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

Almansour, A.I.; Kumar, R.S.; Arumugam, N.; Devi Shree, P.; Suresh, J.

doi:10.1107/S1600536812006332

organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Page o744

doi:10.1107/S1600536812006332

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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 and J. Suresh ^b ^*

^aDepartment of Chemistry, College of Sciences, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia, and ^bDepartment of Physics, Madura College, Madurai 625 011, India
^*Correspondence e-mail: ambujasureshj@yahoo.com

(Received 5 February 2012; accepted 13 February 2012; online 17 February 2012)

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, $[P \overline 1]$
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[F² > 2σ(F²)] = 0.045
wR(F²) = 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

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)
Symmetry codes: (i) -x, -y+1, -z+1; (ii) -x, -y+1, -z; (iii) x+1, y+1, z; (iv) -x, -y, -z; (v) x-1, y, z.

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812006332/tk5055sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536812006332/tk5055Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme.
	Fig. 2. A packing diagram for (I).

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 top

Crystal data top

C₂₆H₁₂FNO₆	Z = 2
M_r = 453.37	F(000) = 464
Triclinic, P1	D_x = 1.595 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8262 (1) Å	Cell parameters from 2000 reflections
b = 10.9278 (1) Å	θ = 2–31°
c = 12.4067 (2) Å	µ = 0.12 mm⁻¹
α = 113.374 (1)°	T = 293 K
β = 94.922 (1)°	Block, colourless
γ = 100.295 (1)°	0.23 × 0.21 × 0.18 mm
V = 943.77 (2) Å³

Data collection top

Bruker Kappa APEXII diffractometer	5504 independent reflections
Radiation source: fine-focus sealed tube	4486 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 0 pixels mm^-1	θ_max = 30.1°, θ_min = 1.8°
ω and ϕ scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
T_min = 0.973, T_max = 0.978	l = −17→12
15720 measured reflections

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0602P)² + 0.4439P] where P = (F_o² + 2F_c²)/3
5504 reflections	(Δ/σ)_max < 0.001
311 parameters	Δρ_max = 0.46 e Å⁻³
1 restraint	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₂₆H₁₂FNO₆	γ = 100.295 (1)°
M_r = 453.37	V = 943.77 (2) Å³
Triclinic, P1	Z = 2
a = 7.8262 (1) Å	Mo Kα radiation
b = 10.9278 (1) Å	µ = 0.12 mm⁻¹
c = 12.4067 (2) Å	T = 293 K
α = 113.374 (1)°	0.23 × 0.21 × 0.18 mm
β = 94.922 (1)°

