Tetra-tert-butyl 13,14-dioxapenta­cyclo­[8.2.1.1^4,7.0^2,9.0^3,8]tetra­deca-5,11-diene-5,6,11,12-tetra­carboxyl­ate

Abstract

The stereochemistry of the title compound, C₃₂H₄₄O₁₀, at the cyclo­butane ring is cis-anti-cis. The mol­ecule lies across an inversion center. In the crystal, weak C—H⋯O hydrogen bonds connect mol­ecules into chains along [100], forming R ₂ ²(6) 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  

• C₃₂H₄₄O₁₀

• M _r = 588.67

• Triclinic,

• a = 5.8376 (10) Å

• b = 9.4895 (17) Å

• c = 14.924 (3) Å

• α = 99.926 (4)°

• β = 98.545 (4)°

• γ = 100.462 (4)°

• V = 786.9 (2) ų

• Z = 1

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 150 K

• 0.45 × 0.25 × 0.15 mm

Data collection  

• Bruker Kappa APEX DUO CCD diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.698, T _max = 0.746

• 6490 measured reflections

• 3559 independent reflections

• 3024 reflections with I > 2σ(I)

• R _int = 0.015

Refinement  

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.104

• S = 1.04

• 3559 reflections

• 196 parameters

• H-atom parameters constrained

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

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 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812039220/hb6953Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1i	1.00	2.47	3.2118 (16)	130

Symmetry code: (i) .

supplementary crystallographic information

Comment

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, tert-butoxy-7-oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylate will dimerize into the title compound (I) (see Fig. 1). The desired product was resolved using fractional crystallization in hexanes. The stereochemistry of the product was determined by this single-crystal X-ray analysis and was found to have a cis-anti-cis stereochemistry at the cyclobutane ring of the dimer.

The molecular structure of (I) is shown in Fig. 2. In the crystal, weak C—H···O hydrogen bonds connect molecules into one-dimensional chains (Fig. 3) along [100] forming R²₂(6) rings (Bernstein et al., 1995).

For related structures see the preceding (Lough et al., 2012a) and following (Lough et al., 2012b) papers

Experimental

tert-Butoxy-7-oxabicyclo[2,2,1]hepta-2,5-diene-2,3-dicarboxylate 1 (45 mg, 0.15 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 (0.5 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 20 h. The crude product was purified by column chromatography (EtOAc:hexanes = 2:3) followed by recrystallization in hexanes to give the dimer (I). Colourless blocks were grown by slow evaportation of a solution of (I) in hexanes.

Refinement

Hydrogen atoms were placed in calculated positions with C—H distances of 0.98 and 1.00 Å. They were included in the refinement in a riding-model approximation with U_iso(H) = 1.2U_eq(C) or 1.5U_eq(C_methyl).

Figures

Fig. 1.

Reaction scheme

Fig. 2.

The molecular structure of (I) showing 30% probability ellipsoids (symmetry code (a): -x + 1, -y + 1, -z).

Fig. 3.

Part of the crystal structure showing weak hydrogen bonds as dashed lines.

Crystal data

C32H44O10	Z = 1
Mr = 588.67	F(000) = 316
Triclinic, P1	Dx = 1.242 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8376 (10) Å	Cell parameters from 4249 reflections
b = 9.4895 (17) Å	θ = 2.2–27.5°
c = 14.924 (3) Å	µ = 0.09 mm−1
α = 99.926 (4)°	T = 150 K
β = 98.545 (4)°	Block, colourless
γ = 100.462 (4)°	0.45 × 0.25 × 0.15 mm
V = 786.9 (2) Å3

Data collection

Bruker Kappa APEX DUO CCD diffractometer	3559 independent reflections
Radiation source: fine-focus sealed tube	3024 reflections with I > 2σ(I)
Bruker Triumph monochromator	Rint = 0.015
φ and ω scans	θmax = 27.5°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −7→4
Tmin = 0.698, Tmax = 0.746	k = −12→12
6490 measured reflections	l = −19→18

