) | −0.04294 (5) | 0.0204 (4) | |
H11A | 0.9934 | 0.2218 | −0.0318 | 0.024* | |
C12 | 0.95736 (16) | 0.31197 (12) | −0.09594 (5) | 0.0198 (4) | |
C13 | 0.82498 (16) | 0.40042 (13) | −0.15740 (5) | 0.0221 (4) | |
C14 | 0.83509 (19) | 0.54896 (15) | −0.20023 (6) | 0.0398 (5) | |
H14A | 0.8350 | 0.6174 | −0.1919 | 0.060* | |
H14B | 0.7607 | 0.5317 | −0.2157 | 0.060* | |
H14C | 0.8983 | 0.5354 | −0.2240 | 0.060* | |
C15 | 1.07098 (16) | 0.31541 (12) | −0.12149 (5) | 0.0194 (4) | |
C16 | 1.16955 (17) | 0.36413 (15) | −0.19566 (6) | 0.0331 (5) | |
H16A | 1.1593 | 0.4087 | −0.2240 | 0.050* | |
H16B | 1.1885 | 0.3004 | −0.2088 | 0.050* | |
H16C | 1.2329 | 0.3867 | −0.1739 | 0.050* | |
C21 | 0.64336 (16) | 0.31957 (14) | −0.07817 (6) | 0.0292 (5) | |
H21A | 0.6325 | 0.2705 | −0.1043 | 0.044* | |
H21B | 0.6134 | 0.3810 | −0.0905 | 0.044* | |
H21C | 0.6013 | 0.3009 | −0.0475 | 0.044* | |
C22 | 0.67345 (17) | 0.55607 (13) | 0.04345 (6) | 0.0271 (4) | |
H22A | 0.6715 | 0.6066 | 0.0692 | 0.041* | |
H22B | 0.5946 | 0.5323 | 0.0375 | 0.041* | |
H22C | 0.7051 | 0.5821 | 0.0119 | 0.041* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0276 (8) | 0.0218 (7) | 0.0189 (5) | −0.0031 (6) | 0.0024 (5) | 0.0019 (5) |
O2 | 0.0201 (7) | 0.0184 (6) | 0.0221 (5) | −0.0020 (5) | 0.0006 (5) | 0.0023 (5) |
O3 | 0.0495 (10) | 0.0499 (9) | 0.0200 (6) | −0.0059 (8) | −0.0140 (6) | −0.0024 (6) |
O4 | 0.0292 (8) | 0.0311 (8) | 0.0185 (5) | −0.0006 (6) | −0.0042 (5) | 0.0084 (5) |
O5 | 0.0239 (8) | 0.0290 (7) | 0.0275 (6) | 0.0066 (6) | −0.0018 (5) | −0.0016 (5) |
O6 | 0.0217 (7) | 0.0445 (8) | 0.0145 (5) | 0.0040 (6) | 0.0054 (5) | 0.0052 (5) |
O7 | 0.0397 (13) | 0.0895 (19) | 0.0218 (9) | −0.0210 (16) | 0.0109 (8) | −0.0115 (13) |
O8 | 0.0193 (9) | 0.037 (4) | 0.0422 (9) | 0.005 (2) | 0.0050 (8) | 0.001 (3) |
O9 | 0.059 (2) | 0.0560 (19) | 0.0152 (8) | 0.0237 (16) | 0.0032 (13) | 0.0002 (10) |
O10 | 0.027 (2) | 0.037 (3) | 0.0225 (12) | 0.007 (2) | −0.0007 (18) | 0.009 (2) |
C17 | 0.0282 (13) | 0.029 (2) | 0.0216 (10) | −0.0092 (13) | 0.0044 (9) | −0.0074 (11) |
C19 | 0.0325 (18) | 0.0246 (12) | 0.0175 (8) | −0.0020 (12) | 0.0043 (9) | 0.0009 (8) |
C18 | 0.0207 (14) | 0.0459 (14) | 0.0696 (15) | 0.0047 (11) | 0.0146 (12) | −0.0102 (12) |