Data collection top

Bruker Kappa APEXII diffractometer	5504 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4486 reflections with I > 2σ(I)
T_min = 0.973, T_max = 0.978	R_int = 0.023
15720 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	1 restraint
wR(F²) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.46 e Å⁻³
5504 reflections	Δρ_min = −0.29 e Å⁻³
311 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
H1	−0.122 (2)	0.3850 (19)	0.4085 (15)	0.025 (5)*
C2	0.12458 (17)	0.34311 (13)	−0.00317 (11)	0.0140 (2)
C3	0.05623 (17)	0.31770 (13)	0.08465 (11)	0.0135 (2)
C4	0.09926 (16)	0.42071 (13)	0.21373 (11)	0.0128 (2)
C5	0.18729 (17)	0.55860 (13)	0.21847 (11)	0.0139 (2)
C6	0.24834 (17)	0.57319 (13)	0.12440 (11)	0.0139 (2)
C21	0.09810 (17)	0.23914 (13)	−0.12381 (11)	0.0148 (2)
C22	0.17434 (19)	0.25796 (14)	−0.21611 (12)	0.0172 (3)
H22	0.2407	0.3436	−0.2034	0.021*
C23	0.15001 (19)	0.14852 (15)	−0.32576 (12)	0.0191 (3)
H23	0.2016	0.1604	−0.3868	0.023*
C24	0.0486 (2)	0.01981 (15)	−0.34611 (12)	0.0199 (3)
H24	0.0344	−0.0533	−0.4203	0.024*
C25	−0.03060 (19)	0.00031 (14)	−0.25711 (12)	0.0194 (3)
H25	−0.1002	−0.0847	−0.2711	0.023*
C26	−0.00412 (17)	0.11020 (14)	−0.14632 (12)	0.0156 (3)
C31	−0.05619 (17)	0.18354 (14)	0.05589 (12)	0.0152 (2)
C41	0.21280 (17)	0.37727 (13)	0.29163 (11)	0.0130 (2)
C42	0.37794 (17)	0.34883 (13)	0.28347 (12)	0.0155 (3)
H42	0.4387	0.3545	0.2238	0.019*
C43	0.44766 (17)	0.31133 (14)	0.36932 (12)	0.0164 (3)
C44	0.36544 (18)	0.30651 (14)	0.46197 (12)	0.0168 (3)
H44	0.4203	0.2841	0.5188	0.020*
C45	0.19881 (18)	0.33555 (13)	0.46972 (12)	0.0156 (3)
H45	0.1405	0.3334	0.5314	0.019*
C46	0.12383 (17)	0.36764 (13)	0.38189 (11)	0.0134 (2)
C48	−0.07059 (17)	0.42709 (13)	0.27287 (11)	0.0140 (2)
C51	0.21637 (17)	0.67890 (13)	0.33197 (12)	0.0157 (3)
C61	0.34501 (17)	0.70292 (14)	0.13272 (12)	0.0151 (2)
C62	0.37581 (17)	0.81431 (14)	0.24372 (12)	0.0162 (3)
C63	0.47226 (19)	0.94335 (14)	0.26308 (13)	0.0196 (3)
H63	0.4916	1.0166	0.3377	0.024*
C64	0.53871 (19)	0.96018 (15)	0.16875 (13)	0.0198 (3)
H64	0.6045	1.0455	0.1803	0.024*
C65	0.50796 (19)	0.85014 (15)	0.05598 (13)	0.0195 (3)
H65	0.5525	0.8632	−0.0068	0.023*
C66	0.41184 (18)	0.72236 (14)	0.03748 (12)	0.0173 (3)
H66	0.3914	0.6496	−0.0375	0.021*
N1	−0.04170 (15)	0.39656 (12)	0.36839 (10)	0.0140 (2)
O1	0.22685 (13)	0.46733 (10)	0.01416 (8)	0.0159 (2)
O2	−0.08257 (13)	0.08560 (10)	−0.05945 (8)	0.0167 (2)
O3	−0.12795 (14)	0.15262 (10)	0.12640 (9)	0.0195 (2)
O4	0.31252 (13)	0.80145 (10)	0.33995 (9)	0.0180 (2)
O5	0.16406 (14)	0.67882 (10)	0.42086 (9)	0.0194 (2)