Refinement

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.0475P)2 + 0.3125P] where P = (Fo2 + 2Fc2)/3
3559 reflections	(Δ/σ)max = 0.001
196 parameters	Δρmax = 0.33 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.22773 (14)	0.65121 (9)	0.02699 (6)	0.01803 (19)
O2	0.35940 (19)	0.52069 (10)	0.29004 (7)	0.0282 (2)
O3	0.26592 (16)	0.74251 (10)	0.32725 (6)	0.0217 (2)
O4	0.68115 (18)	0.95566 (11)	0.29352 (7)	0.0298 (2)
O5	0.80759 (16)	0.97519 (9)	0.15871 (6)	0.0207 (2)
C1	0.3636 (2)	0.67330 (13)	0.18207 (8)	0.0174 (2)
C2	0.2523 (2)	0.55902 (13)	0.09395 (8)	0.0165 (2)
H2A	0.1029	0.4910	0.0973	0.020*
C3	0.4520 (2)	0.48426 (13)	0.06656 (8)	0.0154 (2)
H3	0.5361	0.4416	0.1152	0.018*
C4	0.6083 (2)	0.61021 (12)	0.03288 (8)	0.0146 (2)
H4	0.7801	0.6364	0.0622	0.018*
C5	0.4701 (2)	0.73280 (13)	0.05005 (8)	0.0164 (2)
H5A	0.5070	0.8137	0.0160	0.020*
C6	0.5012 (2)	0.78123 (13)	0.15483 (8)	0.0167 (2)
C7	0.3337 (2)	0.63815 (13)	0.27330 (8)	0.0180 (2)
C8	0.2067 (2)	0.72280 (14)	0.41859 (8)	0.0211 (3)
C9	0.4200 (3)	0.69922 (18)	0.48118 (10)	0.0332 (3)
H9A	0.5579	0.7767	0.4830	0.050*
H9B	0.4535	0.6038	0.4572	0.050*
H9C	0.3865	0.7020	0.5438	0.050*
C10	0.1460 (3)	0.86826 (18)	0.45469 (11)	0.0375 (4)
H10A	0.0047	0.8794	0.4143	0.056*
H10B	0.2793	0.9481	0.4555	0.056*
H10C	0.1146	0.8712	0.5176	0.056*
C11	−0.0074 (3)	0.59823 (18)	0.40294 (11)	0.0347 (3)
H11A	−0.1297	0.6103	0.3540	0.052*
H11B	−0.0703	0.5989	0.4603	0.052*
H11C	0.0392	0.5049	0.3844	0.052*
C12	0.6722 (2)	0.91271 (13)	0.21227 (8)	0.0169 (2)
C13	0.9780 (2)	1.11711 (14)	0.19571 (9)	0.0212 (3)
C14	0.8388 (3)	1.23483 (16)	0.21650 (13)	0.0371 (4)
H14A	0.7595	1.2190	0.2685	0.056*
H14B	0.7199	1.2307	0.1618	0.056*
H14C	0.9469	1.3311	0.2327	0.056*
C15	1.1022 (3)	1.13826 (18)	0.11508 (11)	0.0380 (4)
H15A	0.9856	1.1420	0.0615	0.057*
H15B	1.1795	1.0563	0.0992	0.057*
H15C	1.2216	1.2301	0.1325	0.057*
C16	1.1550 (3)	1.10905 (18)	0.27928 (11)	0.0344 (4)
H16A	1.0756	1.1054	0.3325	0.052*
H16B	1.2846	1.1957	0.2937	0.052*
H16C	1.2190	1.0208	0.2655	0.052*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0147 (4)	0.0190 (4)	0.0187 (4)	0.0016 (3)	0.0010 (3)	0.0033 (3)
O2	0.0417 (6)	0.0206 (5)	0.0259 (5)	0.0099 (4)	0.0126 (4)	0.0059 (4)
O3	0.0300 (5)	0.0195 (4)	0.0184 (4)	0.0067 (4)	0.0118 (4)	0.0039 (3)
O4	0.0303 (5)	0.0322 (6)	0.0183 (5)	−0.0081 (4)	0.0071 (4)	−0.0046 (4)
O5	0.0246 (5)	0.0151 (4)	0.0186 (4)	−0.0039 (3)	0.0061 (3)	0.0003 (3)
C1	0.0169 (6)	0.0167 (6)	0.0176 (6)	0.0030 (4)	0.0048 (4)	0.0004 (4)
C2	0.0154 (6)	0.0167 (6)	0.0158 (6)	−0.0001 (4)	0.0041 (4)	0.0018 (4)
C3	0.0157 (6)	0.0141 (5)	0.0145 (6)	−0.0005 (4)	0.0035 (4)	0.0009 (4)
C4	0.0137 (5)	0.0144 (6)	0.0139 (5)	−0.0002 (4)	0.0029 (4)	0.0009 (4)
C5	0.0160 (6)	0.0155 (6)	0.0160 (6)	0.0004 (4)	0.0025 (4)	0.0017 (4)
C6	0.0169 (6)	0.0159 (6)	0.0166 (6)	0.0036 (4)	0.0045 (4)	0.0005 (4)
C7	0.0159 (6)	0.0175 (6)	0.0181 (6)	−0.0006 (4)	0.0046 (4)	0.0000 (4)
C8	0.0267 (7)	0.0247 (7)	0.0144 (6)	0.0071 (5)	0.0088 (5)	0.0045 (5)
C9	0.0363 (8)	0.0394 (8)	0.0230 (7)	0.0129 (6)	0.0008 (6)	0.0028 (6)
C10	0.0595 (11)	0.0365 (9)	0.0257 (8)	0.0253 (8)	0.0185 (7)	0.0062 (6)
C11	0.0293 (8)	0.0438 (9)	0.0320 (8)	0.0004 (6)	0.0146 (6)	0.0107 (7)
C12	0.0168 (6)	0.0155 (6)	0.0179 (6)	0.0024 (4)	0.0043 (4)	0.0022 (4)
C13	0.0200 (6)	0.0161 (6)	0.0227 (6)	−0.0052 (5)	0.0013 (5)	0.0031 (5)
C14	0.0375 (9)	0.0171 (7)	0.0513 (10)	0.0022 (6)	0.0024 (7)	0.0016 (6)
C15	0.0415 (9)	0.0357 (8)	0.0305 (8)	−0.0128 (7)	0.0109 (6)	0.0080 (6)
C16	0.0213 (7)	0.0430 (9)	0.0339 (8)	−0.0044 (6)	−0.0031 (6)	0.0137 (7)