C20 | 0.0403 (17) | 0.055 (2) | 0.0354 (10) | 0.0094 (18) | −0.0040 (12) | 0.0208 (13) |
O7A | 0.0397 (13) | 0.0895 (19) | 0.0218 (9) | −0.0210 (16) | 0.0109 (8) | −0.0115 (13) |
O8A | 0.0193 (9) | 0.037 (4) | 0.0422 (9) | 0.005 (2) | 0.0050 (8) | 0.001 (3) |
O9A | 0.059 (2) | 0.0560 (19) | 0.0152 (8) | 0.0237 (16) | 0.0032 (13) | 0.0002 (10) |
O10A | 0.027 (2) | 0.037 (3) | 0.0225 (12) | 0.007 (2) | −0.0007 (18) | 0.009 (2) |
C17A | 0.0282 (13) | 0.029 (2) | 0.0216 (10) | −0.0092 (13) | 0.0044 (9) | −0.0074 (11) |
C19A | 0.0325 (18) | 0.0246 (12) | 0.0175 (8) | −0.0020 (12) | 0.0043 (9) | 0.0009 (8) |
C18A | 0.0207 (14) | 0.0459 (14) | 0.0696 (15) | 0.0047 (11) | 0.0146 (12) | −0.0102 (12) |
C20A | 0.0403 (17) | 0.055 (2) | 0.0354 (10) | 0.0094 (18) | −0.0040 (12) | 0.0208 (13) |
C1 | 0.0212 (10) | 0.0244 (10) | 0.0131 (7) | −0.0023 (8) | 0.0007 (7) | −0.0009 (7) |
C2 | 0.0200 (10) | 0.0245 (10) | 0.0154 (7) | −0.0012 (8) | 0.0022 (7) | 0.0018 (7) |
C3 | 0.0158 (9) | 0.0204 (9) | 0.0149 (7) | −0.0001 (7) | 0.0007 (6) | 0.0033 (7) |
C4 | 0.0166 (9) | 0.0206 (9) | 0.0144 (7) | −0.0027 (8) | 0.0015 (6) | 0.0000 (6) |
C5 | 0.0169 (9) | 0.0218 (9) | 0.0182 (7) | −0.0023 (8) | 0.0009 (7) | 0.0004 (7) |
C6 | 0.0243 (10) | 0.0210 (9) | 0.0148 (7) | −0.0039 (8) | 0.0026 (7) | −0.0051 (7) |
C7 | 0.0263 (11) | 0.0189 (9) | 0.0149 (7) | −0.0030 (8) | 0.0012 (7) | −0.0037 (7) |
C8 | 0.0197 (10) | 0.0216 (10) | 0.0158 (7) | 0.0011 (8) | −0.0012 (7) | 0.0030 (7) |
C9 | 0.0207 (10) | 0.0189 (9) | 0.0128 (7) | −0.0001 (7) | 0.0017 (6) | 0.0021 (6) |
C10 | 0.0170 (9) | 0.0205 (9) | 0.0144 (7) | 0.0004 (8) | 0.0014 (6) | 0.0033 (7) |
C11 | 0.0201 (10) | 0.0244 (10) | 0.0167 (7) | 0.0027 (8) | 0.0017 (7) | 0.0025 (7) |
C12 | 0.0235 (10) | 0.0230 (10) | 0.0127 (7) | 0.0005 (8) | 0.0016 (7) | −0.0008 (7) |
C13 | 0.0187 (10) | 0.0326 (11) | 0.0149 (7) | 0.0027 (8) | 0.0032 (7) | 0.0003 (7) |
C14 | 0.0407 (14) | 0.0500 (14) | 0.0286 (9) | 0.0003 (11) | −0.0041 (9) | 0.0220 (9) |
C15 | 0.0226 (11) | 0.0201 (9) | 0.0156 (7) | 0.0021 (8) | −0.0001 (7) | −0.0042 (7) |
C16 | 0.0278 (12) | 0.0469 (13) | 0.0245 (8) | −0.0030 (10) | 0.0118 (8) | −0.0023 (8) |
C21 | 0.0227 (11) | 0.0459 (13) | 0.0191 (8) | −0.0075 (10) | 0.0002 (7) | −0.0012 (8) |
