6,6,8a-Tri­methyl-3a,6,7,8a-tetra­hydro­benzo­[b]­furo­[3,2-d]­furan-2,4(3H,5H)-dione

Nagaraj, B.; Yathirajan, H.S.; Nagaraja, P.; Lynch, D.E.

doi:10.1107/S1600536805008093

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 4| April 2005| Pages o1041-o1042

https://doi.org/10.1107/S1600536805008093

6,6,8a-Trimethyl-3a,6,7,8a-tetrahydrobenzo[b]furo[3,2-d]furan-2,4(3H,5H)-dione

Basavegowda Nagaraj,^a Hemmige S. Yathirajan,^a Padmarajaiah Nagaraja ^b and Daniel E. Lynch ^c ^*

^aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, ^bDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore - 570 006, India, and ^cSchool of Science and the Environment, Coventry University, Coventry CV1 5FB, England
^*Correspondence e-mail: apx106@coventry.ac.uk

(Received 9 March 2005; accepted 14 March 2005; online 18 March 2005)

The structure of the title compound, C₁₃H₁₆O₄, comprises a non-planar chiral molecule where the cyclohexene double bond is distinctly shorter [1.335 (2) Å] than the neighbouring C—C single bonds (>1.4 Å).

Comment

The title compound, (I), a perhydrofurobenzofuran, exhibits hypoglycemic properties. A search of the Cambridge Structural Database (Version 5.26; Allen, 2002 ) for related structures reveals that there are 38 compounds containing a six-membered carbocyclic ring with two linked five-membered furo rings, as in (I). However, in all 38 molecules the C₆ ring is benzene; none are cyclohexane, -ene or -yne variants. The structure of (I) comprises a non-planar chiral molecule where the C5=C10 double bond is distinctly shorter [1.335 (2) Å] than the neighbouring C—C single bonds (>1.4 Å). The two torsion angles that highlight the non-planarity of the molecule are O1—C1—C4—C3 [−127.2 (1)°] and O2—C1—C4—C5 [104.0 (1)°].

Figure 1
The molecular configuration and atom-numbering scheme for (I

). Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as spheres of arbitrary radius.

Experimental

The title compound was prepared according to the literature procedure of Nagarajan et al. (1988 ). Crystals were grown from ethanol.

Crystal data

C₁₃H₁₆O₄
M_r = 236.26
Orthorhombic, P2₁2₁2₁
a = 9.4853 (3) Å
b = 10.2904 (2) Å
c = 12.2872 (4) Å
V = 1199.32 (6) Å³
Z = 4
D_x = 1.309 Mg m⁻³
Mo Kα radiation
Cell parameters from 1560 reflections
θ = 2.9–27.5°
μ = 0.10 mm⁻¹
T = 120 (2) K
Prism, colourless
0.50 × 0.40 × 0.40 mm

Data collection

Nonius KappaCCD diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.953, T_max = 0.962
8608 measured reflections
2343 independent reflections
2235 reflections with I > 2σ(I)
R_int = 0.021
θ_max = 26.0°
h = −11 → 10
k = −12 → 12
l = −14 → 15

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.068
S = 1.04
2343 reflections
158 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0353P)² + 0.2043P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.14 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.045 (6)

All H atoms were included in the refinement at calculated positions, in the riding-model approximation, with C—H distances of 0.98 (CH₃), 0.99 (CH₂) and 1.00 Å (CH). The isotropic displacement parameters for all H atoms were set equal to 1.25U_eq of the carrier atom. In the absence of significant anomalous scattering effects, the 763 Friedel pairs were merged.

Data collection: COLLECT (Hooft, 1998 ); cell refinement: DENZO (Otwinowski & Minor, 1997 ) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536805008093/at6000sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805008093/at6000Isup2.hkl

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.

