1,4,6,9-Tetra-tert-butyl-2,7-dioxa­tricyclo­[6.3.0.03,6]deca-3,8-diene

Sorensen, T.S.; Humayaun Kabir, S.M.; Parvez, M.

doi:10.1107/S1600536813000147

organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page o204

doi:10.1107/S1600536813000147

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1,4,6,9-Tetra-tert-butyl-2,7-dioxatricyclo[6.3.0.0^3,6]deca-3,8-diene

Ted S. Sorensen,^a S. M Humayaun Kabir ^a and Masood Parvez ^a ^*

^aDepartment of Chemistry, The University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4
^*Correspondence e-mail: parvez@ucalgary.ca

(Received 20 December 2012; accepted 2 January 2013; online 9 January 2013)

The title compound, C₂₄H₄₀O₂, lies on an inversion center with a half-molecule in the asymmetric unit. The central dioxane ring adopts a chair conformation. The four-membered ring is slightly puckered with a butterfly angle of 13.50 (14)°.

Related literature

For the synthesis of the title compound, see: Rauk et al. (1995 ). For related structures, see: Masters et al. (1994 ); Bernassau et al. (1987 ).

Experimental

Crystal data

C₂₄H₄₀O₂
M_r = 360.56
Triclinic, $[P \overline 1]$
a = 5.843 (2) Å
b = 9.383 (3) Å
c = 10.126 (4) Å
α = 97.209 (12)°
β = 96.014 (13)°
γ = 100.703 (19)°
V = 536.5 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 170 K
0.20 × 0.15 × 0.05 mm

Data collection

Nonius APEXII CCD diffractometer
Absorption correction: multi-scan (SORTAV; Blessing, 1997 ) T_min = 0.987, T_max = 0.997
4499 measured reflections
2412 independent reflections
1957 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.104
S = 1.04
2412 reflections
124 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813000147/zl2528sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813000147/zl2528Isup2.hkl

checkCIF report

Comment top

Our research on the preparation and structure investigations of simple bicyclo[1.1.0]butanones (Rauk et al. 1995) led to the synthesis of the title compound. The stereochemistry of the title compound was not known at that time. In the title compound (Fig. 1), the central dioxane ring adopts a chair conformation with puckering parameters: Q = 0.3934 (11) Å, θ = 0.74 (1)° and ϕ = 0.0°. The four membered ring (C1/C2/C3/C4ⁱ; ⁱ = -x + 1, -y + 1, -z + 1) is slightly puckered with the dihedral angle between mean planes C1/C2/C3 and C1/C3/C4ⁱ being 13.50 (14)°. The molecular dimesions in the title compound agree very well with the corresponding molecular dimensions reported in closely related compounds (Masters et al., 1994; Bernassau et al., 1987). The crystal structure is devoid of any significant directional intermolecular interactions (Fig. 2).

Related literature top

For the synthesis of the title compound, see: Rauk et al. (1995). For related structures, see: Masters et al. (1994); Bernassau et al. (1987).

Experimental top

The synthesis of the title compound has been reported earlier (Rauk et al., 1995). Crystals suitable for crystallolgraphic studies were grown from pentane/CH₂Cl₂ (1:1).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. ORTEP drawing (Farrugia, 2012) of the title molecule with the displacement ellipsoids plotted at 50% probability level; H atoms are presented as small spheres of arbitrary radius. Symmetry code: ⁱ -x + 1, -y + 1, -z + 1.
	Fig. 2. A view of the unit cell packing of the crystal structure of the title compound. H atoms were omitted for clarity.