O6	−0.20150 (13)	0.45589 (10)	0.23875 (9)	0.0168 (2)
F1	0.60614 (11)	0.27654 (9)	0.36098 (8)	0.02124 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0134 (6)	0.0131 (6)	0.0156 (6)	0.0008 (4)	0.0019 (4)	0.0072 (5)
C3	0.0134 (6)	0.0124 (6)	0.0142 (6)	0.0009 (4)	0.0018 (4)	0.0060 (5)
C4	0.0124 (5)	0.0129 (6)	0.0132 (5)	0.0006 (4)	0.0022 (4)	0.0066 (5)
C5	0.0134 (6)	0.0135 (6)	0.0142 (6)	0.0013 (4)	0.0013 (4)	0.0062 (5)
C6	0.0128 (6)	0.0130 (6)	0.0145 (6)	0.0012 (4)	0.0013 (4)	0.0054 (5)
C21	0.0159 (6)	0.0150 (6)	0.0139 (6)	0.0036 (5)	0.0018 (4)	0.0065 (5)
C22	0.0205 (6)	0.0170 (6)	0.0165 (6)	0.0032 (5)	0.0028 (5)	0.0101 (5)
C23	0.0233 (7)	0.0214 (7)	0.0144 (6)	0.0047 (5)	0.0043 (5)	0.0095 (5)
C24	0.0264 (7)	0.0169 (6)	0.0139 (6)	0.0040 (5)	0.0003 (5)	0.0051 (5)
C25	0.0226 (7)	0.0147 (6)	0.0178 (6)	0.0015 (5)	−0.0009 (5)	0.0059 (5)
C26	0.0146 (6)	0.0167 (6)	0.0157 (6)	0.0021 (5)	0.0014 (5)	0.0080 (5)
C31	0.0144 (6)	0.0151 (6)	0.0157 (6)	0.0023 (5)	0.0017 (4)	0.0067 (5)
C41	0.0142 (6)	0.0113 (5)	0.0122 (5)	0.0000 (4)	0.0009 (4)	0.0050 (4)
C42	0.0146 (6)	0.0147 (6)	0.0164 (6)	0.0010 (5)	0.0029 (5)	0.0066 (5)
C43	0.0117 (6)	0.0148 (6)	0.0209 (6)	0.0014 (5)	0.0009 (5)	0.0068 (5)
C44	0.0172 (6)	0.0157 (6)	0.0173 (6)	0.0017 (5)	−0.0010 (5)	0.0085 (5)
C45	0.0176 (6)	0.0142 (6)	0.0138 (6)	0.0017 (5)	0.0019 (5)	0.0058 (5)
C46	0.0136 (6)	0.0125 (6)	0.0132 (5)	0.0013 (4)	0.0025 (4)	0.0051 (4)
C48	0.0147 (6)	0.0125 (6)	0.0138 (5)	0.0007 (4)	0.0026 (4)	0.0055 (5)
C51	0.0150 (6)	0.0140 (6)	0.0166 (6)	0.0003 (5)	0.0010 (5)	0.0066 (5)
C61	0.0136 (6)	0.0153 (6)	0.0173 (6)	0.0017 (5)	0.0016 (5)	0.0086 (5)
C62	0.0150 (6)	0.0157 (6)	0.0183 (6)	0.0012 (5)	0.0032 (5)	0.0084 (5)
C63	0.0195 (6)	0.0159 (6)	0.0209 (6)	0.0011 (5)	0.0029 (5)	0.0066 (5)
C64	0.0192 (6)	0.0163 (6)	0.0256 (7)	0.0000 (5)	0.0042 (5)	0.0122 (6)
C65	0.0180 (6)	0.0204 (7)	0.0227 (7)	0.0018 (5)	0.0048 (5)	0.0126 (6)
C66	0.0181 (6)	0.0175 (6)	0.0170 (6)	0.0018 (5)	0.0029 (5)	0.0090 (5)
N1	0.0130 (5)	0.0165 (5)	0.0142 (5)	0.0029 (4)	0.0043 (4)	0.0080 (4)
O1	0.0200 (5)	0.0127 (4)	0.0133 (4)	−0.0008 (4)	0.0042 (3)	0.0055 (4)
O2	0.0186 (5)	0.0141 (4)	0.0153 (4)	−0.0010 (4)	0.0031 (4)	0.0062 (4)
O3	0.0216 (5)	0.0177 (5)	0.0188 (5)	−0.0001 (4)	0.0049 (4)	0.0090 (4)
O4	0.0216 (5)	0.0141 (4)	0.0157 (4)	−0.0015 (4)	0.0047 (4)	0.0055 (4)
O5	0.0223 (5)	0.0189 (5)	0.0149 (4)	0.0007 (4)	0.0045 (4)	0.0063 (4)
O6	0.0150 (4)	0.0181 (5)	0.0186 (5)	0.0037 (4)	0.0022 (3)	0.0092 (4)
F1	0.0125 (4)	0.0252 (4)	0.0288 (5)	0.0054 (3)	0.0035 (3)	0.0138 (4)