6,6,8a-Trimethyl-3a,6,7,8a-tetrahydrobenzo[b]furo[3,2-d]furan-2,4(3H,5H)-dione top

Crystal data top

C₁₃H₁₆O₄	D_x = 1.309 Mg m⁻³
M_r = 236.26	Melting point: 434 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1560 reflections
a = 9.4853 (3) Å	θ = 2.9–27.5°
b = 10.2904 (2) Å	µ = 0.10 mm⁻¹
c = 12.2872 (4) Å	T = 120 K
V = 1199.32 (6) Å³	Prism, colourless
Z = 4	0.50 × 0.40 × 0.40 mm
F(000) = 504

Data collection top

Nonius KappaCCD diffractometer	2343 independent reflections
Radiation source: Bruker Nonius FR591 rotating anode	2235 reflections with I > 2σ(I)
10 cm confocal mirrors monochromator	R_int = 0.021
Detector resolution: 9.091 pixels mm^-1	θ_max = 26.0°, θ_min = 2.9°
φ and ω scans	h = −11→10
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −12→12
T_min = 0.953, T_max = 0.962	l = −14→15
8608 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ²(F_o²) + (0.0353P)² + 0.2043P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
2343 reflections	Δρ_max = 0.20 e Å⁻³
158 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.045 (6)

Special details top

Experimental. The minimum and maximum absorption values stated above are those calculated in SHELXL97 from the given crystal dimensions. The ratio of minimum to maximum apparent transmission was determined experimentally as 0.884134.

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

	x	y	z	U_iso*/U_eq
O1	0.16781 (9)	0.17367 (8)	−0.01057 (7)	0.0201 (2)
O2	0.10135 (9)	0.36301 (8)	0.07462 (7)	0.0225 (2)
O3	0.03946 (10)	0.44551 (10)	0.23535 (9)	0.0360 (3)
O4	0.46337 (9)	0.08915 (8)	0.27867 (7)	0.0235 (2)
C1	0.21985 (13)	0.29930 (11)	0.02444 (10)	0.0184 (3)
C2	0.12818 (14)	0.39484 (12)	0.18079 (11)	0.0228 (3)
C3	0.27705 (13)	0.36048 (12)	0.20951 (10)	0.0216 (3)
H31	0.2807	0.3129	0.2795	0.027*
H32	0.3358	0.4397	0.2155	0.027*
C4	0.32810 (12)	0.27457 (11)	0.11621 (10)	0.0172 (3)
H4	0.4266	0.2959	0.0934	0.021*
C5	0.30737 (12)	0.13117 (11)	0.13465 (10)	0.0162 (2)
C6	0.37348 (12)	0.04866 (12)	0.21468 (10)	0.0167 (3)
C7	0.32064 (13)	−0.09032 (12)	0.21643 (10)	0.0184 (3)