1,4,6,9-Tetra-tert-butyl-2,7-dioxatricyclo[6.3.0.0^3,6]deca-3,8-diene top

Crystal data top

C₂₄H₄₀O₂	Z = 1
M_r = 360.56	F(000) = 200
Triclinic, P1	D_x = 1.116 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.843 (2) Å	Cell parameters from 2272 reflections
b = 9.383 (3) Å	θ = 1.0–27.5°
c = 10.126 (4) Å	µ = 0.07 mm⁻¹
α = 97.209 (12)°	T = 170 K
β = 96.014 (13)°	Plate, colorless
γ = 100.703 (19)°	0.20 × 0.15 × 0.05 mm
V = 536.5 (3) Å³

Data collection top

Nonius APEXII CCD diffractometer	2412 independent reflections
Radiation source: fine-focus sealed tube	1957 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω and ϕ scans	θ_max = 27.4°, θ_min = 4.1°
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	h = −7→7
T_min = 0.987, T_max = 0.997	k = −12→12
4499 measured reflections	l = −13→13

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0415P)² + 0.1563P] where P = (F_o² + 2F_c²)/3
2412 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₄H₄₀O₂	γ = 100.703 (19)°
M_r = 360.56	V = 536.5 (3) Å³
Triclinic, P1	Z = 1
a = 5.843 (2) Å	Mo Kα radiation
b = 9.383 (3) Å	µ = 0.07 mm⁻¹
c = 10.126 (4) Å	T = 170 K
α = 97.209 (12)°	0.20 × 0.15 × 0.05 mm
β = 96.014 (13)°

Data collection top

Nonius APEXII CCD diffractometer	2412 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1997)	1957 reflections with I > 2σ(I)
T_min = 0.987, T_max = 0.997	R_int = 0.018
4499 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.04	Δρ_max = 0.27 e Å⁻³
2412 reflections	Δρ_min = −0.19 e Å⁻³
124 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
O1	0.25855 (13)	0.40276 (8)	0.50016 (8)	0.0194 (2)
C1	0.36790 (19)	0.43605 (12)	0.39096 (11)	0.0183 (2)
C2	0.38127 (19)	0.36693 (12)	0.26899 (11)	0.0195 (2)
C3	0.6042 (2)	0.47693 (13)	0.25541 (12)	0.0225 (3)
H3A	0.5931	0.5253	0.1742	0.027*
H3B	0.7506	0.4384	0.2666	0.027*
C4	0.44599 (19)	0.43136 (12)	0.61504 (11)	0.0184 (2)
C5	0.2453 (2)	0.23533 (13)	0.17350 (12)	0.0226 (3)
C6	0.0667 (2)	0.14183 (14)	0.24394 (13)	0.0304 (3)
H6A	−0.0295	0.0617	0.1785	0.037*
H6B	−0.0346	0.2029	0.2839	0.037*
H6C	0.1499	0.1010	0.3146	0.037*
C7	0.4145 (2)	0.14319 (15)	0.11795 (14)	0.0343 (3)
H7A	0.3251	0.0586	0.0549	0.041*
H7B	0.5003	0.1089	0.1921	0.041*
H7C	0.5263	0.2032	0.0714	0.041*
C8	0.1150 (2)	0.28994 (15)	0.05637 (13)	0.0335 (3)
H8A	0.0317	0.2058	−0.0093	0.040*
H8B	0.2283	0.3532	0.0133	0.040*
H8C	0.0017	0.3457	0.0903	0.040*
C9	0.5229 (2)	0.28551 (12)	0.63873 (12)	0.0219 (3)
C10	0.7097 (2)	0.30967 (15)	0.76230 (14)	0.0325 (3)
H10A	0.7518	0.2159	0.7764	0.039*
H10B	0.6468	0.3501	0.8416	0.039*
H10C	0.8497	0.3785	0.7477	0.039*
C11	0.3063 (2)	0.17552 (14)	0.66121 (14)	0.0306 (3)
H11A	0.3515	0.0826	0.6755	0.037*
H11B	0.1872	0.1588	0.5822	0.037*
H11C	0.2418	0.2149	0.7403	0.037*
C12	0.6320 (2)	0.22114 (13)	0.51932 (13)	0.0273 (3)
H12A	0.6876	0.1332	0.5403	0.033*
H12B	0.7646	0.2940	0.5018	0.033*
H12C	0.5136	0.1952	0.4396	0.033*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0169 (4)	0.0215 (4)	0.0192 (4)	0.0009 (3)	0.0034 (3)	0.0036 (3)
C1	0.0168 (5)	0.0176 (5)	0.0209 (6)	0.0029 (4)	0.0030 (4)	0.0050 (4)
C2	0.0194 (5)	0.0186 (5)	0.0202 (6)	0.0028 (4)	0.0029 (4)	0.0033 (4)
C3	0.0249 (6)	0.0216 (6)	0.0204 (6)	0.0019 (5)	0.0060 (5)	0.0022 (5)
C4	0.0179 (5)	0.0192 (5)	0.0173 (6)	0.0016 (4)	0.0023 (4)	0.0026 (4)
C5	0.0223 (6)	0.0224 (6)	0.0212 (6)	0.0024 (5)	0.0022 (5)	−0.0007 (5)
C6	0.0286 (6)	0.0280 (7)	0.0292 (7)	−0.0041 (5)	0.0021 (5)	−0.0005 (5)
C7	0.0310 (7)	0.0306 (7)	0.0373 (8)	0.0061 (6)	0.0040 (6)	−0.0098 (6)
C8	0.0367 (7)	0.0359 (7)	0.0244 (7)	0.0045 (6)	−0.0033 (5)	0.0010 (5)
C9	0.0241 (6)	0.0188 (6)	0.0230 (6)	0.0028 (4)	0.0034 (5)	0.0059 (5)
C10	0.0387 (7)	0.0283 (7)	0.0307 (7)	0.0095 (6)	−0.0036 (6)	0.0081 (5)
C11	0.0340 (7)	0.0208 (6)	0.0382 (7)	0.0020 (5)	0.0091 (6)	0.0098 (5)
C12	0.0305 (6)	0.0226 (6)	0.0312 (7)	0.0106 (5)	0.0054 (5)	0.0046 (5)