Geometric parameters (Å, º) top

C2—C3	1.3555 (18)	C41—C46	1.3968 (18)
C2—O1	1.3712 (16)	C42—C43	1.3880 (18)
C2—C21	1.4448 (18)	C42—H42	0.9300
C3—C31	1.4563 (18)	C43—F1	1.3612 (15)
C3—C4	1.5122 (17)	C43—C44	1.379 (2)
C4—C5	1.5167 (18)	C44—C45	1.3985 (19)
C4—C41	1.5219 (17)	C44—H44	0.9300
C4—C48	1.5716 (18)	C45—C46	1.3862 (18)
C5—C6	1.3535 (18)	C45—H45	0.9300
C5—C51	1.4602 (18)	C46—N1	1.3990 (16)
C6—O1	1.3685 (16)	C48—O6	1.2144 (16)
C6—C61	1.4423 (18)	C48—N1	1.3643 (17)
C21—C26	1.3963 (19)	C51—O5	1.2091 (17)
C21—C22	1.4036 (19)	C51—O4	1.3753 (16)
C22—C23	1.3785 (19)	C61—C62	1.3944 (19)
C22—H22	0.9300	C61—C66	1.4071 (19)
C23—C24	1.399 (2)	C62—O4	1.3785 (16)
C23—H23	0.9300	C62—C63	1.3913 (19)
C24—C25	1.381 (2)	C63—C64	1.384 (2)
C24—H24	0.9300	C63—H63	0.9300
C25—C26	1.3881 (19)	C64—C65	1.402 (2)
C25—H25	0.9300	C64—H64	0.9300
C26—O2	1.3767 (16)	C65—C66	1.3817 (19)
C31—O3	1.2025 (17)	C65—H65	0.9300
C31—O2	1.3751 (16)	C66—H66	0.9300
C41—C42	1.3851 (18)	N1—H1	0.855 (9)

C3—C2—O1	123.63 (12)	C43—C42—H42	121.9
C3—C2—C21	122.30 (12)	F1—C43—C44	118.16 (12)
O1—C2—C21	114.06 (11)	F1—C43—C42	117.95 (12)
C2—C3—C31	119.28 (12)	C44—C43—C42	123.88 (12)
C2—C3—C4	122.74 (11)	C43—C44—C45	119.46 (12)
C31—C3—C4	117.91 (11)	C43—C44—H44	120.3
C3—C4—C5	108.11 (10)	C45—C44—H44	120.3
C3—C4—C41	112.55 (10)	C46—C45—C44	117.45 (12)
C5—C4—C41	111.75 (10)	C46—C45—H45	121.3
C3—C4—C48	111.18 (10)	C44—C45—H45	121.3
C5—C4—C48	112.06 (10)	C45—C46—C41	122.00 (12)
C41—C4—C48	101.17 (10)	C45—C46—N1	128.16 (12)
C6—C5—C51	119.03 (12)	C41—C46—N1	109.83 (11)
C6—C5—C4	122.84 (12)	O6—C48—N1	127.29 (13)
C51—C5—C4	118.03 (11)	O6—C48—C4	125.09 (12)
C5—C6—O1	123.61 (12)	N1—C48—C4	107.61 (11)
C5—C6—C61	122.40 (12)	O5—C51—O4	117.02 (12)
O1—C6—C61	113.99 (11)	O5—C51—C5	124.82 (12)
C26—C21—C22	118.97 (12)	O4—C51—C5	118.15 (12)
C26—C21—C2	116.49 (12)	C62—C61—C66	118.90 (12)
C22—C21—C2	124.47 (12)	C62—C61—C6	116.85 (12)
C23—C22—C21	119.45 (13)	C66—C61—C6	124.23 (12)
C23—C22—H22	120.3	O4—C62—C63	116.74 (12)
C21—C22—H22	120.3	O4—C62—C61	121.41 (12)
C22—C23—C24	120.67 (13)	C63—C62—C61	121.85 (13)
C22—C23—H23	119.7	C64—C63—C62	118.45 (13)
C24—C23—H23	119.7	C64—C63—H63	120.8
C25—C24—C23	120.62 (13)	C62—C63—H63	120.8
C25—C24—H24	119.7	C63—C64—C65	120.78 (13)
C23—C24—H24	119.7	C63—C64—H64	119.6
C24—C25—C26	118.62 (13)	C65—C64—H64	119.6
C24—C25—H25	120.7	C66—C65—C64	120.39 (13)
C26—C25—H25	120.7	C66—C65—H65	119.8
O2—C26—C25	116.72 (12)	C64—C65—H65	119.8
O2—C26—C21	121.62 (12)	C65—C66—C61	119.62 (13)
C25—C26—C21	121.66 (13)	C65—C66—H66	120.2
O3—C31—O2	117.67 (12)	C61—C66—H66	120.2
O3—C31—C3	124.30 (12)	C48—N1—C46	112.25 (11)
O2—C31—C3	118.03 (12)	C48—N1—H1	123.1 (13)
C42—C41—C46	120.82 (12)	C46—N1—H1	124.1 (13)
C42—C41—C4	130.10 (12)	C6—O1—C2	117.29 (10)
C46—C41—C4	109.08 (11)	C31—O2—C26	122.11 (11)
C41—C42—C43	116.28 (12)	C51—O4—C62	122.08 (11)
C41—C42—H42	121.9