H71	0.2375	−0.0952	0.2649	0.023*
H72	0.3950	−0.1463	0.2480	0.023*
C8	0.27957 (13)	−0.14482 (11)	0.10420 (10)	0.0175 (3)
C9	0.17135 (13)	−0.05357 (11)	0.04923 (10)	0.0180 (3)
H91	0.1627	−0.0758	−0.0289	0.022*
H92	0.0778	−0.0648	0.0836	0.022*
C10	0.21803 (12)	0.08331 (11)	0.06087 (9)	0.0163 (3)
C11	0.21468 (14)	−0.27965 (12)	0.11981 (12)	0.0252 (3)
H111	0.1899	−0.3162	0.0487	0.032*
H112	0.1297	−0.2725	0.1647	0.032*
H113	0.2830	−0.3366	0.1560	0.032*
C12	0.41107 (14)	−0.15744 (12)	0.03283 (11)	0.0255 (3)
H121	0.3847	−0.1938	−0.0380	0.032*
H122	0.4792	−0.2150	0.0684	0.032*
H123	0.4535	−0.0715	0.0224	0.032*
C13	0.26637 (16)	0.37458 (13)	−0.07371 (11)	0.0273 (3)
H131	0.1876	0.3821	−0.1249	0.034*
H132	0.3449	0.3293	−0.1090	0.034*
H133	0.2970	0.4615	−0.0514	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0239 (5)	0.0165 (4)	0.0198 (5)	0.0007 (3)	−0.0071 (4)	0.0029 (3)
O2	0.0182 (4)	0.0236 (4)	0.0258 (5)	0.0048 (4)	−0.0010 (4)	−0.0006 (4)
O3	0.0276 (5)	0.0399 (6)	0.0405 (6)	0.0016 (5)	0.0124 (5)	−0.0100 (5)
O4	0.0222 (5)	0.0247 (5)	0.0235 (5)	−0.0021 (4)	−0.0091 (4)	0.0003 (4)
C1	0.0190 (6)	0.0159 (5)	0.0203 (6)	0.0016 (5)	0.0010 (5)	−0.0002 (5)
C2	0.0232 (7)	0.0187 (6)	0.0264 (7)	−0.0034 (5)	0.0041 (5)	−0.0013 (5)
C3	0.0253 (6)	0.0178 (6)	0.0217 (6)	−0.0012 (5)	−0.0001 (5)	−0.0029 (5)
C4	0.0165 (6)	0.0164 (6)	0.0186 (6)	−0.0005 (4)	0.0003 (5)	0.0018 (5)
C5	0.0151 (6)	0.0167 (5)	0.0167 (5)	0.0007 (4)	0.0008 (5)	−0.0001 (4)
C6	0.0144 (6)	0.0203 (6)	0.0154 (6)	0.0006 (4)	0.0009 (5)	−0.0008 (5)
C7	0.0166 (6)	0.0204 (6)	0.0183 (6)	−0.0008 (5)	−0.0040 (5)	0.0044 (5)
C8	0.0171 (6)	0.0159 (5)	0.0195 (6)	0.0003 (5)	−0.0037 (5)	0.0015 (5)
C9	0.0191 (6)	0.0180 (6)	0.0169 (6)	0.0001 (5)	−0.0037 (5)	−0.0005 (5)
C10	0.0144 (5)	0.0186 (6)	0.0158 (6)	0.0030 (5)	−0.0006 (5)	0.0026 (4)
C11	0.0247 (6)	0.0182 (6)	0.0327 (7)	−0.0016 (5)	−0.0080 (6)	0.0033 (5)
C12	0.0237 (7)	0.0222 (6)	0.0306 (7)	0.0038 (5)	0.0035 (5)	−0.0025 (5)
C13	0.0358 (7)	0.0242 (7)	0.0220 (6)	−0.0015 (5)	0.0007 (6)	0.0057 (5)