Geometric parameters (Å, º) top

O1—C1	1.3744 (14)	C7—H7A	0.9800
O1—C4	1.4733 (14)	C7—H7B	0.9800
C1—C2	1.3380 (16)	C7—H7C	0.9800
C1—C4ⁱ	1.5048 (15)	C8—H8A	0.9800
C2—C5	1.5053 (16)	C8—H8B	0.9800
C2—C3	1.5344 (16)	C8—H8C	0.9800
C3—C4ⁱ	1.5615 (16)	C9—C11	1.5338 (17)
C3—H3A	0.9900	C9—C12	1.5347 (17)
C3—H3B	0.9900	C9—C10	1.5361 (18)
C4—C1ⁱ	1.5048 (15)	C10—H10A	0.9800
C4—C9	1.5557 (16)	C10—H10B	0.9800
C4—C3ⁱ	1.5615 (16)	C10—H10C	0.9800
C5—C6	1.5299 (17)	C11—H11A	0.9800
C5—C7	1.5340 (17)	C11—H11B	0.9800
C5—C8	1.5354 (18)	C11—H11C	0.9800
C6—H6A	0.9800	C12—H12A	0.9800
C6—H6B	0.9800	C12—H12B	0.9800
C6—H6C	0.9800	C12—H12C	0.9800

