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

Lough, A.J.; Jack, K.; Tam, W.

doi:10.1107/S1600536812039219

organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2961

https://doi.org/10.1107/S1600536812039219

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Tetramethyl 1,4-dimethyl-13,14-dioxapentacyclo[8.2.1.1^4,7.0^2,9.0^3,8]tetradeca-5,11-diene-5,6,11,12-tetracarboxylate

Alan J. Lough,^a ^* Kelsey Jack ^b and William Tam ^b

^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

(Received 3 September 2012; accepted 13 September 2012; online 22 September 2012)

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

C₂₂H₂₄O₁₀
M_r = 448.41
Orthorhombic, P b c a
a = 11.5170 (14) Å
b = 13.9586 (15) Å
c = 26.413 (3) Å
V = 4246.1 (8) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 147 K
0.33 × 0.22 × 0.06 mm

Data collection

Bruker Kappa APEX DUO CCD diffractometer
Absorption correction: multi-scan (Bruker, 2007 ) T_min = 0.964, T_max = 0.993
19411 measured reflections
4850 independent reflections
2974 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.096
S = 0.90
4850 reflections
322 parameters
32 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007); cell refinement: 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

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536812039219/hb6952sup1.cif

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

checkCIF report

Comment top

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.

Related literature top

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 top

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 column chromatography (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.

Structure description top

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).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: 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).

Figures top

	Fig. 1. Reaction scheme
	Fig. 2. The molecular structure of (I) showing 30% probability ellipsoids. The bonds of the minor component of disorder are shown with dashed lines.
	Fig. 3. Part of the crystal structure showing weak hydrogen bonds as dashed lines. The disorder is not shown.

Tetramethyl 1,4-dimethyl-13,14-dioxapentacyclo[8.2.1.1^4,7.0^2,9.0^3,8]tetradeca- 5,11-diene-5,6,11,12-tetracarboxylate top

Crystal data top

C₂₂H₂₄O₁₀	F(000) = 1888
M_r = 448.41	D_x = 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

Data collection top

Bruker Kappa APEX DUO CCD diffractometer	4850 independent reflections
Radiation source: fine-focus sealed tube	2974 reflections with I > 2σ(I)
Bruker Triumph monochromator	R_int = 0.055
φ and ω scans	θ_max = 27.5°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −14→14
T_min = 0.964, T_max = 0.993	k = −10→18
19411 measured reflections	l = −34→18

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 0.90	w = 1/[σ²(F_o²) + (0.0451P)²] where P = (F_o² + 2F_c²)/3
4850 reflections	(Δ/σ)_max = 0.001
322 parameters	Δρ_max = 0.26 e Å⁻³
32 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₂H₂₄O₁₀	V = 4246.1 (8) Å³
M_r = 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

Data collection top

Bruker Kappa APEX DUO CCD diffractometer	4850 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2974 reflections with I > 2σ(I)
T_min = 0.964, T_max = 0.993	R_int = 0.055
19411 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	32 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 0.90	Δρ_max = 0.26 e Å⁻³
4850 reflections	Δρ_min = −0.20 e Å⁻³
322 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.964, 0.993
No. of measured, independent and observed [I > 2σ(I)] reflections	19411, 4850, 2974
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

Tetramethyl 1,4-dimethyl-13,14-dioxapentacyclo[8.2.1.1^4,7.0^2,9.0^3,8]tetradeca-5,11-diene-5,6,11,12-tetracarboxylate