Geometric parameters (Å, º) top

O1—C10	1.3646 (14)	C7—H71	0.99
O1—C1	1.4492 (14)	C7—H72	0.99
O2—C2	1.3689 (16)	C8—C12	1.5303 (17)
O2—C1	1.4399 (15)	C8—C11	1.5300 (16)
O3—C2	1.1956 (16)	C8—C9	1.5464 (16)
O4—C6	1.2324 (15)	C9—C10	1.4835 (17)
C1—C13	1.4997 (17)	C9—H91	0.99
C1—C4	1.5461 (17)	C9—H92	0.99
C2—C3	1.4978 (18)	C11—H111	0.98
C3—C4	1.5265 (16)	C11—H112	0.98
C3—H31	0.99	C11—H113	0.98
C3—H32	0.99	C12—H121	0.98
C4—C5	1.5059 (16)	C12—H122	0.98
C4—H4	1.00	C12—H123	0.98
C5—C10	1.3351 (17)	C13—H131	0.98
C5—C6	1.4426 (16)	C13—H132	0.98
C6—C7	1.5156 (16)	C13—H133	0.98
C7—C8	1.5388 (17)

C10—O1—C1	107.34 (9)	H71—C7—H72	107.6
C2—O2—C1	111.83 (10)	C12—C8—C11	108.83 (10)
O2—C1—O1	105.50 (9)	C12—C8—C7	109.77 (10)
O2—C1—C13	109.81 (10)	C11—C8—C7	108.66 (10)
O1—C1—C13	108.80 (10)	C12—C8—C9	110.02 (10)
O2—C1—C4	106.33 (9)	C11—C8—C9	109.78 (10)
O1—C1—C4	107.21 (9)	C7—C8—C9	109.76 (9)
C13—C1—C4	118.43 (11)	C10—C9—C8	109.65 (10)
O3—C2—O2	120.52 (12)	C10—C9—H91	109.7
O3—C2—C3	129.37 (12)	C8—C9—H91	109.7
O2—C2—C3	110.08 (11)	C10—C9—H92	109.7
C2—C3—C4	105.00 (10)	C8—C9—H92	109.7
C2—C3—H31	110.7	H91—C9—H92	108.2
C4—C3—H31	110.7	C5—C10—O1	114.02 (10)
C2—C3—H32	110.7	C5—C10—C9	127.24 (11)
C4—C3—H32	110.7	O1—C10—C9	118.74 (10)
H31—C3—H32	108.8	C8—C11—H111	109.5
C5—C4—C3	114.40 (10)	C8—C11—H112	109.5
C5—C4—C1	100.62 (9)	H111—C11—H112	109.5
C3—C4—C1	103.99 (9)	C8—C11—H113	109.5
C5—C4—H4	112.3	H111—C11—H113	109.5
C3—C4—H4	112.3	H112—C11—H113	109.5
C1—C4—H4	112.3	C8—C12—H121	109.5
C10—C5—C6	121.44 (11)	C8—C12—H122	109.5
C10—C5—C4	110.01 (10)	H121—C12—H122	109.5
C6—C5—C4	128.51 (11)	C8—C12—H123	109.5
O4—C6—C5	122.45 (11)	H121—C12—H123	109.5
O4—C6—C7	122.60 (11)	H122—C12—H123	109.5
C5—C6—C7	114.92 (10)	C1—C13—H131	109.5
C6—C7—C8	114.51 (10)	C1—C13—H132	109.5
C6—C7—H71	108.6	H131—C13—H132	109.5
C8—C7—H71	108.6	C1—C13—H133	109.5
C6—C7—H72	108.6	H131—C13—H133	109.5
C8—C7—H72	108.6	H132—C13—H133	109.5

C2—O2—C1—O1	120.97 (10)	C1—C4—C5—C6	−176.76 (11)
C2—O2—C1—C13	−121.94 (11)	C10—C5—C6—O4	174.96 (11)
C2—O2—C1—C4	7.32 (12)	C4—C5—C6—O4	−2.42 (19)
C10—O1—C1—O2	−104.33 (10)	C10—C5—C6—C7	−6.91 (16)
C10—O1—C1—C13	137.90 (10)	C4—C5—C6—C7	175.71 (11)
C10—O1—C1—C4	8.71 (12)	O4—C6—C7—C8	−147.51 (11)
C1—O2—C2—O3	−178.12 (11)	C5—C6—C7—C8	34.36 (14)
C1—O2—C2—C3	3.55 (14)	C6—C7—C8—C12	66.75 (13)
O3—C2—C3—C4	168.91 (13)	C6—C7—C8—C11	−174.33 (10)
O2—C2—C3—C4	−12.95 (13)	C6—C7—C8—C9	−54.28 (13)
C2—C3—C4—C5	−92.39 (12)	C12—C8—C9—C10	−75.43 (12)
C2—C3—C4—C1	16.37 (12)	C11—C8—C9—C10	164.83 (10)
O2—C1—C4—C5	103.98 (10)	C7—C8—C9—C10	45.45 (13)
O1—C1—C4—C5	−8.49 (11)	C6—C5—C10—O1	−178.35 (10)
C13—C1—C4—C5	−131.95 (11)	C4—C5—C10—O1	−0.53 (14)
O2—C1—C4—C3	−14.69 (11)	C6—C5—C10—C9	1.03 (19)
O1—C1—C4—C3	−127.17 (10)	C4—C5—C10—C9	178.85 (11)
C13—C1—C4—C3	109.37 (12)	C1—O1—C10—C5	−5.33 (13)
C3—C4—C5—C10	116.43 (11)	C1—O1—C10—C9	175.23 (10)
C1—C4—C5—C10	5.63 (13)	C8—C9—C10—C5	−21.53 (17)
C3—C4—C5—C6	−65.96 (16)	C8—C9—C10—O1	157.83 (10)

Acknowledgements

The authors thank the EPSRC National Crystallography Service (Southampton, England) and acknowledge the use of the EPSRC's Chemical Database Service at Daresbury, England (Fletcher et al., 1996 ).

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