C22 | 0.0269 (11) | 0.0277 (11) | 0.0266 (8) | 0.0062 (9) | 0.0004 (8) | 0.0005 (8) |
O1—C11 | 1.443 (2) | C20A—H20F | 0.9800 |
O1—C2 | 1.448 (2) | C1—C12 | 1.329 (2) |
O2—C8 | 1.4396 (19) | C1—C13 | 1.490 (2) |
O2—C5 | 1.457 (2) | C1—C2 | 1.539 (2) |
O3—C13 | 1.200 (2) | C2—C21 | 1.502 (3) |
O4—C13 | 1.332 (2) | C2—C3 | 1.552 (2) |
O4—C14 | 1.4584 (19) | C3—C4 | 1.554 (2) |
O5—C15 | 1.208 (2) | C3—C10 | 1.569 (2) |
O6—C15 | 1.3393 (19) | C3—H3A | 1.0000 |
O6—C16 | 1.451 (2) | C4—C5 | 1.544 (2) |
O7—C17 | 1.210 (3) | C4—C9 | 1.560 (2) |
O8—C17 | 1.338 (3) | C4—H4A | 1.0000 |
O8—C18 | 1.461 (3) | C5—C22 | 1.508 (2) |
O9—C19 | 1.207 (3) | C5—C6 | 1.542 (2) |
O10—C19 | 1.337 (3) | C6—C7 | 1.335 (2) |
O10—C20 | 1.458 (3) | C7—C8 | 1.520 (2) |
C17—C6 | 1.486 (3) | C8—C9 | 1.545 (2) |
C19—C7 | 1.492 (3) | C8—H8A | 1.0000 |
C18—H18A | 0.9800 | C9—C10 | 1.553 (2) |
C18—H18B | 0.9800 | C9—H9A | 1.0000 |
C18—H18C | 0.9800 | C10—C11 | 1.537 (2) |
C20—H20A | 0.9800 | C10—H10A | 1.0000 |
C20—H20B | 0.9800 | C11—C12 | 1.525 (2) |
C20—H20C | 0.9800 | C11—H11A | 1.0000 |
O7A—C17A | 1.206 (4) | C12—C15 | 1.473 (2) |
O8A—C17A | 1.337 (4) | C14—H14A | 0.9800 |
O8A—C18A | 1.460 (4) | C14—H14B | 0.9800 |
O9A—C19A | 1.203 (4) | C14—H14C | 0.9800 |
O10A—C19A | 1.337 (4) | C16—H16A | 0.9800 |
O10A—C20A | 1.459 (4) | C16—H16B | 0.9800 |
C17A—C6 | 1.488 (4) | C16—H16C | 0.9800 |
C19A—C7 | 1.490 (4) | C21—H21A | 0.9800 |
C18A—H18D | 0.9800 | C21—H21B | 0.9800 |
C18A—H18E | 0.9800 | C21—H21C | 0.9800 |
C18A—H18F | 0.9800 | C22—H22A | 0.9800 |
C20A—H20D | 0.9800 | C22—H22B | 0.9800 |
C20A—H20E | 0.9800 | C22—H22C | 0.9800 |
C11—O1—C2 | 97.18 (12) | C17A—C6—C5 | 120.0 (2) |
C8—O2—C5 | 97.27 (12) | C6—C7—C19A | 124.8 (3) |
C13—O4—C14 | 115.79 (13) | C6—C7—C19 | 133.23 (19) |
C15—O6—C16 | 115.78 (14) | C6—C7—C8 | 105.71 (12) |
C17—O8—C18 | 113.7 (10) | C19A—C7—C8 | 128.5 (3) |
C19—O10—C20 | 114.7 (8) | C19—C7—C8 | 121.00 (19) |
O7—C17—O8 | 125.6 (7) | O2—C8—C7 | 100.78 (13) |
O7—C17—C6 | 124.4 (3) | O2—C8—C9 | 102.40 (12) |
O8—C17—C6 | 110.0 (7) | C7—C8—C9 | 106.10 (13) |
O9—C19—O10 | 121.6 (6) | O2—C8—H8A | 115.3 |
O9—C19—C7 | 126.5 (3) | C7—C8—H8A | 115.3 |
O10—C19—C7 | 111.9 (6) | C9—C8—H8A | 115.3 |