O1—C2—C3—C31	177.76 (11)	C42—C43—C44—C45	2.5 (2)
C21—C2—C3—C31	−3.55 (19)	C43—C44—C45—C46	0.25 (19)
O1—C2—C3—C4	−5.5 (2)	C44—C45—C46—C41	−2.90 (19)
C21—C2—C3—C4	173.14 (11)	C44—C45—C46—N1	178.11 (12)
C2—C3—C4—C5	13.71 (17)	C42—C41—C46—C45	2.91 (19)
C31—C3—C4—C5	−169.55 (11)	C4—C41—C46—C45	−177.21 (12)
C2—C3—C4—C41	−110.20 (14)	C42—C41—C46—N1	−177.93 (11)
C31—C3—C4—C41	66.54 (15)	C4—C41—C46—N1	1.94 (14)
C2—C3—C4—C48	137.11 (13)	C3—C4—C48—O6	−59.04 (17)
C31—C3—C4—C48	−46.15 (15)	C5—C4—C48—O6	62.07 (16)
C3—C4—C5—C6	−13.18 (17)	C41—C4—C48—O6	−178.75 (12)
C41—C4—C5—C6	111.21 (14)	C3—C4—C48—N1	121.75 (11)
C48—C4—C5—C6	−136.05 (13)	C5—C4—C48—N1	−117.14 (11)
C3—C4—C5—C51	170.66 (11)	C41—C4—C48—N1	2.04 (13)
C41—C4—C5—C51	−64.95 (15)	C6—C5—C51—O5	178.02 (13)
C48—C4—C5—C51	47.79 (15)	C4—C5—C51—O5	−5.7 (2)
C51—C5—C6—O1	−179.49 (11)	C6—C5—C51—O4	−3.06 (18)
C4—C5—C6—O1	4.4 (2)	C4—C5—C51—O4	173.26 (11)
C51—C5—C6—C61	1.49 (19)	C5—C6—C61—C62	0.86 (19)
C4—C5—C6—C61	−174.63 (11)	O1—C6—C61—C62	−178.25 (11)
C3—C2—C21—C26	0.75 (19)	C5—C6—C61—C66	179.52 (12)
O1—C2—C21—C26	179.55 (11)	O1—C6—C61—C66	0.41 (19)
C3—C2—C21—C22	−176.13 (12)	C66—C61—C62—O4	179.57 (12)
O1—C2—C21—C22	2.68 (18)	C6—C61—C62—O4	−1.69 (19)
C26—C21—C22—C23	−1.41 (19)	C66—C61—C62—C63	−0.7 (2)
C2—C21—C22—C23	175.39 (12)	C6—C61—C62—C63	177.99 (12)
C21—C22—C23—C24	0.8 (2)	O4—C62—C63—C64	179.70 (12)
C22—C23—C24—C25	0.7 (2)	C61—C62—C63—C64	0.0 (2)
C23—C24—C25—C26	−1.5 (2)	C62—C63—C64—C65	0.7 (2)
C24—C25—C26—O2	−178.75 (12)	C63—C64—C65—C66	−0.6 (2)
C24—C25—C26—C21	0.8 (2)	C64—C65—C66—C61	−0.2 (2)
C22—C21—C26—O2	−179.85 (11)	C62—C61—C66—C65	0.8 (2)
C2—C21—C26—O2	3.10 (18)	C6—C61—C66—C65	−177.82 (12)
C22—C21—C26—C25	0.6 (2)	O6—C48—N1—C46	179.76 (13)
C2—C21—C26—C25	−176.44 (12)	C4—C48—N1—C46	−1.05 (14)
C2—C3—C31—O3	−177.26 (13)	C45—C46—N1—C48	178.55 (13)
C4—C3—C31—O3	5.88 (19)	C41—C46—N1—C48	−0.54 (15)
C2—C3—C31—O2	2.63 (18)	C5—C6—O1—C2	5.83 (18)
C4—C3—C31—O2	−174.23 (11)	C61—C6—O1—C2	−175.07 (11)
C3—C4—C41—C42	58.76 (18)	C3—C2—O1—C6	−5.26 (18)
C5—C4—C41—C42	−63.11 (17)	C21—C2—O1—C6	175.95 (11)
C48—C4—C41—C42	177.49 (13)	O3—C31—O2—C26	−178.97 (11)
C3—C4—C41—C46	−121.10 (12)	C3—C31—O2—C26	1.14 (17)
C5—C4—C41—C46	117.03 (12)	C25—C26—O2—C31	175.47 (12)
C48—C4—C41—C46	−2.37 (13)	C21—C26—O2—C31	−4.09 (18)
C46—C41—C42—C43	−0.17 (18)	O5—C51—O4—C62	−178.69 (12)
C4—C41—C42—C43	179.98 (12)	C5—C51—O4—C62	2.31 (18)
C41—C42—C43—F1	177.06 (11)	C63—C62—O4—C51	−179.61 (12)
C41—C42—C43—C44	−2.6 (2)	C61—C62—O4—C51	0.08 (19)
F1—C43—C44—C45	−177.07 (11)

