4-Meth­oxy-5-[4-(4-meth­oxy-1,3-benzodioxol-5-yl)perhydro-1H,3H-furo[3,4-c]furan-1-yl]-1,3-benzodioxole

Rukmani Perumal Ezhilmuthu; Nagarajan Vembu; Nagarajan Sulochana

doi:10.1107/S1600536808018138

. 2008 Jun 19;64(Pt 7):o1306–o1307. doi: 10.1107/S1600536808018138

4-Methoxy-5-[4-(4-methoxy-1,3-benzodioxol-5-yl)perhydro-1H,3H-furo[3,4-c]furan-1-yl]-1,3-benzodioxole

Rukmani Perumal Ezhilmuthu ^a, Nagarajan Vembu ^b,^*, Nagarajan Sulochana ^c

PMCID: PMC2961785 PMID: 21202935

Abstract

The 1,3-benzodioxole ring systems in the title compound, C₂₂H₂₂O₈, are almost planar. The perhydrofurofuranyl system linking them adopts a distorted double-envelope conformation. Supramolecular aggregation is effected by C—H⋯O, C—H⋯π and π–π [centroid–centroid distance of 3.755 Å, interplanar distance of 3.633 Å and dihedral angle of 14.6°] interactions.

Related literature

For related literature, see: Fu et al. (2006 ▶); Sonar et al. (2006 ▶); Hu et al. (2007 ▶); Zhou et al. (2007 ▶); Liang (2004 ▶); Wang et al. (2004 ▶); Zheng et al. (2005a ▶,b ▶); Hu et al. (2005 ▶); Qi et al. (2006 ▶); Hussain et al. (2006 ▶); Yu et al. (2006 ▶); Zhang et al. (2007 ▶); Betz et al. (2007 ▶); Yin et al. (2007 ▶); Beroza & Barthel (1957 ▶); Mitscher et al. (1979 ▶); Chien & Cheng (1970 ▶); Rao et al. (1981 ▶). For hydrogen bonds, see: Desiraju & Steiner (1999 ▶); Desiraju (1989 ▶). For graph-set notations, see: Bernstein et al. (1995 ▶); Etter (1990 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₂H₂₂O₈
M _r = 414.40
Monoclinic,
a = 4.754 (5) Å
b = 13.982 (4) Å
c = 14.672 (5) Å
β = 97.97 (6)°
V = 965.8 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 (2) K
0.3 × 0.3 × 0.3 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.805, T _max = 0.999
2000 measured reflections
1777 independent reflections
1505 reflections with I > 2σ(I)
R _int = 0.009
2 standard reflections every 100 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.110
S = 1.05
1777 reflections
272 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808018138/dn2355sup1.cif

e-64-o1306-sup1.cif^{(23.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808018138/dn2355Isup2.hkl

e-64-o1306-Isup2.hkl^{(87.5KB, hkl)}

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

Table 1. Selected torsion angles (°).

O2—C7—C8—C9	−13.3 (3)
C7—C8—C9—C10	−10.7 (3)
C11—C8—C9—C12	−9.0 (3)
C8—C9—C10—O2	32.0 (3)
C9—C8—C11—O1	−11.5 (3)
C8—C9—C12—O1	26.4 (3)

Open in a new tab

Table 2. Hydrogen-bond geometry (Å, °).

Cg5 is the centroid of the C1–C6 ring and Cg6 is the centroid of the C13—C18 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O2	0.93	2.34	2.721 (5)	104
C9—H9⋯O3	0.98	2.48	2.997 (4)	113
C11—H11B⋯O4	0.97	2.56	3.042 (5)	111
C14—H14⋯O1	0.93	2.45	2.808 (5)	103
C19—H19C⋯O7	0.96	2.41	3.065 (6)	125
C20—H20B⋯O5	0.96	2.33	2.939 (7)	121
C7—H7⋯Cg5ⁱ	0.98	2.85	3.724	148
C22—H22A⋯Cg6ⁱⁱ	0.97	2.97	3.646	128

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

NV thanks Dr Frank R. Fronczek, Department of Chemistry, Louisiana State University, Baton Rouge, USA, for discussions. RPE thanks Mr P. Perumal and Mr M. K. Senthilkumar, JKK Natarajah College of Pharmacy, Komarapalayam, Namakkal District, Tamil Nadu, India, for their help with the IR and HPLC experiments and extraction of the title compound from plant sources, respectively.