C17A—O8A—C18A | 114.4 (17) | C8—C9—C10 | 113.73 (13) |
C19A—O10A—C20A | 115.1 (14) | C8—C9—C4 | 100.73 (13) |
O7A—C17A—O8A | 119.5 (12) | C10—C9—C4 | 90.51 (11) |
O7A—C17A—C6 | 126.5 (5) | C8—C9—H9A | 116.0 |
O8A—C17A—C6 | 114.0 (11) | C10—C9—H9A | 116.0 |
O9A—C19A—O10A | 128.9 (10) | C4—C9—H9A | 116.0 |
O9A—C19A—C7 | 123.5 (5) | C11—C10—C9 | 115.72 (13) |
O10A—C19A—C7 | 107.6 (10) | C11—C10—C3 | 100.46 (13) |
O8A—C18A—H18D | 109.5 | C9—C10—C3 | 89.52 (12) |
O8A—C18A—H18E | 109.5 | C11—C10—H10A | 115.7 |
H18D—C18A—H18E | 109.5 | C9—C10—H10A | 115.7 |
O8A—C18A—H18F | 109.5 | C3—C10—H10A | 115.7 |
H18D—C18A—H18F | 109.5 | O1—C11—C12 | 101.45 (12) |
H18E—C18A—H18F | 109.5 | O1—C11—C10 | 102.78 (13) |
O10A—C20A—H20D | 109.5 | C12—C11—C10 | 105.27 (13) |
O10A—C20A—H20E | 109.5 | O1—C11—H11A | 115.2 |
H20D—C20A—H20E | 109.5 | C12—C11—H11A | 115.2 |
O10A—C20A—H20F | 109.5 | C10—C11—H11A | 115.2 |
H20D—C20A—H20F | 109.5 | C1—C12—C15 | 129.97 (14) |
H20E—C20A—H20F | 109.5 | C1—C12—C11 | 105.13 (14) |
C12—C1—C13 | 129.05 (15) | C15—C12—C11 | 124.67 (15) |
C12—C1—C2 | 106.68 (13) | O3—C13—O4 | 125.16 (15) |
C13—C1—C2 | 124.23 (15) | O3—C13—C1 | 123.18 (17) |
O1—C2—C21 | 111.47 (14) | O4—C13—C1 | 111.62 (14) |
O1—C2—C1 | 100.22 (13) | O4—C14—H14A | 109.5 |
C21—C2—C1 | 118.67 (13) | O4—C14—H14B | 109.5 |
O1—C2—C3 | 101.44 (12) | H14A—C14—H14B | 109.5 |
C21—C2—C3 | 118.86 (15) | O4—C14—H14C | 109.5 |
C1—C2—C3 | 103.33 (13) | H14A—C14—H14C | 109.5 |
C2—C3—C4 | 115.13 (14) | H14B—C14—H14C | 109.5 |
C2—C3—C10 | 101.93 (13) | O5—C15—O6 | 124.55 (16) |
C4—C3—C10 | 90.16 (11) | O5—C15—C12 | 124.31 (15) |
C2—C3—H3A | 115.4 | O6—C15—C12 | 111.12 (15) |
C4—C3—H3A | 115.4 | O6—C16—H16A | 109.5 |
C10—C3—H3A | 115.4 | O6—C16—H16B | 109.5 |
C5—C4—C3 | 114.29 (13) | H16A—C16—H16B | 109.5 |
C5—C4—C9 | 102.18 (13) | O6—C16—H16C | 109.5 |
C3—C4—C9 | 89.81 (12) | H16A—C16—H16C | 109.5 |
C5—C4—H4A | 115.7 | H16B—C16—H16C | 109.5 |
C3—C4—H4A | 115.7 | C2—C21—H21A | 109.5 |
C9—C4—H4A | 115.7 | C2—C21—H21B | 109.5 |
O2—C5—C22 | 110.97 (14) | H21A—C21—H21B | 109.5 |
O2—C5—C6 | 99.57 (12) | C2—C21—H21C | 109.5 |
C22—C5—C6 | 118.73 (14) | H21A—C21—H21C | 109.5 |
O2—C5—C4 | 101.11 (13) | H21B—C21—H21C | 109.5 |
C22—C5—C4 | 118.51 (13) | C5—C22—H22A | 109.5 |