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z; (iii) x+1, y+1, z; (iv) −x, −y, −z; (v) x−1, y, z.

Experimental details

Crystal data
Chemical formula	C₂₆H₁₂FNO₆
M_r	453.37
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.8262 (1), 10.9278 (1), 12.4067 (2)
α, β, γ (°)	113.374 (1), 94.922 (1), 100.295 (1)
V (Å³)	943.77 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.23 × 0.21 × 0.18

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.973, 0.978
No. of measured, independent and observed [I > 2σ(I)] reflections	15720, 5504, 4486
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.124, 1.04
No. of reflections	5504
No. of parameters	311
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.29

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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)

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x, −y+1, −z; (iii) x+1, y+1, z; (iv) −x, −y, −z; (v) x−1, y, z.

Acknowledgements

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

References

Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Joshi, K. C. & Jain, R. (1985). Heterocycles, 23, 957–996. CAS Google Scholar
Kobayashi, G. & Matsuda, Y. (1970). Jpn Patent No. 7025894. Google Scholar
Martin, E. J. & Critchlow, R. E. (1999). J. Combin. Chem. 1, 32–45. Web of Science CrossRef CAS Google Scholar
Ninamiya, K. (1980). Jpn Patent No. 80164683. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Teague, S. J. & Davis, A. M. (1999). Angew. Chem. Int. Ed. 38, 3743–3748. Web of Science CrossRef CAS Google Scholar

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doi:10.1107/S1600536812006332

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

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