5-Fluoro-6′H,7′H,8′H-spiro­[indoline-3,7′-pyrano[3,2-c:5,6-c′]di-1-benzopyran]-2,6′,8′-trione

Abdulrahman I Almansour; Raju Suresh Kumar; Natarajan Arumugam; P Devi Shree; J Suresh

doi:10.1107/S1600536812006332

. 2012 Feb 17;68(Pt 3):o744. doi: 10.1107/S1600536812006332

5-Fluoro-6′H,7′H,8′H-spiro[indoline-3,7′-pyrano[3,2-c:5,6-c′]di-1-benzopyran]-2,6′,8′-trione

Abdulrahman I Almansour ^a, Raju Suresh Kumar ^a, Natarajan Arumugam ^a, P Devi Shree ^b, J Suresh ^b,^*

PMCID: PMC3295512 PMID: 22412623

Abstract

In the title compound, C₂₆H₁₂FNO₆, the central pyran ring and both benzopyran systems are nonplanar, having total puckering amplitudes of 0.139 (2), 0.050 (1) and 0.112 (2) Å, respectively. The central pyran ring adopts a boat conformation. The crystal structure is stabilized by C—H⋯O, N—H⋯O, N—H⋯F and C—H⋯π interactions.

Related literature

For the background to benzopyran derivatives, see: Martin & Critchlow (1999 ▶); Teague & Davis (1999 ▶); Joshi & Jain (1985 ▶); Ninamiya (1980 ▶); Kobayashi & Matsuda (1970 ▶). For hydrogen-bonding motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₆H₁₂FNO₆
M _r = 453.37
Triclinic,
a = 7.8262 (1) Å
b = 10.9278 (1) Å
c = 12.4067 (2) Å
α = 113.374 (1)°
β = 94.922 (1)°
γ = 100.295 (1)°
V = 943.77 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.23 × 0.21 × 0.18 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.973, T _max = 0.978
15720 measured reflections
5504 independent reflections
4486 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.124
S = 1.04
5504 reflections
311 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812006332/tk5055sup1.cif

e-68-0o744-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812006332/tk5055Isup2.hkl

e-68-0o744-Isup2.hkl^{(269.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812006332/tk5055Isup3.cml

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

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

Cg1 is the centroid of the C41–C46 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C45—H45⋯O5ⁱ	0.93	2.50	3.2564 (18)	139
C22—H22⋯O6ⁱⁱ	0.93	2.46	3.2205 (17)	139
C66—H66⋯O6ⁱⁱ	0.93	2.50	3.2921 (17)	144
C64—H64⋯O3ⁱⁱⁱ	0.93	2.49	3.2641 (18)	141
C25—H25⋯Cg1^iv	0.93	2.65	3.5482 (17)	163
N1—H1⋯F1^v	0.86 (2)	2.15 (2)	2.810 (2)	134 (2)
N1—H1⋯O5ⁱ	0.86 (2)	2.51 (2)	3.208 (2)	140 (2)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

This project was supported by the Research Center, Deanship of Scientific Research, College of Science, King Saud University.

supplementary crystallographic information

Comment

Benzopyran is a structural motif observed in many biologically active natural products and it plays an important role in binding to various biopolymers (Martin & Critchlow, 1999; Teague & Davis, 1999). Spiro indoles are also known for their broad spectrum of biological activities (Joshi & Jain, 1985). Of the various spiro indoles, the spiro[indole-pyran] system has attracted attention owing to its interesting pharmacological properties (Ninamiya, 1980; Kobayashi & Matsuda, 1970). The biological importance of these heterocycles in conjunction with our research interests, prompted us to synthesize and report the X-ray structure of the title compound, (I).

In (I), Fig. 1, the central pyrano ring A (O1–C6) and both the benzopyran rings B (C5/C6/C61–C66/O4/C51), C (C3/C3/C21–C26/O2/C31) are non-planar, having total puckering amplitudes, Q_T, of 0.139 (2), 0.050 (1) and 0.112 (2) Å, respectively. The central pyrano ring adopts a boat conformation [Φ = 357.6 (6)° and θ = 109.0 (6)°]. In the indolin-2-one system, the benzene and pyrrole rings are individually planar and make a dihedral angle of 2.20 (1)°. The indoline-2-one system is in a perpendicular configuration with respect to the pyrano ring, as can be seen from the dihedral angle [89.83 (2)°]. The sum of the angles at atom N1 of the indolin-2-one moiety is in accordance with sp²-hybridization [359.41 (2)°].

The N1—H1···O5 hydrogen bonds connect two centrosymmetrically related molecules and generate the graph set motif R₂²(14) (Bernstein et al., 1995). The centrosymmetric dimers are interconnected into zig-zag linear chain of C—H···O hydrogen bonds and the molecules form a layered structure (Fig. 2). In addition, there is a weak C—H···π interaction, viz. C25—H25···Cg1 (Cg1 is the centroid of the ring C41–C46; symmetry codes are given in Table 1).

Experimental

A mixture of 5-fluoroindoline-2,3-dione (0.100 g, 0.60 mmol), 4-hydroxy-2H-chromen-2-one (0.194 g, 1.20 mmol), and paratoluene sulfonic acid (0.114 g, 0.60 mmol) were dissolved in 5 ml of ethanol:water (1:1 v/v) and refluxed for 2 h. After completion of the reaction as evident from TLC, the precipitated solid was filtered and washed with water to afford the product which was recrystallized from ethanol to provide colourless crystals. Yield 72%, m.p. 541–543 K.