C6—C5—C4 | 104.99 (13) | C5—C22—H22B | 109.5 |
C7—C6—C17 | 123.8 (2) | H22A—C22—H22B | 109.5 |
C7—C6—C17A | 133.9 (2) | C5—C22—H22C | 109.5 |
C7—C6—C5 | 106.09 (14) | H22A—C22—H22C | 109.5 |
C17—C6—C5 | 128.9 (2) | H22B—C22—H22C | 109.5 |
C18—O8—C17—O7 | 1.3 (6) | C17A—C6—C7—C8 | −179.3 (3) |
C18—O8—C17—C6 | −179.2 (4) | C5—C6—C7—C8 | −0.99 (17) |
C20—O10—C19—O9 | 0.2 (4) | O9A—C19A—C7—C6 | −25.8 (5) |
C20—O10—C19—C7 | 179.9 (2) | O10A—C19A—C7—C6 | 154.4 (5) |
C18A—O8A—C17A—O7A | 0.3 (6) | O9A—C19A—C7—C19 | 121 (2) |
C18A—O8A—C17A—C6 | −179.8 (4) | O10A—C19A—C7—C19 | −59 (2) |
C20A—O10A—C19A—O9A | 0.1 (4) | O9A—C19A—C7—C8 | 167.3 (4) |
C20A—O10A—C19A—C7 | 179.9 (2) | O10A—C19A—C7—C8 | −12.5 (4) |
C11—O1—C2—C21 | 176.12 (12) | O9—C19—C7—C6 | −51.3 (4) |
C11—O1—C2—C1 | 49.62 (12) | O10—C19—C7—C6 | 129.0 (4) |
C11—O1—C2—C3 | −56.37 (13) | O9—C19—C7—C19A | −89 (2) |
C12—C1—C2—O1 | −31.08 (16) | O10—C19—C7—C19A | 91.3 (19) |
C13—C1—C2—O1 | 151.18 (16) | O9—C19—C7—C8 | 132.0 (3) |
C12—C1—C2—C21 | −152.58 (16) | O10—C19—C7—C8 | −47.6 (3) |
C13—C1—C2—C21 | 29.7 (2) | C5—O2—C8—C7 | −51.98 (13) |
C12—C1—C2—C3 | 73.39 (17) | C5—O2—C8—C9 | 57.35 (13) |
C13—C1—C2—C3 | −104.35 (18) | C6—C7—C8—O2 | 33.57 (16) |
O1—C2—C3—C4 | −62.06 (17) | C19A—C7—C8—O2 | −157.5 (3) |
C21—C2—C3—C4 | 60.5 (2) | C19—C7—C8—O2 | −148.9 (2) |
C1—C2—C3—C4 | −165.59 (14) | C6—C7—C8—C9 | −72.84 (16) |
O1—C2—C3—C10 | 33.81 (14) | C19A—C7—C8—C9 | 96.0 (3) |
C21—C2—C3—C10 | 156.36 (14) | C19—C7—C8—C9 | 104.6 (2) |
C1—C2—C3—C10 | −69.72 (15) | O2—C8—C9—C10 | 60.81 (17) |
C2—C3—C4—C5 | −153.67 (15) | C7—C8—C9—C10 | 166.05 (13) |
C10—C3—C4—C5 | 103.05 (15) | O2—C8—C9—C4 | −34.53 (14) |
C2—C3—C4—C9 | 103.03 (15) | C7—C8—C9—C4 | 70.71 (14) |
C10—C3—C4—C9 | −0.25 (12) | C5—C4—C9—C8 | −0.31 (14) |
C8—O2—C5—C22 | 176.56 (12) | C3—C4—C9—C8 | 114.53 (12) |
C8—O2—C5—C6 | 50.64 (13) | C5—C4—C9—C10 | −114.60 (12) |
C8—O2—C5—C4 | −56.84 (12) | C3—C4—C9—C10 | 0.25 (12) |
C3—C4—C5—O2 | −60.95 (16) | C8—C9—C10—C11 | 156.40 (14) |
C9—C4—C5—O2 | 34.43 (13) | C4—C9—C10—C11 | −101.64 (15) |
C3—C4—C5—C22 | 60.5 (2) | C8—C9—C10—C3 | −102.21 (15) |
C9—C4—C5—C22 | 155.88 (15) | C4—C9—C10—C3 | −0.25 (12) |
C3—C4—C5—C6 | −164.12 (14) | C2—C3—C10—C11 | 0.57 (14) |