supplementary crystallographic information

Comment

1,3-benzodioxole (methylenedioxyphenyl) moiety is frequently found in natural products, and has been reported to possess some interesting biological activities (Beroza & Barthel, 1957 ; Hu et al., 2005 ; Hu et al., 2007 ; Sonar et al., 2006 ; Wang et al., 2004 ; Yin et al., 2007 ; Yu et al., 2006 ; Zheng et al., 2005a,b). The methylenedioxy positional isomers of oxolinic acid have been found to have widespread clinical applications and are used in the treatment of urinary tract infections (Mitscher et al., 1979). They are also used for the synthesis of antimalarial drugs (Chien & Cheng, 1970). The title compound, (I), is obtained as part of our investigation on 1,3-benzodioxole derivatives.

In (I) (Fig. 1), both the 1,3-benzodioxole rings are almost planar. The planarity of the dioxole moiety is similar to those observed in related compounds (Zhou et al. 2007; Liang 2004, Zhang et al. 2007; Betz et al. 2007) and in contrast to the envelope conformation observed for these rings in few related compounds (Fu et al. 2006; Qi et al. 2006; Hussain et al. 2006). The O-methoxy group attached to each of the 1,3-benzodioxole rings differ in their orientation as shown by the corresponding torsion angles which probably explains the acentricity of the crystal. The tetrahydro furofuranyl ring adopts a distorted envelope-distorted envelope conformation as shown by the corresponding torsion angles (Table 1). The two five membered rings are fused in such a way that they share a common base described by the bond C8—C9 (Fig. 1). The Cremer & Pople (1975) puckering parameters for the O1—C11—C8—C9—C12 ring are Q(2) = 0.311 (3)Å and φ(2) = 163.0 (6)° whereas those for the O2—C7—C8—C9—C10 ring are Q(2) = 0.371 (3)Å and φ(2) = 162.9 (5)°. These values indicate that the extent of puckering is almost similar in both the rings. The pseudorotation parameters (Rao et al. 1981) for O1—C11—C8—C9—C12 ring are P = 254.8 (3)° & τ(M) = 34.7 (2)° for the C8—C9 reference bond with the closest pucker descriptor being twisted on C12—O1 and those for O2—C7—C8—C9—C10 ring are P = 254.1 (3)° and τ(M) = 41.4 (2)° for the C8—C9 reference bond with the closest puckering descriptor being twisted on C10—O2.

The crystal structure of (I) is stabilized by the interplay of intramolecular C—H···O, intermolecular C—H···π (Table 2) and π–π interactions (Fig. 2). The H-bond distances found in (I) agree with those reported in literature (Desiraju & Steiner, 1999; Desiraju, 1989). S(5) motifs (Bernstein et al., 1995; Etter, 1990) are generated by each of C5—H5···O2 and C14—H14···O1 interactions. Each of the C9—H9···O3, C19—H19C···O7 and C20—H20B···O5 interactions generate an S(6) motif. An S(7) motif is generated by C11—H11B···O4 interaction. In Table 2, Cg3 refers to the centroid of the ring formed by O5, C2, C3, O6 & C21, Cg4 refers to the centroid of the ring formed by O7, C17, C16, O8 & C22, Cg5 refers to the centroid of the ring formed by C1—C6 and Cg6 refers to the centroid of the ring formed by C13—C18. A significant π–π stacking is observed between Cg4 and Cg6 (1 + x, y, z) with a centroid to centroid distance of 3.755 Å, a plane to plane distance of 3.633Å and an offset angle of 14.6°.

Experimental

Ethanolic extract of powdered root of Ecbolium Viride (Forssk) spring was charged on a column and eluted with solvents ranging from non-polar to polar at the rate of 30 drops per minute. 34 fractions were collected, each of volume 25 ml with different ratios of solvents. The fractions collected were monitored by thin layer chromatography (TLC) for homogenity and similar fractions were pooled together. The title compound was isolated from one such pool. Diffraction quality crystals of the title compound were obtained by recrystallization from chloroform.