Geometric parameters (Å, º)

O1—C5	1.4442 (14)	C8—C10	1.5164 (19)
O1—C2	1.4453 (14)	C8—C9	1.5171 (19)
O2—C7	1.2135 (16)	C9—H9A	0.9800
O3—C7	1.3220 (15)	C9—H9B	0.9800
O3—C8	1.4892 (15)	C9—H9C	0.9800
O4—C12	1.2010 (16)	C10—H10A	0.9800
O5—C12	1.3402 (15)	C10—H10B	0.9800
O5—C13	1.4840 (14)	C10—H10C	0.9800
C1—C6	1.3421 (17)	C11—H11A	0.9800
C1—C7	1.4839 (17)	C11—H11B	0.9800
C1—C2	1.5253 (16)	C11—H11C	0.9800
C2—C3	1.5401 (16)	C13—C14	1.513 (2)
C2—H2A	1.0000	C13—C15	1.518 (2)
C3—C4i	1.5498 (16)	C13—C16	1.5190 (18)
C3—C4	1.5686 (16)	C14—H14A	0.9800
C3—H3	1.0000	C14—H14B	0.9800
C4—C5	1.5392 (16)	C14—H14C	0.9800
C4—C3i	1.5498 (16)	C15—H15A	0.9800
C4—H4	1.0000	C15—H15B	0.9800
C5—C6	1.5255 (16)	C15—H15C	0.9800
C5—H5A	1.0000	C16—H16A	0.9800
C6—C12	1.4876 (16)	C16—H16B	0.9800
C8—C11	1.515 (2)	C16—H16C	0.9800
C5—O1—C2	96.18 (8)	H9A—C9—H9B	109.5
C7—O3—C8	120.96 (10)	C8—C9—H9C	109.5
C12—O5—C13	121.03 (10)	H9A—C9—H9C	109.5
C6—C1—C7	134.31 (11)	H9B—C9—H9C	109.5
C6—C1—C2	105.44 (10)	C8—C10—H10A	109.5
C7—C1—C2	119.46 (10)	C8—C10—H10B	109.5
O1—C2—C1	101.00 (9)	H10A—C10—H10B	109.5
O1—C2—C3	102.44 (9)	C8—C10—H10C	109.5
C1—C2—C3	105.96 (9)	H10A—C10—H10C	109.5
O1—C2—H2A	115.2	H10B—C10—H10C	109.5
C1—C2—H2A	115.2	C8—C11—H11A	109.5
C3—C2—H2A	115.2	C8—C11—H11B	109.5
C2—C3—C4i	113.90 (9)	H11A—C11—H11B	109.5
C2—C3—C4	100.76 (9)	C8—C11—H11C	109.5
C4i—C3—C4	90.45 (9)	H11A—C11—H11C	109.5
C2—C3—H3	116.0	H11B—C11—H11C	109.5
C4i—C3—H3	116.0	O4—C12—O5	126.38 (11)
C4—C3—H3	116.0	O4—C12—C6	124.31 (11)
C5—C4—C3i	115.39 (9)	O5—C12—C6	109.30 (10)
C5—C4—C3	101.01 (9)	O5—C13—C14	108.34 (11)
C3i—C4—C3	89.55 (9)	O5—C13—C15	102.62 (10)
C5—C4—H4	115.7	C14—C13—C15	110.74 (13)
C3i—C4—H4	115.7	O5—C13—C16	111.42 (11)
C3—C4—H4	115.7	C14—C13—C16	112.83 (13)
O1—C5—C6	101.33 (9)	C15—C13—C16	110.40 (12)
O1—C5—C4	101.79 (9)	C13—C14—H14A	109.5
C6—C5—C4	106.44 (9)	C13—C14—H14B	109.5