C9—C4—C5—C6 | −68.74 (15) | C4—C3—C10—C11 | 116.34 (12) |
O7—C17—C6—C7 | 21.3 (4) | C2—C3—C10—C9 | −115.52 (12) |
O8—C17—C6—C7 | −158.1 (4) | C4—C3—C10—C9 | 0.25 (12) |
O7—C17—C6—C17A | −116.9 (14) | C2—O1—C11—C12 | −50.97 (13) |
O8—C17—C6—C17A | 63.7 (13) | C2—O1—C11—C10 | 57.78 (12) |
O7—C17—C6—C5 | −173.1 (2) | C9—C10—C11—O1 | 59.43 (16) |
O8—C17—C6—C5 | 7.5 (3) | C3—C10—C11—O1 | −35.13 (14) |
O7A—C17A—C6—C7 | 51.7 (6) | C9—C10—C11—C12 | 165.26 (14) |
O8A—C17A—C6—C7 | −128.1 (6) | C3—C10—C11—C12 | 70.70 (15) |
O7A—C17A—C6—C17 | 101.9 (14) | C13—C1—C12—C15 | 2.2 (3) |
O8A—C17A—C6—C17 | −77.9 (14) | C2—C1—C12—C15 | −175.43 (17) |
O7A—C17A—C6—C5 | −126.4 (4) | C13—C1—C12—C11 | 176.74 (17) |
O8A—C17A—C6—C5 | 53.8 (5) | C2—C1—C12—C11 | −0.86 (18) |
O2—C5—C6—C7 | −31.31 (16) | O1—C11—C12—C1 | 32.81 (17) |
C22—C5—C6—C7 | −151.73 (16) | C10—C11—C12—C1 | −74.00 (17) |
C4—C5—C6—C7 | 73.01 (17) | O1—C11—C12—C15 | −152.24 (15) |
O2—C5—C6—C17 | 161.13 (19) | C10—C11—C12—C15 | 100.94 (18) |
C22—C5—C6—C17 | 40.7 (3) | C14—O4—C13—O3 | −7.5 (3) |
C4—C5—C6—C17 | −94.5 (2) | C14—O4—C13—C1 | 174.64 (15) |
O2—C5—C6—C17A | 147.2 (3) | C12—C1—C13—O3 | 99.2 (2) |
C22—C5—C6—C17A | 26.8 (3) | C2—C1—C13—O3 | −83.6 (2) |
C4—C5—C6—C17A | −108.4 (3) | C12—C1—C13—O4 | −82.9 (2) |
C17—C6—C7—C19A | −2.0 (3) | C2—C1—C13—O4 | 94.3 (2) |
C17A—C6—C7—C19A | 11.3 (5) | C16—O6—C15—O5 | 0.1 (2) |
C5—C6—C7—C19A | −170.4 (3) | C16—O6—C15—C12 | −178.24 (14) |
C17—C6—C7—C19 | −9.7 (4) | C1—C12—C15—O5 | 178.80 (18) |
C17A—C6—C7—C19 | 3.7 (5) | C11—C12—C15—O5 | 5.2 (3) |
C5—C6—C7—C19 | −178.0 (3) | C1—C12—C15—O6 | −2.9 (3) |
C17—C6—C7—C8 | 167.37 (18) | C11—C12—C15—O6 | −176.48 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O2i | 1.00 | 2.45 | 3.332 (2) | 146 |
C14—H14C···O7ii | 0.98 | 2.48 | 3.063 (3) | 118 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C22H24O10 |
Mr | 448.41 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 147 |
a, b, c (Å) | 11.5170 (14), 13.9586 (15), 26.413 (3) |
V (Å3) | 4246.1 (8) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.33 × 0.22 × 0.06 |
Data collection | |
Diffractometer | Bruker Kappa APEX DUO CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2007) |