C1—O1—C4	105.98 (8)	C5—C7—H7C	109.5
C2—C1—O1	136.58 (10)	H7A—C7—H7C	109.5
C2—C1—C4ⁱ	95.84 (9)	H7B—C7—H7C	109.5
O1—C1—C4ⁱ	127.01 (10)	C5—C8—H8A	109.5
C1—C2—C5	137.73 (11)	C5—C8—H8B	109.5
C1—C2—C3	91.75 (9)	H8A—C8—H8B	109.5
C5—C2—C3	130.52 (10)	C5—C8—H8C	109.5
C2—C3—C4ⁱ	86.07 (8)	H8A—C8—H8C	109.5
C2—C3—H3A	114.3	H8B—C8—H8C	109.5
C4ⁱ—C3—H3A	114.3	C11—C9—C12	109.70 (10)
C2—C3—H3B	114.3	C11—C9—C10	109.15 (10)
C4ⁱ—C3—H3B	114.3	C12—C9—C10	106.61 (10)
H3A—C3—H3B	111.5	C11—C9—C4	108.43 (10)
O1—C4—C1ⁱ	112.31 (9)	C12—C9—C4	111.81 (10)
O1—C4—C9	109.61 (9)	C10—C9—C4	111.11 (10)
C1ⁱ—C4—C9	118.82 (9)	C9—C10—H10A	109.5
O1—C4—C3ⁱ	115.51 (9)	C9—C10—H10B	109.5
C1ⁱ—C4—C3ⁱ	84.71 (8)	H10A—C10—H10B	109.5
C9—C4—C3ⁱ	114.21 (9)	C9—C10—H10C	109.5
C2—C5—C6	110.63 (10)	H10A—C10—H10C	109.5
C2—C5—C7	109.91 (10)	H10B—C10—H10C	109.5
C6—C5—C7	109.95 (11)	C9—C11—H11A	109.5
C2—C5—C8	108.22 (10)	C9—C11—H11B	109.5
C6—C5—C8	109.26 (11)	H11A—C11—H11B	109.5
C7—C5—C8	108.82 (11)	C9—C11—H11C	109.5
C5—C6—H6A	109.5	H11A—C11—H11C	109.5
C5—C6—H6B	109.5	H11B—C11—H11C	109.5
H6A—C6—H6B	109.5	C9—C12—H12A	109.5
C5—C6—H6C	109.5	C9—C12—H12B	109.5
H6A—C6—H6C	109.5	H12A—C12—H12B	109.5
H6B—C6—H6C	109.5	C9—C12—H12C	109.5
C5—C7—H7A	109.5	H12A—C12—H12C	109.5
C5—C7—H7B	109.5	H12B—C12—H12C	109.5
H7A—C7—H7B	109.5

C4—O1—C1—C2	124.33 (14)	C1—C2—C5—C7	−133.88 (15)
C4—O1—C1—C4ⁱ	−44.73 (14)	C3—C2—C5—C7	46.30 (16)
O1—C1—C2—C5	19.1 (2)	C1—C2—C5—C8	107.40 (16)
C4ⁱ—C1—C2—C5	−169.70 (13)	C3—C2—C5—C8	−72.42 (15)
O1—C1—C2—C3	−161.07 (13)	O1—C4—C9—C11	−57.21 (12)
C4ⁱ—C1—C2—C3	10.17 (9)	C1ⁱ—C4—C9—C11	171.79 (10)
C1—C2—C3—C4ⁱ	−9.77 (9)	C3ⁱ—C4—C9—C11	74.21 (12)
C5—C2—C3—C4ⁱ	170.11 (12)	O1—C4—C9—C12	63.86 (12)
C1—O1—C4—C1ⁱ	37.41 (12)	C1ⁱ—C4—C9—C12	−67.14 (13)
C1—O1—C4—C9	−96.97 (10)	C3ⁱ—C4—C9—C12	−164.73 (9)
C1—O1—C4—C3ⁱ	132.31 (10)	O1—C4—C9—C10	−177.16 (9)
C1—C2—C5—C6	−12.26 (19)	C1ⁱ—C4—C9—C10	51.84 (14)
C3—C2—C5—C6	167.92 (11)	C3ⁱ—C4—C9—C10	−45.74 (13)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₄H₄₀O₂
M_r	360.56
Crystal system, space group	Triclinic, P1
Temperature (K)	170
a, b, c (Å)	5.843 (2), 9.383 (3), 10.126 (4)
α, β, γ (°)	97.209 (12), 96.014 (13), 100.703 (19)
V (Å³)	536.5 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.20 × 0.15 × 0.05

Data collection
Diffractometer	Nonius APEXII CCD diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1997)
T_min, T_max	0.987, 0.997
No. of measured, independent and observed [I > 2σ(I)] reflections	4499, 2412, 1957
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.648

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.104, 1.04
No. of reflections	2412
No. of parameters	124
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.19

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997), SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012).

References

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