O1—C5—H5A	115.2	H14A—C14—H14B	109.5
C6—C5—H5A	115.2	C13—C14—H14C	109.5
C4—C5—H5A	115.2	H14A—C14—H14C	109.5
C1—C6—C12	129.04 (11)	H14B—C14—H14C	109.5
C1—C6—C5	105.29 (10)	C13—C15—H15A	109.5
C12—C6—C5	125.30 (11)	C13—C15—H15B	109.5
O2—C7—O3	126.77 (12)	H15A—C15—H15B	109.5
O2—C7—C1	120.41 (11)	C13—C15—H15C	109.5
O3—C7—C1	112.71 (10)	H15A—C15—H15C	109.5
O3—C8—C11	108.87 (10)	H15B—C15—H15C	109.5
O3—C8—C10	101.91 (10)	C13—C16—H16A	109.5
C11—C8—C10	111.03 (12)	C13—C16—H16B	109.5
O3—C8—C9	110.50 (11)	H16A—C16—H16B	109.5
C11—C8—C9	112.93 (12)	C13—C16—H16C	109.5
C10—C8—C9	111.03 (12)	H16A—C16—H16C	109.5
C8—C9—H9A	109.5	H16B—C16—H16C	109.5
C8—C9—H9B	109.5
C5—O1—C2—C1	51.53 (10)	C2—C1—C6—C5	0.72 (12)
C5—O1—C2—C3	−57.73 (10)	O1—C5—C6—C1	32.18 (12)
C6—C1—C2—O1	−33.35 (12)	C4—C5—C6—C1	−73.86 (12)
C7—C1—C2—O1	155.41 (10)	O1—C5—C6—C12	−154.29 (11)
C6—C1—C2—C3	73.14 (12)	C4—C5—C6—C12	99.66 (13)
C7—C1—C2—C3	−98.11 (12)	C8—O3—C7—O2	−1.27 (19)
O1—C2—C3—C4i	−61.22 (11)	C8—O3—C7—C1	174.85 (10)
C1—C2—C3—C4i	−166.66 (9)	C6—C1—C7—O2	−123.53 (16)
O1—C2—C3—C4	34.11 (10)	C2—C1—C7—O2	44.64 (17)
C1—C2—C3—C4	−71.33 (11)	C6—C1—C7—O3	60.08 (18)
C2—C3—C4—C5	1.36 (10)	C2—C1—C7—O3	−131.75 (11)
C4i—C3—C4—C5	115.81 (10)	C7—O3—C8—C11	−63.78 (15)
C2—C3—C4—C3i	−114.45 (10)	C7—O3—C8—C10	178.84 (12)
C4i—C3—C4—C3i	0.0	C7—O3—C8—C9	60.78 (15)
C2—O1—C5—C6	−51.21 (10)	C13—O5—C12—O4	−4.86 (19)
C2—O1—C5—C4	58.47 (10)	C13—O5—C12—C6	173.80 (10)
C3i—C4—C5—O1	58.36 (12)	C1—C6—C12—O4	−14.3 (2)
C3—C4—C5—O1	−36.43 (10)	C5—C6—C12—O4	173.77 (12)
C3i—C4—C5—C6	164.08 (10)	C1—C6—C12—O5	167.03 (12)
C3—C4—C5—C6	69.28 (11)	C5—C6—C12—O5	−4.92 (16)
C7—C1—C6—C12	−3.2 (2)	C12—O5—C13—C14	−67.15 (15)
C2—C1—C6—C12	−172.48 (11)	C12—O5—C13—C15	175.69 (12)
C7—C1—C6—C5	170.05 (13)	C12—O5—C13—C16	57.55 (16)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ii	1.00	2.47	3.2118 (16)	130

Symmetry code: (ii) −x, −y+1, −z.