Tmin, Tmax | 0.964, 0.993 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19411, 4850, 2974 |
Rint | 0.055 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.096, 0.90 |
No. of reflections | 4850 |
No. of parameters | 322 |
No. of restraints | 32 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.20 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10A···O2i | 1.00 | 2.45 | 3.332 (2) | 146 |
C14—H14C···O7ii | 0.98 | 2.48 | 3.063 (3) | 118 |
Symmetry codes: (i) −x+2, −y+1, −z; (ii) −x+3/2, −y+1, z−1/2. |
Acknowledgements
The University of Toronto thanks NSERC Canada for funding.
References
Ballantine, M., Menard, M. L. & Tam, W. (2009). J. Org. Chem. 74, 7570–7573. Web of Science CrossRef PubMed CAS Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N. L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2007). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Lough, A. J., Jack, K. & Tam, W. (2012a). Acta Cryst. E68, o2962. CSD CrossRef IUCr Journals Google Scholar
Lough, A. J., Jack, K. & Tam, W. (2012b). Acta Cryst. E68, o2963. CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
We have recently investigated the Ru-catalyzed isomerization and dimerization reaction of oxanorbornadiene compounds (Ballantine et al., 2009). When dissolved in 1,2-dichloroethane in the presence of Cp*Ru(COD)Cl, 1-methyl-2,3-dimethyl-7-oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylate will dimerize into (I) (Fig. 1). The desired product was resolved using fractional crystallization in methanol. The stereochemistry and regioschemistry of the product was determined by this single-crystal X-ray analysis. The only dimer product obtained was found to have a cis-anti-cis stereochemistry at the cyclobutane ring of the dimer, and the two Me groups in the bicyclic rings were found to be syn to each other.
The molecular structure of (I) is shown in Fig. 2. Two of the carboxylate groups attached to the same –C═C– bond were refined as disordered over two sets of sites with refined occupancies 0.603 (2) and 0.397 (2). In the crystal, weak C—H···O hydrogen bonds connect molecules into C(12) chains (Bernstein et al., 1995) along [001] (Fig. 3) incorporating R22(10) rings.
Related structures (Lough et al., 2012a,b) are reported in the two following papers.